Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/058—Construction or manufacture
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
  • H01M50/251—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders specially adapted for stationary devices, e.g. power plant buffering or backup power supplies
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
  • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
  • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
  • H01M10/3909—Sodium-sulfur cells
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/4214—Arrangements for moving electrodes or electrolyte
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/10—Primary casings; Jackets or wrappings
  • H01M50/138—Primary casings; Jackets or wrappings adapted for specific cells, e.g. electrochemical cells operating at high temperature
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
  • H01M50/233—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions
  • H01M50/24—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions adapted for protecting batteries from their environment, e.g. from corrosion
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
  • H01M8/184—Regeneration by electrochemical means
  • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/04—Construction or manufacture in general
  • H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
  • H01M10/0562—Solid materials
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
  • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
  • H01M10/3909—Sodium-sulfur cells
  • H01M10/3945—Sodium-sulfur cells containing additives or special arrangements in the sodium compartment
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
  • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
  • H01M10/3909—Sodium-sulfur cells
  • H01M10/3954—Sodium-sulfur cells containing additives or special arrangement in the sulfur compartment
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
  • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
  • H01M10/3909—Sodium-sulfur cells
  • H01M10/3963—Sealing means between the solid electrolyte and holders
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/60—Heating or cooling; Temperature control
  • H01M10/65—Means for temperature control structurally associated with the cells
  • H01M10/654—Means for temperature control structurally associated with the cells located inside the innermost case of the cells, e.g. mandrels, electrodes or electrolytes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
  • H01M2250/40—Combination of fuel cells with other energy production systems
  • H01M2250/405—Cogeneration of heat or hot water
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0065—Solid electrolytes
  • H01M2300/0068—Solid electrolytes inorganic
  • H01M2300/0071—Oxides
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
  • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
  • H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
  • H01M50/213—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for cells having curved cross-section, e.g. round or elliptic
• • 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
  • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
  • Y02B90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02B90/10—Applications of fuel cells in buildings
• • 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
  • Y02E60/10—Energy storage using batteries
• • 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
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the invention relates to an improved technical device for large-scale storage of energy and a method for storing and transporting electrical energy by means of this device.
• the generation of electrical energy in the case of fossil power plants is associated with the production of C0 2 and thus has a significant impact on the greenhouse effect.
• Energy generation based on renewable energy sources, eg. As wind, solar, geothermal or hydropower avoids this disadvantage.
• these regenerative energy sources are not available at any time in terms of load.
• the location of energy production may differ from the location of the energy demand.
• To compensate for this systemic disadvantage is a storage, buffering and possibly also a transport of the energy generated required.
• renewable sources such as wind turbines, solar systems
• demand and availability are not consistent.
• An electricity grid based solely on renewable energies and yet stable can not exist under these conditions. There is a need to balance and buffer these fluctuations with low cost and energy efficient high efficiency systems.
• a battery which contains at least one molten alkali metal as an anode and a cathodic reactant which is electrochemically reversible with the anodic reactant.
• the cathodic reactant consists of molten polysulfide salts or a biphasic mass of molten sulfur and molten sulfur saturated polysulfide salts.
• This battery also has cation-permeable barrier layers for mass transport between the anodic and cathodic reaction zones.
• DE-A-2610222 discloses a battery comprising a plurality of sulfur sodium cells, each cell 1) comprising a cathodic compartment having a cathodic reactant 2) at its operating temperature of sulfur, phosphorus or selenium or alkaline salts of these elements, at least a solid electrolyte tube having liquid anode anodic reactant at the operating temperature of an alkali metal, in particular sodium, and an anodic container 3) containing a reserve of the anodic reagent.
• a flow battery for storage and release of electrical energy in an electrochemical cell with an anode and a cathode compartment is known, which are separated by a semipermeable ion exchange membrane, wherein the anode compartment with a so-called Anolyte ion, an oxidizable compound that remains substantially dissolved in the anolyte ion and can be redissolved from its oxidized form, charges, removes the oxidized anolyte ion from the anolyte compartment and stores the oxidized anolyte ion.
• the catholyte compartment is charged with a catholyte ion, a reducible compound which essentially remains dissolved in the catholyte solvent and can be re-oxidized from its reduced form.
• the anolyte and catholyte ions can be stored in two corresponding containers and circulated through the anode and cathode compartments with circulating pumps.
• the catholyte ionization may, for example, contain hexavalent chromium and the anolyte solution divalent chromium.
• a system for obtaining electrical energy by electrochemical combination of sodium and sulfur comprises a sodium ion-permeable diapragma with adjacent spaces for sodium and sulfur a container for storing the sodium outside the cell, conduits for conveying the sodium from the storage container to the fuel cell, a container for storing the sulfur outside the cells, and conduits for conveying the sulfur from the storage container to the cell.
• the cells may be electrically connected in series.
• JP-A-2001 1 18598 it is known to operate sodium sulfur batteries with two or more cylinders in matrix form for molten sodium or molten sulfur.
• JP-A-2002184456 it is known to operate a sodium sulfur battery with an external storage tank for sulfur, which is fixedly connected to the battery.
• the energy stored in the educts sodium and sulfur energy and the discharge by reaction of sodium and sulfur to form sodium sulfide or sodium polysulfides is temporally and locally coupled.
• the object of the invention was to provide an improved device and an improved method for an electrochemical power plant based on redox partners, in particular alkali, especially sodium and, for example, sulfur.
• the invention relates to a device for storing electrical energy by means of the substances A and S, which form a redox couple and are present separately, characterized in that a) the device contains substances A and S.
• the containers BA and BS are contained in an over-container, characterized in that the device contains at least two over-containers containing containers BA and BS connected by means of a solid electrolyte E.
• the substance A is an alkali metal, in particular sodium, and the substance S is sulfur.
• the containers BA and BS connected by the electrolyte E constitute a cell; In a preferred embodiment, this cell is present as a drum (hereinafter drum cell).
• the invention further relates to a method for storage and delivery, optionally for the transport of electrical energy using an electrochemical reactor, which is characterized in that a device according to the invention is used, in a particularly preferred embodiment with an alkali metal as substance A, in particular Sodium, and sulfur as a substance S.
• a device according to the invention is used, in a particularly preferred embodiment with an alkali metal as substance A, in particular Sodium, and sulfur as a substance S.
• the invention further relates to a method for transporting and delivering electrochemical energy in an electrochemical power plant, wherein at a location of the energy demand
• At least one electrochemical alkali metal / sulfur cell is provided, this cell each comprising at least the following components:
• compartments A and K are separated by a solid electrolyte E which is permeable at the operating temperature of the cell to cations formed by oxidation of the alkali metal;
• reservoir BA with the anode compartment A and reservoir BS are connected to the cathode compartment K under supply of liquid alkali metal in the anode compartment A and liquid sulfur in the cathode compartment K.
• the alkali sulfides collected in the reservoir BAS are transported to a second electrochemical cell at a location of high energy availability and electrolysis in the electrochemical cell to form sulfur and high purity sodium,
• step 6 sulfur and alkali metal is transported to a place of energy demand and fed into a connected as a power generator electrochemical power plant, characterized in that a device according to the invention is used.
• the redox potential of sodium and sulfur is utilized.
• the system of sodium and sodium chloride / heavy metal chloride forms the potential difference for energy storage.
• Preferred heavy metal chlorides are nickel-II-chloride and iron-II-chloride.
• the sulfur electrode is the plus side of the energy storage there.
• This positive pole is formed by a sulfur / sodium polysulfide-impregnated carbon surface structure, in particular a corresponding felt or fleece.
• the carbon electrodes are arranged concentrically around the ceramic electrolyte tubes. Through the installation a nonconductive open porous spacer layer, the direct contact of the carbon electrode with the ceramic electrolyte is prevented. This prevents sodium-free, non-conductive sulfur from settling on the ceramic electrolytes and limiting the flow of current.
• the carbon electrodes are connected via a system of Stromableitern (15) with the Stromammenischiene at the bottom of the drum cell low-resistance electrically conductive.
• the liquid sulfur is added in the cathode compartment with a Leitzusatz.
• Preferred conductive additives are selenium, tetracyanoethylene, graphites and carbon black.
• the alkali metal sulfides formed in the cathode compartment may comprise alkali metal sulfide and / or the corresponding polysulfides, in particular polysulfides of the formula M 2 S X , where x is a number> 2, in particular sodium polysulfides Na 2 S x .
• alkali metals especially sodium
• the electrolyte consists in a preferred embodiment of ⁇ -alumina or ⁇ "alumina, which is preferably stabilized, preferably with MgO or Li 2 0th
• Ceramics are used in a particularly preferred embodiment. Ceramic materials such as NASICON®, the composition of which is given in EP-A 0 553 400, are suitable as the material for the ceramics. A particularly preferred ceramic is the ceramic, which is also referred to as ceramic. Also sodium ion conductive glasses are suitable as well as zeolites and feldspars. However, preferred are sodium beta "alumina, sodium beta alumina, sodium beta / beta" alumina.
• the sodium-ion-conducting ceramics are preferably unilaterally closed-down, open-top, thin-walled tubes (FIG. 2, (7)) . The number is at least 1 maximum 200, in a preferred embodiment 50-150.
• Ceramic tubes with a diameter of The wall thickness is between 0.5 mm and 3 mm, preferably between 1.5 mm and 2 mm
• the sodium-ion-conducting ceramic tubes are preferably on the drum lid ( Figure 2) , 8) of the lower barrel attached so that they protrude from above into the contents of the sulfur barrel. They are operated in electrical parallel connection.
• alkali metal in the anode compartment is oxidized on the electrolyte E, with the alkali metal cations formed migrating through the semipermeable wall of the electrolyte E into the cathode compartment where they react with the sulfur to form alkali metal sulfides.
• the operating temperature of the electrochemical cell is preferably at least 250 ° C, and is preferably in a range of 300 to 350 ° C.
• the containers BA and BS are barrels, in particular in a cylindrical form, in particular with a sizing volume of 10 to 400, in particular 100 to 300 liters.
• these barrels are arranged one above the other in alignment, wherein when using the sodium / sulfur redox couple, the sodium keg is arranged in alignment over the sulfur barrel.
• Both barrels are electrically isolated from each other.
• a connecting electrolyte particularly a conductive ceramic, they are modified to function as electrochemical cells.
• the two barrels arranged one above the other are set in a common overhang (10). Between the walls of the two inner drums and the outer drum, a thermal insulation (1 1) is introduced, so that the inner drums can be kept at the operating temperature of 300 ° C ⁇ 30 ° C, at ambient temperature on the outer drum.
• the energy storage device according to the invention is constructed analogously to a drum bearing.
• these barrels can communicate with a tank farm.
• the solid electrolyte E in particular a sodium ion conducting ceramic, separates the liquid reactants.
• Several single cells can be combined into modules. To optimize the performance are several by the Electrolyte separated cell units connected in parallel. Regardless of the type, the individual cells, each with a cell voltage of around 2 V, are connected in series or in parallel. The set voltage level results additively from the voltages of the cell modules connected in series.
• the supplied amount of sodium and sulfur optionally in addition from storage tanks, is adapted to the generation of electricity.
• the product supply and Eduktab Entry can be carried out continuously or discontinuously.
• Alkali metal, sulfur and alkali metal polysulfide may optionally be stored in separate, heated storage tanks, in particular tanks.
• the power plant capacity has no limit. Power plant blocks of> 1 MW, in particular 1 - 1,000 MW are therefore readily possible.
• the voltage of the power plant unit can be fed into the grid after conversion into three-phase current.
• the optimization of the electrochemical reactor aims at the largest possible surface volume ratio of the sodium-ion-conducting ceramic to the volume of the reactants, so that even in large-scale systems, a compact design is possible and the power density per volume is as high as possible.
• the liquid alkali metal is high purity sodium, preferably having a maximum bivalent cation content of less than 3 ppm.
• the liquid non-metal is sulfur.
• the cell is preferably operated in a preferred process by circulating the liquid alkali metal with the aid of an inert gas introduced with positive pressure. Electrical connections and insulation
• the redox potential-forming substances for each voltage stage are stored separately from one another in the electrochemical reactor in a decentralized manner.
• the wiring and the mass transport must be carried out so that electrical short circuits are avoided.
• special devices for potential separation for the mass transfer between central tanks and the individual electrochemical reactors are required.
• the current density in the charging and discharging of the memory referred to the surface of the ceramic is between 100 A / m 2 and 3000 A / m 2 , preferably 1000 A / m 2 .
• the sulfur electrode is on the outside of the ceramic tubes. On the inside is the sodium melt.
• the sodium melt in the interior of the ceramic tube communicates via a riser (9) with the contents of the sodium reservoir (4).
• the sodium hydrostatically flows from the storage container into the ceramic during the discharge process. When charging the electrochemically generated pressure pushes the sodium back into the reservoir.
• the electrical power of the system is determined by the usable surface area of the sodium ion-conducting ceramics.
• the capacity of the storage unit is determined by the mass of the redox partner present in the deficit.
• the device according to the invention is constructed in the modular principle.
• the kit makes it possible to vary the number of ceramic tubes per drum cell.
• the number of ceramic tubes installed in the drum cell can be varied within a range of 1: 200, preferably 1:10, and thus adapted to the requirements of the customer.
• the requirement for a longer charge and discharge cycle at a fixed nominal capacity means that more redox chemicals are stored in total, meaning that more barrels are used.
• the number of ceramic tubes per barrel cell is reduced by the same factor, so that the number of ceramic tubes for the sum of all barrel cells remains the same.
• a total of 15 ceramic tubes are distributed over 3 barrels.
• the requirement of a 1,60-fold performance cycle is fulfilled by distributing the 15 ceramic tubes into 5 barrels (variant).
• the maximum performance of a drum is limited by the maximum number of ceramic tubes that can be accommodated in a drum cell.
• the nominal charge or discharge period of a maximum loaded barrel lasts a minimum of 8 hours, preferably 10 hours, a maximum of 20 hours.
• the series-produced drum cells are set in a preferred embodiment in a transport container and there electrically connected in series connected.
• a transport container By installing any number of transport containers an electrochemical storage power plant of any capacity can be built.
• the connection to the power grid is done with rectifiers and inverters that are state of the art.
• a container has a discharge capacity of 500 kW with a storage capacity of 7.6 MWh, which can be unloaded.
• the nominal charging and discharging current is 6400 A.
• a DC voltage of 98 V per container must be provided via a mains rectifier. When unloading the inverter is fed with 80 volts per container.
• the electrolyte E is present as a ceramic tube, via which the sodium supply is also effected. In the event of an unwanted discharge, the resulting short-circuit current is used to trip a fuse, breaking both the current and sodium flow.
• FIG. 1 schematically shows an upper steel sheet drum (3) for receiving sodium and a barrel (1) arranged flush therewith for receiving sulfur, both barrels being set in a common overhang (10).
• Figure 2 shows the main body of the lower barrel (1). It is a sheet steel drum with a set inner lining (2) made of an aluminum magnesium sheet, preferably of the alloy AI-Mg-5083.
• the drum content (6) is, for example, sulfur / sodium polysulfide or sodium chloride / heavy metal chloride with the NaAICI 4 Leitsalzschmelze.
• the barrel diameter is a minimum of 150mm, a maximum of 1500mm, preferably 600mm.
• the barrel height is minimum 300mm, maximum 2500mm, preferably 900mm.
• the main body of the upper drum is a bottom open steel drum (3) with a set down closed and open top insert (4) made of sheet steel, the sodium reservoir.
• the sodium reservoir is designed with bottom holes and tube inserts so that the sodium content (5) can communicate freely around the tube inserts without allowing sodium to flow through the apertures on the bottom ( Figure 3).
• the space above the sodium level and in the free core of the tube inserts remains filled with inert gas (nitrogen).
• inert gas nitrogen
• the power supply (12) serves in a dual function as a conduit for the sodium transport between the inside of the ceramic (7) and the sodium reservoir (4).
• the power supply of each individual ceramic tube is via a hollow drilled fuse (13) connected to the collective power supply of the negative side (14).
• both chambers are covered with inert gas (nitrogen or argon).
• the pressure on the sodium side is kept 100 mm higher than on the sulfur side. This prevents sulfur vapor from flowing into the sodium chamber in the case of defective ceramics.
• FIG. 4 shows possible distribution forms of the electrolytes present as ceramic tubes per drum cell.
• Figure 5 shows the possible arrangement of the device according to the invention in the form of a container.
• FIG. 6 shows a particular embodiment of the present in the form of a ceramic electrolyte E:
• a ceramic insulator ring (20) is soldered with glass so that a hermetically sealed connection.
• This electrically insulating insulator ring preferably of alpha-Al 2 0 3 , is hermetically sealed on its underside with a sealing adapter ring (19), preferably of an aluminum alloy, by means of a ceramic-metal compound (22).
• the ceramic-metal compound (22) is preferably produced by diffusion welding, particularly preferably ultrasonic welding.
• the seal adapter ring (19) is welded at its free end into the drum lid of the lower drum.
• This seal adapter ring (24) is welded to the displacement body which also acts as a power supply (17), so that the interior of the ceramic forms a closed space.
• This interior is connected to the overlying sodium reservoir (4) via a bore (9) in the power supply (12), the special fuse (13) and the dip tube.
• the sodium reservoir (4) rests on many insulating rings (27) which are centered and supported by the upper seal adapter ring (24).
• FIG. 1 A variant of the installation of the ceramic which is improved in terms of mass production is shown in FIG.
• the ceramic insulator ring (20) is modified so that the two ceramic-metal compounds (22), (23) can be made from above.
• FIG. 1 A further variant of the installation of the ceramic, which is improved in terms of mass production, installation and mechanical stability, is shown in FIG.
• the ceramic insulator ring (20) is modified so that the two ceramic-metal compounds (22), (23) can be made from above.
• the barrel lid is through two sheets (8) (8b) are formed, whereby the lower ceramic-metal compound (22) and the weld (25) of the lower seal adapter ring (20) are mechanically relieved.
• the assembly is facilitated by the fact that the lower drum cover plate (8b) carries the installation of the ceramic before welding.
• FIG. 9 shows the installation of the ceramic and the complete system as an assembly drawing.
• the device according to the invention therefore contains heat exchanger tubes (16) via which the heat loss is dissipated by means of a heat carrier, such as heat transfer oil.
• a heat carrier such as heat transfer oil.
• the functional integration of power supply (12) and sodium transport (9) counteracts the unwanted discharge of the energy storage in the failure of a single ceramic.
• a short-circuit current occurs in the affected power supply, which leads to the response of the fuse (13), whereby the current flow and also the sodium flow are interrupted.
• the storage system can continue to operate even after the failure of individual functional units.
• at least one container BA or BS contains a displacer which reduces the mass of the particular reactant in the volume. Such an embodiment may serve as an additional safety device. Examples Example 1 A) Apparatus
• the apparatus shown in FIG. 2 was used.
• In the lower steel sheet barrel (1) (2) 121 pieces of closed bottom ceramic tubes, made of beta "-AI203, appeared.
• Each ceramic tube had an internal minus-polarity power supply (12). These power supply lines were secured against short-circuit with fuses and routed on top of a common busbar (14).
• the plus-pole power supply lines (15) were arranged between the ceramic tubes and contacted the graphite fleece, which was fixed around the ceramic tubes.
• Each ceramic tube formed with the two redox partners inside and outside, the graphite fleece and the power supply an electrochemical unit cell.
• All unit cells of a drum cell were electrically connected in parallel. They were at the same potential. The currents of all unit cells added up to the total flow of the drum cell. A 4 quadrant thyristor rectifier / inverter (15000 A, 3 volts) was used, which allowed controlled unloading and loading of the drum cell. The electrical connection was made with aluminum rails.
• the surface of the ceramic tube on the inside is calculated to 0.0515 m 2 .
• the entire barrel had 6.23 m 2 electrode area.
• the two inner drums of the apparatus were heated to 290 ° C.
• the temperature was maintained at ⁇ 10K by controlling the heat transfer circuit in the heat exchanger tubes (16) to the appropriate temperature.
• Example 2 In automated operation, the cell was subjected to 1000 charge / discharge cycles, discharged for 10 hours, and charged for 10 hours. It was discharged with 1 1, 6 kW and charged with 14.3 kW. The current was ⁇ 6230 A.
• Example 2 In automated operation, the cell was subjected to 1000 charge / discharge cycles, discharged for 10 hours, and charged for 10 hours. It was discharged with 1 1, 6 kW and charged with 14.3 kW. The current was ⁇ 6230 A.
• Example 2 Example 2:
• Example 2 Forty-three pieces of the drum cells described in Example 1 were placed in a 40 'marine transport container. The drum cells were connected in electrical series with aluminum rails. As a result, the open circuit voltage increased to 89.4 volts. A 4-quadrant thyristor rectifier / inverter (10000 A, 120 volts) was used, which allowed controlled unloading and loading of the drum cell. The electrical connection was made with aluminum rails.
• the cell assembly was subjected to 1000 charge / discharge cycles. It was discharged for more than 10 hours and then charged for more than 10 hours.
• the discharge capacity was 0.5 MW.
• the load was 0.613 MW.
• the current was ⁇ 6230 A.

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