• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:

    公开号:SU1838848A3
    申请号:SU904831893
    申请日:1990-11-30
    公开日:1993-08-30
    发明作者:Dzhon Bones Rodzher；Kh Yug Dunkan Dzhejms；Gerkules De Dzhazher Dzhakobus
    申请人:Lillivit Sosete Anonim；
    IPC主号:
    专利说明:

    The invention relates to a laterally compressed solid electrolyte cassette for use as an electrode holder in an electrochemical cell: to a method for manufacturing such a cassette. and a cassette made by this method and an electrochemical cell containing electrodes in such a cassette.
    GB 2,100,498 discloses the use of solid electro sides of a solid electrolyte cassette 10 for holding electrode material, comprising corrugated sheets joined at the edges. The sheets are aligned according to their mutual position so that their corrugations extend parallel to each other along the cartridge, forming a cavity. The corrugations of the sheets enter each other there. where the sheets are connected to each other. The corrugations of the sheets, at least part of the length of the cartridge are phase shifted by 180 °. Inside the cassette there is a spacer for spreading sheets from each other and for communication between all parts of the internal cavity. A method of manufacturing a cartridge includes molding snow from a solid electrode material and a binder with thermoplastic and thermosetting properties, molding snow into sheet corrugated material, joining sheets to each other into a cartridge, heat treatment and sintering into a refractory cartridge. An electric cell with anode and cathode cavities separated by a solid electrolyte uses a cassette as a holder for electrode material. 3 sec and 11 z.p. f-ly, 14 ill.
    Rolita. made of / - aluminum. British patent GB 1274211. in turn, discloses a method for producing a sintered refractory product, comprising the following steps: forming a mixture of a powder of a refractory material and a binder with thermoplastic and thermosetting properties, molding the mixture into corrugated sheet material by passing it between heated corrugations
    1838848 with AZ rolls, the joining of two sheets to each other by squeezing and rolling and the evaporation of volatile from the binder by heating, followed by sintering. UK patent application 2228137 discloses an electrode holder for an electrochemical cell, the holder being in the form of a cassette consisting of two opposite sheets joined together along their edges to create a peripheral edge of the cassette and to form a cavity between them to hold the electrode material, one of sheets has a corrugated surface, and the other is made of solid electrolyte material.
    In accordance with one of the distinguishing features, a laterally compressed cassette has been created for use as an electrode holder in an electrochemical cell. consisting of a pair of opposite sheets joined together along their edges to create a peripheral edge of the cartridge and to form a cavity between them to hold the electrode material, one of the sheets having a corrugated surface and the other made of solid electrolyte material, both sheets are made of solid electrolyte material and both sheets have a corrugated surface, the sheets form a pair of opposed corrugated main surfaces of the cassette, and the main surfaces are matched to each other with each other so that their corrugations extend along the length of the shell parallel to each other, the corrugations of each main surface enter the corrugations of the other surface at the ends of the cassette, where the sheets are connected to each other.
    The main surfaces can be so coordinated with each other that the corrugations of each main surface, at least for part of the length of the cartridge, are not phased with each other, i.e. at least partially offset from each other in a direction perpendicular to the length of the corrugations.
    The corrugations of each main surface on most of the length of the cartridge can be phase shifted 180 ° relative to the corrugations of the other surface, so that the sheets enclose with each other on the indicated most of their length many tubular cavities that extend parallel to each other.
    Instead, the corrugations of each main surface on a smaller part of their length can be phase shifted 180 ° relative to the corrugations of the opposite surface of the cartridge and enclose a plurality of tubular cavities next to each other and parallel to each other, and the tubular cavities are located near and / or near one end of the cartridge, and the corrugations of each main surface between the specified tubular cavities and the junction between the sheets at the opposite end of the cartridge are in phase and enter each other for most of the length of the boxes children, and the sheets are spaced from each other along the specified most of the length of the cartridge.
    Instead, the corrugations of each main surface along their full length between the joints between the sheets at the ends of the cartridge can be in phase and enter into each other, and the sheets are spaced from each other along the indicated parts of the corrugations.
    The cartridge may have an inward opening for passing material through it during use of the cartridge as an electrode holder.
    The sheet spacing means may be located between the sheets inside the cassette for spreading the sheets from each other and to facilitate communication and fluid flow between all parts of the inside of the cassette. The spacing means may be in the form of a porous spacer sheet located between the main surfaces of the cartridge, the spacer sheet having corrugations that are smaller in magnitude and amplitude than the corrugations of the main surfaces.
    The cassette is conveniently made entirely of sintered alumina, at least the sheets forming the main surfaces of the cassette are made of beta-alumina.
    In accordance with another distinctive feature of the invention, a method for manufacturing a laterally compressed shell of solid electrolyte material for use as an electrode holder in an electrochemical cell, a shell consisting of a pair of opposite sheets connected to each other along their edges to create a peripheral edge of the shell and for the formation of a cavity between them to hold the electrode material, and one of the sheets has a corrugated surface, and the other is made of electrolyte Ma terial, a method comprising the steps of: forming a mixture consisting of a solid electrolyte material or its semi-finished product in the form of particles together with a binder that has both thermoplastic and thermosetting properties, molding the mixture into corrugated sheet material5, joining two sheets of said corrugated sheet material with each other at the edges with the formation of the shell, processing the shell to cure the binder, heating the shell after curing to evaporate volatile and sintering of the shell after evaporation volatiles with the transformation of the shell into a sintered refractory shell, the sheets of corrugated sheet material being arranged so that the shell is formed by two opposite corrugated main surfaces, the main surfaces being aligned with each other during the formation of the shell of corrugated sheets in such a way. that their corrugations extend along the length of the shell parallel to each other and so that the corrugations of each main surface are in phase and enter each other with the corrugations of the other main surface at the ends of the shell, where the sheets are connected to each other.
    The mixture can be formed into corrugated sheets by passing the mixture through corrugated rolls, the edges of the sheets can be joined together by compressing them at an elevated temperature, at which the binder undergoes thermoplastic softening, and the compression is performed with at least one roller.
    The method may include the step of placing spacers between sheets of corrugated sheet material when assembling cassettes from them. Thus, spacer means in the form of a corrugated gasket can be placed between these sheets with an edge clamp between the edges of the sheets in the joint along the edge of the cassette, the method comprising molding the gasket from a powder mixture of the same solid electrolyte material or its semi-finished product and a binder having the properties of both thermoplastic and thermosetting materials, and the components of the mixture are chosen so that the spacer gasket becomes porous with the specified sintering.
    The method may include the step of making an opening inside the cassette by winding a sheet of material made by molding particles of a ceramic material or its semi-finished product and a binder having the properties of thermoplastic and thermosetting material onto a mandrel with the formation of a short neck, connecting the end of the neck to the specified sheets of the cassette under pressure, until the binder cures at a temperature when the binder in the neck and sheets is softened, then remove the mandrel from the neck so that it sintering tightly connected to the cassette and defines an opening in the cassette.
    The invention extends to solid electrolyte cassette material. used as an electrode holder in an electrochemical cell if it is manufactured by the method described here.
    The invention also extends to an electrochemical cell containing a cassette, as described herein, the cell having an electrode located in the cassette and an electrode outside the cassette, the cassette forming a solid electrolyte, whereby the electrodes are electrochemically connected to each other.
    The cassette is preferably entirely made of sintered alumina, as described above, and the electrode inside the cassette is the anode of the element and contains sodium, which is molten at the operating temperature of the element. The other electrode may be a cathode, or catholyte. Such a catholyte, for example, may consist of a sphere (sodium sulfide) of sodium polysulfide or it may contain a cathode with a liquid electrolyte, for example, as described in UK patent No. 2114803.
    In principle, a cassette can be used as a cathode holder. In this case, the cathode may be, for example, of the type described in US patent application 4772875, from particles of a cathode prefabricated impregnated with an electrolyte that is placed in a cassette after molding and converted into a cathode by conducting at least one electric charge cycle in the sodium element anode. However, the cassette is mainly designed to accommodate the anode, and contains, for example, molten sodium anode material, as shown above, and the cathode is located outside the cassette, and not inside it.
    In this case, the solid electrolyte is typically beta-alumina, and in this description ι beta-oxide contains / ϊ ’’ - alumina. In fact, it is β'-alumina that is usually used in this method due to its increased ability, in comparison with aluminum beta-oxide: to conduct sodium ions.
    It is preferable to use beta-alumina, or preferably β-alumina, in a mixture with binders, one or more, having the properties of both thermoplastic and germanium "" 4 "reactive plastic, for the manufacture of sheet material for cassettes. However, instead of this and, as indicated above, a prefabricated beta-oxide or β-alumina can be used, which is a powder mixture containing a suitable alumina or hydroxide, together with sodium oxide and lithium or magnesium oxide (or a semi-finished product) in appropriate proportions, which mixture is known to be among the specialists and forms beta or / '- aluminum oxide during sintering. A semi-finished product of oxide, such as beta-alumina, sodium oxide or lithium oxide, is a substance that, when heated to 15,700 ° C in air, turns into the corresponding oxide.
    Binders of the thermoplastic and thermosetting type for our invention are described, for example, in Great Britain patent 1274211. As mentioned in this patent, one binder can also be used, provided that it has the required thermoplastic and thermosetting properties.
    So, you can use polyvinylbut-25 tyral as both a thermoplastic and thermosetting binder, together with a plasticizer, such as dibutyl phthalate and a solvent, such as methyl ethyl ketone, and the solvent and 30 plasticizer help mix the binder with the beta-alumina powder to form a uniform mixtures. If vigorous mixing is used, such as in a Banbury-type mixer, then 35 can in principle be dispensed with a plasticizer and a solvent.
    Forming the mixture into sheet material can also be carried out as described in British Patent 1274211, for example 40. on calendars, rolling or doctor blade technology. The sheet material can also be compacted, as described in British Patent 1274211, for example by crimping in rolls or pressing 45. As the final stage of the production of sheet material, as mentioned above, it can be passed through a pair of corrugated rolls, and the corrugations on the rolls can have, for example, a sinusoid-50 long profile of the corresponding module and height so that the cassette has the desired internal capacity, as will be explained below, or the material can be corrugated when casting into a mold, or when casting under 55 pressure into an appropriate mold.
    The formation of sheet material in a flat cassette can be done by superimposing two sheets of material of the same size and shape (for example, a rectangular shape with corrugations parallel to each other) and compressing their side edges together with sufficient force to obtain a permanent deformation of them into each other to form a strong joint along the specified lateral edges. The compression of these edges can be carried out by means of a roller and, if desired, for sheet materials with an elevated temperature in the range of 50-100 ° C, for example 60 ° C, in which the binder is softened thermoplastic. Instead, especially when compressing at the bottom of the indicated temperature range, the above solvent can be used at the edges of the sheets before they are compressed, so that the compressive strength can be reduced, if desired, such a solvent can be used to compress the edges at room temperature to seal them.
    If the corrugations of the main surfaces are completely out of phase, i.e. 180 ° C, as described above, over most of the length of the cartridge, the corrugations of at least one sheet will be shifted sideways so that they coincide in phase with the corrugations of another sheet at the junction at each end of the cartridge. Thus, at each end of the cassette, the corrugations of each sheet surface can be shifted by 30 ° or a quarter wavelength sideways in one direction, and on the other sheet in the opposite direction by the same amount. In this configuration, the cassette for most of the length will have protrusions of the corrugations and troughs of the corrugations against each other, so that many tubular cavities are formed between them parallel to each other.
    However, at the opposite ends of the cassette, two corrugations are in phase, the sheets in a plastic state will be deformed so that they merge together in the longitudinal outer direction, which will allow sealing the joint under the action of heat and pressure, as described above, using the appropriate shape of the press surfaces or rolls for joining sheets at elevated temperatures, or using the specified solvent, or using both. If desired, a strip of the same 8 phase corrugated material can be laid between the sheets with the corrugations of the ends of the sheets when sealing in order to improve sealing.
    The applicant found that, with appropriate softening at elevated temperatures, it is possible to mechanically shift parts of the sheets to the side, keeping the corrugations parallel over most of their length, while the end parts of the corrugations go into the main ones in the section of the oblique direction of the corrugations in the transition zone, and in these transition zones the corrugations of one sheet intersect the corrugations of the other at an angle. However, for mass production, it is better to have ready-made sheets with the desired offset of the corrugations at the ends due to their preliminary casting or pressing in the appropriate form. Naturally, instead of shifting the corrugations relative to each other by 90 ° on each outer side of the sheet, or by a quarter of the wavelength in the opposite direction, it is possible to shift the corrugations in only one sheet of a pair by 180 °. or half-wave, at the end of the cassette, and have another sheet with straight ribs along its entire length. This will also combine the corrugations at the ends of the cassette and allow them to be sealed at the ends, as described above.
    Although, in principle, it is possible to connect the side edges and the edges along the length together as described above, so that in the middle part of the cartridge the corrugations inside only slightly touch each other, or have small gaps between them if the corrugations are out of phase, which will allow the liquid to flow and communication inside, usually internal spacers between the central parts are still used to provide the clearances necessary for communication between the internal cavities.
    To use the cassette as a holder for the sodium anode, the composition of the corrugated sheets is preferably selected such that after sintering beta-alumina in the sheets is as close to the solid state as possible. The beta-alumina powder should preferably have an average particle size of a maximum of 70 microns, and preferably 10-50 microns, with a maximum particle size of not more than 100 microns, and it is desirable that the particles are basically the same size.
    According to a particular feature of the invention, the spacers should be relatively porous and thin so that they are permeable and actually saturated with the contents of the cartridge and provide electronic conductivity and / or, in the optimal case, the passage of the contents of the cartridge through the spacers.
    It is convenient to carry out spacer gaskets also from beta-alumina. They can be made relatively porous from beta-alumina powder (for example, with relatively large particles of approximately the same size) in a mixture with binders similar to that used for the outer sheets forming the main surfaces of the cartridge. This mixture is then formed into spacers in unreacted or plastic form, then the spacers are introduced between the outer sheets in the central part, after which the temperature is increased for the binder to solidify, the temperature is further increased for the binder to evaporate, and then sintered together with the material of the outer sheets. The required porosity can also be achieved by the inclusion of particles, for example carbon, cellulosic materials, or volatile organic materials, which are burned during evaporation and / or sintering.
    A particularly convenient method according to this invention involves the use of technology borrowed from the production of corrugated cardboard (which can be used to produce sheets for the main surfaces of the cassette) to obtain a thin corrugated panel made from a mixture of beta-alumina described above, the composition of which provides porosity after sintering, at least one such spacer is inserted between the two outer sheets, the size of the spacer is taken to be the same as the sheets in the central parts, and the edges are compressed between the edges of the outer sheets in the manufacturing process of the cartridge. Typically, a corrugated spacer panel is also formed by rolling between the profile rolls, and has, for example, sinusoidal corrugations of a suitable small module, for example, less than half the module of the base sheets, and with an amplitude equal to the desired distance between the outer sheets. The outer sheets will be pressed to the tops of the corrugations of the spacer panel on both sides when molding in an unreacted state, and will be held in this position when the edges are compressed. Instead, two spacer panels can be used, each with small corrugations of less than, for example, half the amplitude and the corrugation module of the outer sheets, and two spacer panels can be inside the cassette in the form of spacers between the inner surfaces of the outer sheets, bending and entering between the corrugation vertices of the specified outer sheets.
    Another means of creating corrugations on spacer panels (or outer sheets) is to enclose them between sheets of thin metal foil, such as aluminum. This sandwich is then passed through the profile rolls. All three layers become corrugated at the same time. According to this method, the corrugation can be carried out at room temperature. The aluminum foil can then be removed from the corrugated panel when necessary.
    The neck or passage into the cassette can be made from a mixture used for corrugated sheets, or instead, from a mixture in which the beta aluminum oxide of the outer sheets is replaced with alpha aluminum oxide of the same particle size. When sintering after pressing or clamping the neck into the outer sheets of alpha-alumina, it forms insulation for ions and electrons in the neck or passage connected and sintered to the cartridge.
    In this embodiment, with the main central part and smaller end parts, when used for example as a sodium anode holder, all the sodium of the anode in a charged state will be in the tubular cavities of the central part.
    However, if you want to use a sodium anode holder as a holder, another version of the cartridge with a relatively short enlarged part with tubular cavities located at one end of the cartridge can be used. In this embodiment, the outer sheets can be arranged so that most of the length of each sheet from one end of the short central part has corrugations in phase with the corrugations of the other sheet, and enter into them, and this part extends from one end of the enlarged part, with the sheets connected to the edge remote from it, In the part where the corrugations enter into each other between the enlarged part and the specified sealed edge, the corrugations entering into each other are kept at a distance by a gasket so that sodium is between them, using the corrugated above okladkoy in which the corrugations of the module and • amplitude less than half than in the outer leaves, and the gasket is curved, so that> enter the corrugated outer sheet and fit the outer sheets is obtained on both sides of the gasket.
    In this case, the enlarged part can again be obtained as described above by mixing the corrugations of one outer sheet relative to the other by 180 ° in phase to form the specified tubular cavities between the sheets, at the opposite ends of the enlarged part, the corrugations of the sheets are again shifted to coincide in phase to obtain the majority where the corrugations of the sheets enter each other, and are sealed at the edges and from the side of the thickened part.
    This design is intended for use in the upper position of the thickened part, which serves as a reservoir for sodium, which can pass downward under the influence of gravity into a larger part with corrugations entering each other, as sodium is consumed during the discharge of the electrochemical cell, in which sodium is an anode material.
    In this case, the side edges of the outer sheets can again be sealed by compression, as described above. Unreacted holes or passage can be made as described above, or the central hole can be provided in length through the adjacent edge of the cartridge in its Central part, and a separately made neck can be strengthened ng glaze in the hole, after sintering of the cartridge. And even if the neck is made on the mandrel and sealed in the cassette in an unreacted form, as described above, the seam of the passage into the cassette can be additionally covered with glaze after sintering.
    Whereas the outer sheets described above are obtained with the desired displacement of the corrugations by acting on them while they are in the plastic state, it is possible to produce them with pre-displaced corrugations. This will probably be preferable in mass production, and as mentioned above, can be produced by molding with or without pressure.
    The reaction in the binder can optionally be carried out in any way, for example, by irradiation or using a catalyst, but it is convenient to heat a thermosetting binder, such as polyvinyl butyral, for example 100-200 ° C.
    Heating to evaporate volatile material from the cassette can be carried out in any way, but it is necessary to conduct heating slowly enough to drive off volatile materials without damaging the material of the cassette, and it is preferable that the cassette does not adhere to most of the surface of the furnace during the operation.
    A typical heating mode may have a maximum speed of 60 ° C per hour from ambient temperature to a reaction temperature of say 200 ° C, slower heating at a speed of maximum 30 ° C per hour, but preferably not more than 1 ° C per hour, for example 60 ° C per hour from the reaction temperature to a temperature of, say, 450 ° С, at which all volatile substances, including carbon, have already found a comparatively increased speed after that, a maximum of 180 ° С per hour to the temperature is 10-20 ° С lower than the maximum, and final heating at a lower slew rate - maximum 60 ° C per hour - d maximum temperature. After holding for for example 10-20 min at the maximum temperature for annealing, if desired, cooling can be at a maximum speed of up to 240 ° C per hour to say 1000 ° C, then cooling is carried out at an increased speed to a maximum of 360 ° C per hour before room temperature. Preferably, after the volatiles are distilled off, the cassette is kept in a completely dry atmosphere until it is sintered to avoid cracking. caused by moisture.
    Since the cartridge is corrugated, it will lie horizontally on the floor of the furnace, in contact only with the tops of the corrugations with the floor, which reduces the risk of formation of bubbles and cracks from the bottom of the cartridge during the removal of volatiles, the resistance to the formation of bubbles and cracks can be increased by installing cartridges on linings made of corrugated sheets of beta-alumina, the corrugations of which are perpendicular to the corrugations of the outer surface of the cassettes.
    While a flat cassette or lining usually has a flat rectangular shape, it can also be rolled up into a spiral, before the reaction of the binder, while still in a plastic state, with the axis of the spiral. parallel to the corrugation, one edge of the spiral is internal and the other external. In this configuration, the cartridge can stand in the furnace at one of the ends and resist cracking and bubble formation during the removal of volatiles, which happens when the surface of the cartridge lies on the furnace floor. The spiral electrode inside the cassette on one or the other side can be opposite the spiral other electrode, or the spiral cassette in which the other electrode is located.
    The invention is described by way of example in the accompanying schematic sketches in which: in FIG. 1 is a perspective view of one embodiment of a beta-alumina anode cartridge according to the method of the invention: FIG. 2-5 are sectional views of the cartridge of FIG. 1 along the lines P-P + y-y of FIG. 1: in FIG. 6 is a section according to FIG. 2 of another design of the cassette of FIG. 1: in FIG. 7 is a perspective view of yet another embodiment of a beta aluminum oxide cartridge according to the method of the invention: FIG. 8 and 9 are sectional views of the cartridge of FIG. 7 along lines VIII — VIII and IX — IX; in FIG. 10 is a perspective view of an electrochemical cell with a plurality of cassettes of FIG. 7: FIGS. 11 and 12 are sectional views of collapsed versions of the cartridge of FIG. 1 and 7; nafig. 13 is a view of the type of FIG. 1 and 7 of yet another embodiment of the beta alumina cassette of the invention: FIG. 14 a portion of the cassette set of FIG. 13 in sectional view.
    Turning first to FIG. 1-5. the number 10 designates flat cassettes of / (- aluminum oxide according to the invention. The cassette is rectangular in shape and has a tubular anode passage 12 at one end leading to the hollow interior through one edge. The cassette 10 has two outer sheets in the form of sintered panels 14, 16 / (- alumina of maximum density, which are spaced in the Central part 18 (Fig. 1) to form a cavity inside the cassette. The sheets of the panels 14, 16 in the Central part have a spacer panel 20 of beta-alumina, located between the panels 14, 16.
    The sheets of panels 14, 16 have longitudinal corrugations of a sinusoidal profile and in the central part 18 of the cartridge (see Fig. 2), the corrugations of 22 sheets or panels 14, 16 are parallel to each other, and the corrugations 22 of the panel 14 are 180 ° out of phase, i.e. are opposite in phase with respect to the corrugations 22 of the panel 16. The vertices of the corrugations of the panel 14 thus coincide and are opposite to the depressions of the corrugations of the panel 16 and vice versa, so that tubular cavities are formed between the panels 24. Typically, the amplitude A and the module P of the corrugations 22 of the panels 14, 16 are respectively 10 mm and about 7 mm, and the thickness of said panel typically 0.9-1 mm, such that it is clear that several drawings are schematic and not to scale.
    The spacer panels 20 have corrugations 26 much smaller than the corrugations 22 of the panels 14, 16 for which the module P and the amplitude A, respectively, are less than half of these values for the panels 14, 16 and they divide the cavities 24 between them, sandwiched between the panels 14, 16, in half, however do not isolate these halves from each other, since the panel 20, as mentioned above, is porous for molten sodium.
    The passage 12 is made in the middle through one of the edges of the cassette Yu and extends parallel to the corrugation 22. 26 panels
    14.16 and 18.
    At the opposite ends of the central part of the cartridge 10, the corrugations 22 of the panel 14 are laterally shifted to one side, and the corrugations 22 of the panel 16 are laterally shifted to the other side, in the transition zones 28 (Fig. 1), where the corrugations deviate from the direction parallel to the corrugations of the central part 18, so that the corrugations 22 of the panel 14 intersect the corrugations 22 of the panel 16. On the side of the transition zone 28. remote from the Central part, the cassette has end parts 30, where these corrugations again parallel to the direction in which they go in the Central part.
    A cross section of one of the transition zones 28 is shown in FIG. 3, a section of the cartridge in its end part ZR near the transition zone 28, remote from the central part, is shown in FIG. 4, and a section of the end portion 30 near the end remote from the transition zone 28. shown in FIG. 5.
    As can be seen from FIG. 4 and 5, the lateral displacement of the corrugations 22 in the panels 14 and 16 takes place at 90 °, respectively, or a quarter of the wavelength / module of the corrugations in each direction, so that the end parts 30. as shown in FIG. 4 and 5, completely coincided in phase with the corrugations 22 of the panels 14 and 16. In the transition zones 28 of the panel 14. 16 are spaced from each other by the same amount as in the central part 18 and the gasket panel 20 extends across the width of the inner part of the cassette between side edges 32 in the central part and transition zones 28. However, the spacer panel 18 does not extend outward in the opposite direction beyond the transition zones 28.
    The panels 14 and 16 longitudinally outward from the transition zones converge to each other until they merge at the ends 34 of the cassette, as shown in FIG. 5, where they are fastened together. The panels 14, 16 are sealed together at the edges 32, as described below.
    Naturally, and in some cases, it is preferable if the spacer panel 22 shown in FIG. 2 and 3, replaced by a narrow strip of the same finely-corrugated material between the panels 14, 16 at the end of the central part, remote from the passage 12, and the corrugations of this narrow strip extend along the length of the narrow strip, and the narrow strip and its corrugations extend perpendicular to the corrugations 22 and gaps 24 .
    In FIG. 6, which corresponds to FIG. 2, another construction of the cartridge 10 is shown, which has two spacer panels 36 instead of one spacer panel 20 shown in FIG. 2. These spacer panels 36 are also corrugated with small corrugations parallel to the corrugations 22 of the panels 14. 16, but instead of being located in the plane between the panels 14, 16 and dividing their cavities 24 in half, as shown in FIG. 2 for the panels 20, the panels 36 are curved and enter the corrugations and touch the inner surfaces of the panels 14, 16. The tubular cavities 24 thus appear between the spacer panels 36. The panels 36 respectively extend inside the corrugations and come into contact with the inner surfaces 38, 40 of the panels 14 , 16.
    In FIGS. 7-9, the same reference numbers indicate the same panels as in FIG. 1-6.
    However, in FIG. 7-9, the central part 18 does not have spacer panels 20 or 36. Further, one of the ends, designated 30.1, is longer than the central part 18 and extends over most of the length of the cartridge 10, the other end, designated 30.2, is the same as in FIG. 1-6.
    At the ends 30.1,30.2, the cassettes of the panels 14 and 16 have corrugations 22 that fit into each other, and at the end of 30.1, a spacer panel 42, similar to the spacer panels 36 in FIG. 1 (see Fig. 9), in contact with the inner surfaces 38 and 40 of the panels 14, 16.
    At the end of the part 30.1, remote from the center, and near the edge 34, the panels 14, 16 converge closely to each other and are connected at the indicated edge 34 with their sealing (as in Fig. 5).
    In FIG. 10, the numeral 44 generally denotes the high temperature rechargeable electrochemical cell of the present invention. The element has a box casing 46. made of flat panels of alpha-oxide, in which there are several flat cathode structures 48 with a spacing, parallel and face to face. These cathodes are of the type described in UK Patent 2114803 and are impregnated and immersed in molten salt electrolyte (not shown), also of the type described in UK Patent 2114803. These cathode structures 48 are connected in parallel to a common cell cathode bus 50.
    Element 44 further comprises several anode structures, each in the form of a cartridge 10 according to the invention, and containing molten sodium anode material.
    The cassettes in FIG. 10 of the type shown in FIG. 7-9, their central parts 18 are on top and filled with sodium and serve as sodium reservoirs for supplying sodium downward under the influence of gravity, as it is consumed when the element is discharged, into the narrow lower ends 32.1 of the holders 10, which are arranged in a row. alternately with cathode structures 48, face to face with them and with small gaps. The electrolyte level in the casing 46 is such that the cathode structures 48 are always immersed in it. The tubes 12 of the cassettes 10 are all connected to a common passage or collector 52, which goes to an external trap (not shown) and then into the free cavity of the casing 46, above the level of the electrolyte. The passage 52 is made of steel and has steel branch pipes.
    passing through the passages 12 (to which they are hermetically connected) and immersed in sodium in the central parts 18, so that the passage 52 serves as a common anode busbar connecting the anode structures in parallel.
    In FIG. 10, the function of the passage 52 with its steam trap is to equalize the pressure between the inside of the cassettes Jus on one side and the inside of the casing 46 outside the cassettes 10 on the other side. This pressure equalization is desirable to compensate for the movement of sodium during charge and discharge of the cell due to exchange with the electrolyte through the external panels 14, 16. Without this balancing, the pressure drop in the cassettes and the increase in pressure in the electrolyte during the discharge of the cell can in particular cause stresses in the cassettes and damage them. For this reason, it is also desirable that the panels 20, 36, 42 (see FIGS. 2, 6 and 9) have corrugations, since they strengthen the cassettes against external pressures. They also slow down the free flow of sodium in the event of cracking or breakdown of the cassettes, which contributes to safety.
    It should be noted that the casing 46 in FIG. 10 is indicated by a dotted line, and the rest of the element inside is shown by solid lines.
    In FIG. 11 and 12, the numbers 10.1 and 10.2 respectively indicate the spiral wound holders of the invention, when they are still plastic, for firing when installed on the floor of the furnace on one of the side edges 32 to reduce the formation of bubbles and cracks. They can be used with the holder, and the opposite electrode is inside the holder. The section in FIG. 11 through the central part 18 (see FIG. 2), but for ease of understanding, the spacer panel 20 (see FIG. 2) is not shown. The section in FIG. 12 - through the end part 30.1 (see Fig. 9), again with the missing spacer panel 42 (see Fig. 9). Otherwise, the same reference numbers indicate the same details as in FIG. 1-10.
    In FIG. 13 and 14, the same reference numbers are used as in FIG. 1-12 unless otherwise indicated.
    Cartridge 10 in FIG. 13 is basically the same as in FIG. 1, and has a spacer panel (not shown) similar to 20 of FIG. 2. The main s'i <ich between cassette 10 on F ".- 'J and in Fig. 1 consists in the fact that the Juice displacement of the corrugations 22 at each end of the cassette is made only on one of the panels 14.16, and the corrugations on the other panel 14, 16 at the end of the cassette are straight and have no displacement. This offset is thus on
    180 ° or half-wave or half-module, and not 90 ° or a quarter of the wavelength or module, as in FIG. 1, but the effect is the same - the corrugations of the panels 14, 16 at the ends coincide and enter into each other, as shown. It follows that the transition zones 28 differ in that the corrugations 22 of one of the panels are straight and the other oblique and intersect the corrugations of the first panel. Each panel has a shift of corrugations at one end, the panels are thus the same, although you can use one panel with offset corrugations at both ends, then the other panel will be straight along the entire length.
    As in FIG. 1. where passage 12 enters cassette 10, the cavity between the pair of corrugations is bent from the opposite panel so that there is an opening between the panels at 35, into which the passage enters the adjacent tubular cavity (see 24 in Fig. 2).
    In FIG. 14 shows three cassettes mounted on top of each other with matching corrugations 22. With this installation, tubular cavities 37 (similar in shape to the tubular cavities 24 inside the cassettes) are also obtained between the cassettes. If the cartridges contain, for example, sodium inside, then outside are cathode structures (not shown) that perform the same functions as the cathode structures 48 of FIG. 10, but cylindrical in cavities 37. Similarly, these cathode structures can be immersed in an electrolyte and equipped with collectors with which they are connected in parallel, and the sodium anode material inside the cassettes is also connected in parallel through passages 12. If desired, the cassettes 10 can be immersed in a catholyte, such as sodium sulfide polysulfide.
    The advantage of the structure shown in FIG. 14 is that a stack of several cassettes 10 instead of three in FIG. 14 may consist of many cassettes in a suitable housing (see 46 in FIG. 10). and the stack will have significant strength due to the resulting honeycomb structure reinforced with corrugations of 22 different cassettes 10.
    Example. For example, the applicant proposes to use in cartridges 10 a mixture for sheets of external panels 14 of the following composition:
    Components Amount of alumina (size 10-50 microns) 80-120 g binder 14-18 g plasticizer 5-10 g solvent 0-50 ml
    Binder, plasticizer and solvent of the type described in UK patent 1274211.
    By mixing the components, a semi-dry mixture of powders is obtained. It is passed through a hot rolling machine with many rolls at 50 ~ 150 ° C (depending on the composition used), at this temperature the binder will become plastic. The mixture is rolled into a flat sheet with a thickness of about 0.6 mm with a density after rolling of about 2.1-2.3 g / cm 3 and then rolled with a sinusoidal roll to produce sheet material for the outer panels or sheets 14, 16, which then can be cut to size.
    Another sheet is made in the same way and passed at 50 ~ 70 ° C between two corrugated rolls to obtain corrugations with a module, for example, about 5 mm and an amplitude of about 2 mm for spacer panels 20, 36, 42 and cut to the desired size . These corrugated panel gaskets will then be clamped, where required, between the panels 14, 16 to form spacer gaskets 20, 36, 42 and can be molded while they are hot and plastic, if necessary, adjacent to the corrugations 22 of the panels 14, 16 (see Fig. 6 and 9). The corrugations 22 of the panels 14.16 will be out of phase for the formation of tubular cavities 24. The edges 32 of the cassette 10 can be sealed at a temperature of 50-70 ° C using a small roller with hand pressure, and the neck can be clamped and sealed between the ends of the sheets 14.16 before removing the mandrel from it. The end edges 34 are sealed with a sinusoidally shaped roll after the displacement of the end sections 30, 30.1. 30.2, when the panels 14, 16 are still plastic, so that the corrugations of the panels 14, 16 are not in phase only in the central part 18, but in phase and enter into each other at the indicated end sections,
    The free-carrying unreacted cartridge obtained in this way can be heated and fired in the following modes:
    from room temperature to 450 ° C, at a speed of 10 ° C per hour from 450 to 1600 ° C at 180 ° C per hour from 1600 to 1617 ° C at 6 ° C per hour 1617 ° C - exposure for 15 minutes 1617 ° C - 1000 0 С at 240 ° С per hour 1000 ° С - room, at 360 ° per hour.
    After this firing cycle, a continuous cassette of β-alumina is obtained. The content of β-alumina is approximately
    98% by weight, its density is 3.1-3.2 g / cm 3 . After firing, a (linear) shrinkage of sizes of 17-18% is expected.
    This example shows the feasibility of the method of the present invention for producing β-alumina cassettes of the indicated type of acceptable quality and density.
    权利要求:
    Claims (14)
    [1]
    Claim
    1. A laterally compressed cassette for use as an electrode holder in an electrochemical cell, formed by a pair of opposed sheets joined together along their edges to obtain a peripheral edge of the cassette and to form a cavity between them to hold the electrode material, one of the sheets having a corrugated surface and the other is made of solid electrolyte material, characterized in that both sheets are made of solid electrolyte material and have a corrugated surface, while the sheets form a pair of opposed corrugated main surfaces of the cassette, and the main surfaces are aligned with each other so that their corrugations extend along the length of the cassette parallel to each other, and the corrugations of each main surface enter the corrugations of the other surface at the ends of the cassette, where the sheets are connected to each other .
    [2]
    2. The cassette according to claim 1. characterized in that the main surfaces are coordinated so that the corrugations of each main surface at least on a portion of the length of the cassette are not in phase with the corrugations 22 of the other main surface in a direction perpendicular to the length of the corrugations.
    [3]
    3. The cassette according to claim 2, characterized in that the corrugations of each main surface in most of the cassette length are 180 ° out of phase with respect to the corrugations of the other main surface, so that the sheets form, in the majority of their length indicated, a plurality of tubular cavities . extending parallel to each other next to each other.
    [4]
    4. The cassette according to claim 2, characterized in that the corrugations of each main surface in a smaller part of the length of the cassette are 180 ° out of phase with respect to the corrugations of the other main surface, forming between the sheets a plurality of tubular cavities extending parallel to each other and next to each other, moreover, the tubular cavities are located near or adjacent to one end of the cartridge, and the corrugations of each main surface between these tubular cavities and the joint between the sheets at the opposite end of the cartridge are in phase with each other and enter to each other over the greater part of the length of the cartridge, the sheets being spaced apart from each other along the indicated majority of the length of the cartridge.
    [5]
    5. The cartridge according to claim 1, characterized in that the corrugations of each main surface along their entire length between the joints of the sheets at the ends of the cartridge are in phase with each other and enter into each other, and the sheets are spaced from each other along these incoming corrugations.
    [6]
    6. The cartridge according to any one of claims 1 to 5, characterized in that. that it has an opening for passing a material stream inside it when using the cartridge as an electrode holder.
    [7]
    7. The cassette according to any one of claims 1 to 6, with the fact that the spacer is located between the sheets inside the cassette, for spacing the sheets apart and to ensure communication between all parts of the inside of the cassette.
    [8]
    8. The cartridge according to claim 7, characterized in that the spacer means is in the form of a corrugated porous spacer sheet placed between the main surfaces of the cartridge, the spacer sheet having corrugations smaller in magnitude and amplitude than the corrugations of the main surface.
    [9]
    9. A method of manufacturing a laterally compressed cassette for use as an electrode holder in an electrochemical cell having a pair of opposed sheets joined together along their edges to create a peripheral edge of the cassette and to form a cavity between them to hold electrolyte material, one of the sheets having corrugated surface, and the other is made of electrolyte material, the method includes the steps of forming a mixture consisting of solid electrolyte material or its semi-factory that in the form of particles together with a binder that has both thermoplastic and thermosetting properties, molding the mixture into corrugated sheet material, joining two sheets of said corrugated sheet material with each other at the edges to form a cassette, processing the cassette to cure the binder, heating the cassette after hardening for evaporation from the binder of volatile elements and sintering of the cartridge after evaporation of volatile elements with the transformation of the shell into a sintered refractory cartridge, characterized in that. that the sheets of corrugated sheet material are laid on top of each other with the formation of the cassette by two opposite corrugated main surfaces, the main surfaces being aligned with each other during the formation of the cassette of corrugated sheets so that their corrugations extend along the length of the cassette parallel to each other and so, that the corrugations of each main surface are in phase and coincide with the corrugations of the other main surface at the ends of the cassette, where the sheets are connected to each other.
    [10]
    10. The method according to claim 9, characterized in that the pressing of the sheets to each other is performed by squeezing the edges of the sheets together by means of at least one roll.
    [11]
    11. The method according to claim 10, with the fact that when forming a cartridge from sheets of corrugated material, a spacer is placed between them.
    [12]
    12. The method of pop. 11, distinguished by that. that a spacer in the form of a corrugated spacer-gasket is placed between said sheets by clamping the edge between the sheets in the peripheral joint along the edge of the cassette, and the spacer is formed from a mixture of particles containing solid electrolyte material or its semi-finished product and a binder having both thermoplastic and thermosetting properties, and the composition of the mixture components ensures the porosity of the panel after sintering.
    [13]
    13. The method according to any one of p. 9-12, characterized in that the hole inside the cassette is performed by winding sheet material formed from a mixture of particles of ceramic material or its semi-finished product and a binder having both thermoplastic and thermosetting properties around the mandrel for education neck, connections of one end of the neck to said cassette sheets by squeezing before curing at elevated temperature, providing plasticity of the binder in the neck and sheets and removal of the mandrel of the neck and then sintering the cassette and form an aperture in the cassette.
    [14]
    14. An electrochemical cell comprising a housing, an anode and a cathode, the anode and the cathode being separated from each other by a gasket in the form of an electrode holder made of solid electrolyte material, characterized in that the electrode holder is a cartridge according to any one of claims 1 to 8.
    Fig.Z
    Figure 4
    6
    Fi 7
    TIGP
    G Τ '
    Editor S. Kulakova Compiled by S. GredanoeaTehred M. Morgenthal Corrector L. Pilipenko
    Order 2927 Circulation Subscription
    VNIIIPI of the State Committee for Inventions and Discoveries at the State Committee for Science and Technology
    113035. Moscow, Zh-35, Raushskaya nab., 4/5
    Production and Publishing Plant Patent, Uzhgorod, Gagarin St. 101
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1838848A3|1993-08-30|Cassette compressed on sides used as electric holder in electrochemical element, process of its manufacture and electrochemical element
    JP2004349262A|2004-12-09|Electric connector and support for solid oxide electrolyte fuel cell combining foam nickel and expanded nickel screen
    US4176447A|1979-12-04|Method for making an electrode
    US6021039A|2000-02-01|Electric double-layer capacitor
    CA2042322A1|1991-11-17|Electrochemical cells
    CA2327940A1|1999-10-28|Method of making closed end ceramic fuel cell tubes
    JPH0758626B2|1995-06-21|Method for producing flat envelope made of solid electrolyte for use as electrode holder of electrochemical cell and envelope produced by the method
    US5279908A|1994-01-18|Electrochemical cell
    US5385700A|1995-01-31|Method of making a holder of ceramic material
    CN108463899B|2021-08-31|Device for storing electrical energy and method for the assembly and activation thereof and for the operation thereof
    JPH05144426A|1993-06-11|Electrochemical battery
    JP4103707B2|2008-06-18|Method for producing composite porous body
    JP4696442B2|2011-06-08|Composite porous body
    US5776384A|1998-07-07|Method for making carbon super capacitor electrode materials
    EP0239051A1|1987-09-30|Procedure and means for manufacturing storage battery plate assemblies
    GB2255309A|1992-11-04|Making a ceramic holder for active electrode material
    DE4116053A1|1991-11-21|ELECTROCHEMICAL CELL
    GB2042244A|1980-09-17|Making electrodes for sodium sulphur cells
    US4243733A|1981-01-06|Electrode structures
    JPH10189016A|1998-07-21|Solid electrolyte fuel cell
    EP0117238B1|1988-12-07|Sandwich electrode and a battery comprising the same
    JP4501385B2|2010-07-14|Gas diffusion layer member and cell member for polymer electrolyte fuel cell, polymer electrolyte fuel cell
    JP3677387B2|2005-07-27|Solid oxide fuel cell
    JP2662081B2|1997-10-08|Method for producing sodium-sulfur battery and method for producing molded anode
    JPH10275622A|1998-10-13|Cylindrical solid electrolyte fuel cell
    同族专利:
    公开号 | 公开日
    IT1243936B|1994-06-28|
    SE9003819D0|1990-11-30|
    AU6685690A|1991-06-06|
    GB9025943D0|1991-01-16|
    GB2240424B|1993-08-11|
    KR910013606A|1991-08-08|
    GB8927274D0|1990-01-31|
    CA2030461A1|1991-06-02|
    CN1053325A|1991-07-24|
    IT9022203A1|1991-06-02|
    JPH03187161A|1991-08-15|
    AU628010B2|1992-09-03|
    SE9003819L|1991-06-02|
    US5057384A|1991-10-15|
    ZA909269B|1991-08-28|
    DE4037882A1|1991-06-06|
    BR9006110A|1991-09-24|
    FR2655480A1|1991-06-07|
    IT9022203D0|1990-11-27|
    GB2240424A|1991-07-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2014160226A1|2013-03-14|2014-10-02|Enerdel, Inc.|Battery system with internal cooling passages|
    RU2669572C2|2015-02-11|2018-10-12|ФОРД ГЛОУБАЛ ТЕКНОЛОДЖИЗ, ЭлЭлСи|Casing for accumulator battery of traction electric motor for electric vehicles and method for providing impact absorbing casing of accumulator battery for accumulator battery of vehicles |
    RU2742351C2|2016-03-04|2021-02-05|Бродбит Баттериз Ой|Rechargeable sodium cells for high energy density battery use|BE435330A|1932-07-30|
    GB1274211A|1968-04-03|1972-05-17|Atomic Energy Authority Uk|Improvements in or relating to the production of refractory artefacts|
    FR2153134B1|1971-09-20|1974-03-29|Comp Generale Electricite|
    US4279974A|1977-09-02|1981-07-21|Ngk Spark Plug Co., Ltd.|Solid electrolytic material and use thereof|
    DE2811169A1|1978-03-15|1979-09-20|Bbc Brown Boveri & Cie|ELECTROCHEMICAL STORAGE CELL|
    US4190500A|1978-06-19|1980-02-26|E. I. Du Pont De Nemours And Company|Sodium ion conducting sodium aluminum borate glasses|
    DE3032552A1|1980-08-29|1982-04-29|Varta Batterie Ag, 3000 Hannover|METHOD FOR PRODUCING A ELECTROCHEMICAL HIGH TEMPERATURE CELL|
    DE3117384A1|1981-05-02|1982-12-16|Brown, Boveri & Cie Ag, 6800 Mannheim|"ELECTROCHEMICAL STORAGE CELL"|
    US4568502A|1981-09-08|1986-02-04|Ford Motor Company|Process for molding complex beta"-alumina shapes for sodium/sulfur batteries|
    DK156859C|1984-06-20|1990-02-26|Energiforskning Lab|ELECTRIC BATTERY FOR A PRIMARY OR SECONDARY ELECTRIC BATTERY, ELECTRIC BATTERY INCLUDING SUCH ELECTRODS AND PROCEDURES FOR MANUFACTURING SUCH AN ELECTRODE|
    GB8723408D0|1987-10-06|1987-11-11|Lilliwyte Sa|Electrolyte separator|
    GB8828230D0|1988-12-02|1989-01-05|Lilliwyte Sa|Electrochemical cell|CA2041632A1|1990-05-16|1991-11-17|Johan Coetzer|Electrochemical cell|
    CA2042322A1|1990-05-16|1991-11-17|Roger J. Bones|Electrochemical cells|
    GB9011035D0|1990-05-16|1990-07-04|Programme 3 Patent Holdings|Electrochemical cell|
    GB9017284D0|1990-08-07|1990-09-19|Programme 3 Patent Holdings|Electrochemical cell|
    US5283135A|1991-10-10|1994-02-01|University Of Chicago|Electrochemical cell|
    ZA95443B|1994-02-02|1995-08-02|Programme 3 Patent Holdings|Electrochemical cell|
    US5554457A|1995-03-01|1996-09-10|Bugga; Ratnakumar V.|Foil positive electrodes in sodium-nickel chloride batteries|
    GB9512971D0|1995-06-26|1995-08-30|Programme 3 Patent Holdings|Electrochemical cell|
    AU5998598A|1997-02-06|1998-08-26|Aabh Patent Holdings Societe Anonyme|Electrochemical cell|
    JP2001102087A|1999-08-25|2001-04-13|Bi Patent Holding Sa|Electrical-chemical cell separator|
    DE102011001536A1|2011-03-10|2012-09-13|Hagemann-Systems Gmbh|Stacked battery cell spacer plates|
    CN102959760B|2011-04-11|2016-04-27|松下电器产业株式会社|Flexible battery and manufacture method thereof|
    ITMI20120771A1|2012-05-08|2013-11-09|Politec Polimeri Tecnici Sa|TRANSPARENT STRUCTURAL ELEMENT FOR ROOFING|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB898927274A|GB8927274D0|1989-12-01|1989-12-01|Electrode holder|
    [返回顶部]