WO2012031346A1 - Cellule électrochimique bipolaire - Google Patents

Cellule électrochimique bipolaire Download PDF

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Publication number
WO2012031346A1
WO2012031346A1 PCT/CA2010/001355 CA2010001355W WO2012031346A1 WO 2012031346 A1 WO2012031346 A1 WO 2012031346A1 CA 2010001355 W CA2010001355 W CA 2010001355W WO 2012031346 A1 WO2012031346 A1 WO 2012031346A1
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WO
WIPO (PCT)
Prior art keywords
electrochemical cell
cell
cell wall
solid electrolyte
cathode material
Prior art date
Application number
PCT/CA2010/001355
Other languages
English (en)
Inventor
Stephen Nicholas Heavens
Malcolm John Shemmans
Erik Jacobus Spek
Original Assignee
Aloxsys Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aloxsys Inc. filed Critical Aloxsys Inc.
Priority to PCT/CA2010/001355 priority Critical patent/WO2012031346A1/fr
Publication of WO2012031346A1 publication Critical patent/WO2012031346A1/fr

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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
    • H01M10/36—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
    • 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
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members
    • 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
    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/191—Inorganic material
    • 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
    • H01M50/258—Modular batteries; Casings provided with means for assembling
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • H01M50/466—U-shaped, bag-shaped or folded
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/025—Electrodes composed of, or comprising, active material with shapes other than plane or cylindrical
    • 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
    • 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

  • Example embodiments relate generally to the field of electrochemical cells, and in particular to bi-polar electrochemical cells having a solid electrolyte.
  • Some disadvantages which such existing cells have are a high proportion of parts that are not contributors to energy or power production, high probability for quality non-conformance issues due to complexity and processing sensitivities, risk of external short circuit paths emanating from inside the cell through protruding metallic paths, and/or high production cost.
  • Example embodiments generally relate to a modular electrochemical cell including a solid electrolyte and an electrochemical cell stack assembled from same.
  • a modular electrochemical cell for axial assembly with a corresponding electrochemical cell to form a stack, which includes a conductive separating member, a cathode material, a solid electrolyte, and a cell wall sealed around the solid electrolyte.
  • the cell wall is configured to join axially at an interface with a corresponding cell wall of the corresponding electrochemical cell in the stack, the cell wall and corresponding cell wall being dimensioned to surround collectively an entire perimeter of the interface.
  • the cell walls may define an anode compartment when joined.
  • the solid electrolyte may be shaped to include a three-dimensional dome shape having a basal radius and a height dimensioned to be at least the basal radius.
  • Figure 1A shows a perspective view of a bi-polar electrochemical cell stack in accordance with an example embodiment
  • Figure IB shows a side cross-section of the cell stack of Figure 1A
  • Figure 1C shows a perspective section of the cell stack of Figure 1A
  • Figure 2A shows a side cross-section of a cathode unit in accordance with an example embodiment
  • Figure 2B shows an exploded perspective view of the cathode unit of Figure 2A;
  • Figure 3A shows a side cross-section of a sealing unit in accordance with an example embodiment;
  • Figure 3B shows an exploded perspective view of the sealing unit of Figure 3A
  • Figure 4 shows a side cross-section of stacked interior cells, in accordance with an example embodiment
  • Figure 5 shows a side cross-section of an anode end unit in accordance with an example embodiment
  • Figure 6 shows a side cross-section of a cathode end unit in accordance with an example embodiment
  • Figure 7A shows a side view of a sealing unit in accordance with another example embodiment
  • Figure 7B shows a top view of the sealing unit of Figure 7A
  • Figure 7C shows a sectional view of the sealing unit taken along 7C-7C of Figure 7B;
  • Figure 7D shows a perspective view of the sealing unit of Figure 7A.
  • Example embodiments generally relate to a modular electrochemical cell including a solid electrolyte and an electrochemical cell stack assembled from same.
  • modular electrochemical cells can be formed from prefabricated components in an assembly. Further, the cells may be each configured for axially assembling with a corresponding or adjacent cell in a stack. In one aspect of some example embodiments, the cells may be dimensioned to assemble flushly with the adjacent cell to surround an interface between the cells. In another aspect of some example embodiments, the cells may include components which are dome shaped at a curvature or having a height to assist in facilitating structural integrity, power distribution or stacking alignment.
  • an electrochemical cell for axial assembly with a corresponding electrochemical cell to form a stack, which includes a conductive separating member, a cathode material adjoined to the conductive separating member, a solid electrolyte adjoined to the cathode material, and an electrically insulating cell wall sealed around the solid electrolyte.
  • the cell wall is configured to join axially at an interface with a corresponding cell wall of the corresponding electrochemical cell in the stack, the cell wall and corresponding cell wall being dimensioned to surround collectively an entire perimeter of the interface.
  • the solid electrolyte may be shaped to include a three-dimensional dome shape having a basal radius and a height dimensioned to be at least the basal radius.
  • an electrochemical cell which includes a conductive separating member, a cathode material adjoined to the conductive separating member, a solid electrolyte adjoined to the cathode material, the solid electrolyte being shaped to include a three- dimensional dome shape having a basal radius and a height dimensioned to be at least the basal radius, and a cell wall sealed around said solid electrolyte at the basal radius.
  • a method of assembling an electrochemical cell which includes forming a solid cathode material, adjoining said solid cathode material to a conductive separating member, sealing an electrically insulating cell wall around a solid electrolyte, and assembling the conductive separating member to the cell wall to adjoin the solid cathode material to the solid electrolyte.
  • FIGS 1A to 1C show a bi-polar electrochemical cell stack 20 in accordance with an example embodiment.
  • the cell stack 20 includes at least one, or a plurality of, modular interior electrochemical cells 22a, 22b, 22g (each or collectively referred to as 22) which are axially stacked in series.
  • a cathode end unit 24 is assembled at a cathode end of the cell stack 20.
  • An anode end unit 26 is assembled at an anode end of the cell stack 20.
  • the cells 22 are cylindrically symmetrical about a central axis. It can be appreciated that the configuration may be optimized for strength, sealing or cell stacking.
  • each cell 22 may each be formed from prefabricated components in an assembly. Further, each cell may be each configured for axially assembling with a corresponding or adjacent cell in the stack 20. In one aspect of some example embodiments, each cell 22 may be dimensioned to assemble with an adjacent cell to prevent hazardous or unnecessary protruding electrically conductive leads between each of the cells 22. In another aspect of some example embodiments, each cell 22 may include components which are dome shaped at a height or a curvature to assist in facilitating structural integrity, power distribution or stacking alignment.
  • FIG 4 shows a first interior cell 22a and a neighbouring second interior cell 22b axially assembled together in a stack in accordance with an example embodiment.
  • the interior cells 22a, 22b are modular and are of like construction.
  • the interior cells 22a, 22b may each be assembled from prefabricated components in an assembly.
  • a prefabricated cathode unit 44 as shown, may be used in the assembly of the interior cell 22a.
  • a prefabricated sealing unit 46 as shown, may be used in the assembly of the interior cell 22a.
  • the first interior cell 22a includes a conductive separating member 28a which may be formed of an electron- conductive material.
  • the separating member 28a may also be referred to as a cathode backplane or a bipolar plate, as is understood in the art.
  • a cathode material 30a contained within a cathode compartment is axially adjoined to the separating member 28a during assembly.
  • a solid electrolyte 32a which can be a solid electrolyte membrane, may be formed from sodium beta double prime ( ⁇ ") ⁇ alumina, as is understood in the art, is adjoined axially to the cathode material 30a.
  • the cathode compartment is defined as between the separating member 28a and the solid electrolyte 32a.
  • a first cell wall 34a in the form of a shell or sealing ring is sealed around the solid electrolyte 32a, for example, using a glass seal 36a.
  • the cell wall 34a may be formed from a suitable electrical and ionic insulating material, for example alpha (a) - alumina.
  • the cell wall 34a accordingly acts as an insulating housing for the cell 22a (and therefore for the stack 20 of Figure 1A).
  • the particular recipe, elements or materials which form the alpha alumina is understood in the art and not described in detail herein.
  • the cathode material 30a is typically in solid form for assembly but liquefies within the cathode compartment at operating temperature.
  • the cathode compartment is defined between the separating member 28a and the solid electrolyte 32a.
  • the second interior cell 22b includes a separating member 28b, a solid cathode material 30b axially adjoined to the separating member 28b, and a solid electrolyte 32b axially adjoined to the solid cathode material 30b.
  • a second cell wall 34b is sealed around the solid electrolyte 32b using, for example, a glass seal 36b.
  • each cell wall 34a, 34b is generally configured and dimensioned to join axially to each other at an interface 38.
  • the cell walls 34a, 34b are dimensioned to surround collectively an entire perimeter (e.g., a circumference in this example) of the interface 38.
  • anode compartment 42 is defined between the solid electrolyte 32a and the separating member 28b.
  • the anode compartment 42 is evacuated and, on charge, an anode material 40 becomes filled within the anode compartment 42 (as is understood in the art).
  • a simplex or multiplex carbon felt can be included inside the anode compartment 42 for wicking of the anode material 40 (e.g. sodium) in order to ensure complete wetting between the anode material 40 and the electrolyte 32a (independent from the status of charge).
  • the anode material 40 e.g. sodium
  • the interface 38 will now be described in greater detail.
  • the first cell wall 34a overlaps with the second cell wall 34b, wherein cell wall 34a includes a cell wall body 48a, and a flange member 50a which extends there from towards the second cell wall 34b.
  • Second cell wall 34b also includes a cell wall body 48b, and which defines a groove 52b which corresponds to the shape of the flange member 50a.
  • cell walls 34a, 34b interlock to surround collectively the entire circumference at the interface 38.
  • the interface 38 may include a glass seal 39 (as best shown in Figure 3B) with laser sealing or other suitable corrosion resistant material glass or recipes. It can be appreciated that such a configuration assists to prevent or minimize hazardous or unnecessary protruding conductive leads between the cell walls 34a, 34b.
  • cell walls 34a, 34b engage flushly each other at interface 38.
  • the first cell wall 34a defines the groove (not shown) while the second cell wall 34b includes the flange (not shown) for interlocking there between.
  • first cell wall 34a also defines a groove 52a for assembly with another cell (e.g., cathode end unit 24 as shown in Figure IB).
  • Second cell wall 34b also includes a flange member 50b for assembly with yet another cell (e.g. third interior cell 22c as shown in Figure IB).
  • dome shape feature will now be described in greater detail.
  • some other existing conventional cells include a thin flat disc or slightly domed beta alumina solid electrolytes. These were aimed at improvements over the traditional tubular single cells, but many may suffer from the various disadvantages of mechanical weakness and a reduced ability to withstand the stresses occurring during cell charge-discharge cycling (as is understood in the art), and in particular to the changes in pressure between cathode and anode that occur during charge-discharge cycling. For example, in discharge, cations are transferred from an anode chamber, across an electrolyte, to a cathode chamber.
  • the solid electrolyte 32a, solid cathode material 30a, and separating member 28a are each three-dimensional dome shaped.
  • the particular height 57 ( Figure 3A) or curvature may be used to assist in facilitating structural integrity, power distribution or stacking alignment.
  • the cathode material 30a is located on a convex side of the solid electrolyte 32a and the anode compartment 42 is located on a concave side of the solid electrolyte 32a.
  • the anode compartment 42 pressure after assembly is typically low ambient pressure (less than one bar or one bar) or evacuated. This pressure is less than the cathode compartment pressure and creates a differential force with the more positive value on the cathode side under operating conditions.
  • the dome shape having its convex side at the cathode side results in minimum bending stress and a compressive preload in the solid electrolyte 32a.
  • the anode compartment 42 fills with anode material 40, as is understood in the art.
  • An interior of the first cell wall body 48a includes a radially inward protruding lip 54a for sealing with and supporting of the solid electrolyte 32a.
  • the second cell wall body 48b includes a radially inward protruding lip 54b for sealing with and supporting of the solid electrolyte 32b.
  • the dome shape of the solid electrolyte 32a defines a basal radius 56 and a height 57.
  • the height 57 is dimensioned to be at least the basal radius 56.
  • the height 57 is dimensioned to be at least two times the basal radius 56. It is recognized herein that the height 57 can be much larger than the basal radius 56.
  • the non-circular bases, the basal radius 56 can be appreciated as being a length from its center at the base to the periphery.
  • the solid electrolyte 32a includes a radius of curvature at the apex 59 of the solid electrolyte 32a which is at least a same or smaller than the basal radius 56.
  • the radius of curvature is at least two times smaller than said basal radius 56 of said solid electrolyte 32a.
  • the radius of curvature is at least ten times smaller than said basal radius 56.
  • the cell wall 34a may also be shaped to continue generally the dome shape of the solid electrolyte 32a.
  • the flange member 50a may also act as a leg member to continue generally the dome shape to support the solid electrolyte 32a from the lip 54a.
  • the load from the solid electrolyte 32a and thereabove is generally axially distributed to the second cell wall 34b of the second interior cell 22b via the flange member 50a.
  • the dome shape may also assist in stacking.
  • at least a portion 58b of the separating member 28b and the cathode material 30b are shaped to protrude axially beyond the cell wall 34b.
  • an apex of this protrusion assists in axially aligning the second cell wall 34b to a concave side of the first cell wall 34a.
  • This feature may be used in combination with the flange and groove interlocking of the cell walls 34a, 34b.
  • the first cell wall 34a surrounds the at least a portion 58b which is protruding from the second cell wall 34b, when the cell walls 34a, 34b are joined at the interface 38.
  • the three-dimensional dome shape or two-dimensional profile can be shaped as a rounded cone, arch, semicircular, segmental, parabolic, catenary, lancet and/or elliptical.
  • the choice of design and the degree of arching may be suitably determined by practical considerations such as strength, surface area, and ease of stacking. Ease of stacking may be important in order to allow for electrodes whose depth is acceptably uniform from the outer edge to the centre, for operation during charge-discharge cycling.
  • Example embodiments allow for arching of considerable depth, with may result in greatly increased surface area and high strength, with minimal loss of electrode uniformity.
  • the prefabricated cathode unit 44 used to assemble the interior cell 22a will now be described in greater detail.
  • the cathode material 30a may include a porous structure of a metal powder like nickel or/and iron mixed with NaCI and additives and impregnated with the molten salt NaAICI4, or suitable sodium metal chloride.
  • the cathode mass may be formed or moulded in the dome shape of the cathode compartment as shown in Figure 2A. This step typically occurs at a high temperature and/or pressure.
  • the active cathode mass can be produced by pressing a mixture of the suitable components which may include the metal powder of Ni and/or Fe, NaCI, AICI3 and additives in the shape of the cathode compartment as shown in Figure 2A.
  • the cathode unit 44 further includes a plurality of longitudinal current collectors 60 for providing an electrical current pathway, and which are positioned within the cathode mass and axially extend from the separating member 28a.
  • the longitudinal current collectors 60 are shaped as needle-like members which provide an electrical current pathway to the separating member 28a.
  • the separating member 28a provides conductivity as well as serving as the separation between the anode compartment 42 ( Figure 4) and the cathode material 30a.
  • the separating member 28a may be formed of a conductive material which includes nickel or nickel-plated steel which is corrosion resistant against the cathode material 30a and may be metallurgically joined for the junction 62, for example by welding.
  • the multiple current collectors 60 can also be formed of a fibre structured carbon which is connected to the separating member 28a either directly (as shown) or alternatively through an electrically conducting and NaAICI4 chemically resistant layer such as graphite foil 64. It can therefore be appreciated that the cathode unit 44 and the solid cathode material 30a may be preformed prior to stacking, and assembly with the sealing unit 46. It can also be appreciated that the cathode material 30a typically liquefies during operating temperature of the cell 22a (i.e., after assembly).
  • the sealing unit 46 used to assemble the interior cell 22a will now be described in greater detail.
  • the sealing unit 46 may be prefabricated and includes a thin solid electrolyte 32a of ⁇ ''-alumina or other ionically conductive ceramic and a cell wall 34a in the form of an a-alumina sealing ring (or other ceramic) which are sealed together using glass joint 36a.
  • a weld ring 66 is also sealed to ceramic ring 48a by means of a glassed joint 68.
  • the weld ring 66 is glass joined 68 to the cell wall 34a.
  • the glass joints 36a, 68 are joined in a glassing process which may be performed in a single curing or heating step.
  • the prefabricated cathode unit 44 is assembled to the sealing unit 46.
  • the separating member 28a is metaliurgicaliy joined to the weld ring 66 by welding at joint 62, using for example a laser beam.
  • This step may for example be performed at a ambient temperature and/or under vacuum or low pressure. It can be appreciated that this step may avoid manufacturing conditions which require high temperature and/or high pressure, which could cause damage to the cathode material 30a.
  • the anode compartment 42 is evacuated.
  • the dimensions, the radius of curvature, and the support by the a- alumina cell wall 34a are designed to minimize bending stress in the electrolyte 32a so that the electrolyte 32a may have a minimal wall thickness.
  • This minimal wall thickness allows a minimum contribution to cell internal resistance by the ⁇ "- alumina electrolyte.
  • An example wall thickness of the electrolyte 32a is in the order of 0.1 millimetres.
  • the glass joint 36a forms a hermetically leak-tight seal between the ⁇ ''-alumina electrolyte 32a and cell wall 34a. In this configuration, the joint 36a is also exposed to the liquid anode material 40 and the cathode material 30a which has a liquid component, NaAICI4, at operating temperature.
  • the interface 38 may also include a glass seal 39 which during operation is exposed to a liquid anode material 40, for example liquid sodium, at operating temperature.
  • the joints 36a, 36b, 39 and 68 may use different material glass or recipes.
  • FIG. 5 shows an anode end unit 26 in accordance with an example embodiment.
  • the anode end unit 26 includes a cathode unit having the same construction as cathode unit 44 ( Figure 2A) .
  • a sealing unit 73 is similar to sealing unit 46 in Figure 3A, except for the cell wall, wherein the cell wall 72 includes an a-alumina sealing ring and includes a flattened bottom .
  • the cathode unit 44 is metallurgically joined (e.g . welded) via ring 66 and glass joint 68 to the cell wall 72 as described above.
  • An insulating or ceramic end plate 74 (which may be formed of a-alumina) is glass joined to the cell wall 72 using a seal 76, which can be effected by laser, glassing or other suitable joint.
  • the ceramic end plate 74 and the sealing unit 73 define an anode compartment 78 for housing of anode material 80.
  • a positive terminal 82 formed of conductive material provides conductivity between the anode material 80 and external leads (not shown) .
  • the cathode end plate 74 is glass-joined to the cell wall 72 followed by welding of the cathode assembly 44 followed by insertion of the positive terminal 82 (which allows evacuation of the anode compartment 78) .
  • FIG. 6 shows a cathode end unit 24 in accordance with an example embodiment.
  • the cathode end unit 24 includes the same cathode unit 44 ( Figure 2A) and sealing unit 46 ( Figure 3A) .
  • An insulating or ceramic end plate 92 is joined to the cathode unit 44 at seal 96, which can be effected by laser, glassing or other suitable joint.
  • a negative terminal 94 formed of conductive material provides conductivity between the separating member 28a and external leads (not shown) .
  • FIG. 5 the assembly of the cell stack 20 is started with the anode end unit 26, having the ceramic end plate 74 and positive terminal 82.
  • the sealing unit 73 is joined to the ceramic end plate 74 at seal 76.
  • the cathode end unit 44 is then stacked to the sealing unit 73.
  • the assembly is built up from interior cells 22 and repeated for "n" number of pre-determined cells 22.
  • the cathode end unit 24 is assembled at the cathode end of the stack 20.
  • the alignment of the cell stack 20 is facilitated by the shapes and corresponding alignment features of the cell walls 34a, 34b. Accordingly, it can be appreciated that "n" can be a relatively large number because of these features.
  • the cell stack 20 may then be moved into a protective chamber having low and/or ambient pressure with one or more lasers positioned relative to the glass seals 39 at interface 38.
  • this stage of the assembly process may avoid unnecessarily high surrounding temperature and/or pressures.
  • the anode compartment 42 is evacuated.
  • Multiple seals of the interface 38 may then be simultaneously or in a short sequence completed by the laser beams.
  • cement can be applied to each seal at each interface 38 and cured simultaneously.
  • no protruding cell connections are required between individual cells 22 and no voltage potential occurs outside the cell stack 20 except at the positive and negative terminals.
  • the current flows through all cells 22 in the direction of the stack axis which is low resistive because of the large electric contact surface areas in each cell 22. It can be appreciated that the height and curvature of the electrolyte 32a, 32b offers a relatively larger surface area compared to a flat or slightly domed disc, thereby reducing the internal resistance.
  • the cell wall 34a is formed as a unitary component. In other example embodiment, the cell wall 34a is formed from two or more separate parts which are attached or formed together.
  • FIGS 7A to 7D show a sealing unit 100 in accordance with another example embodiment.
  • the sealing unit 100 may for example be assembled with a cathode unit (e.g., cathode unit 44 as shown in Figure 2A), and form a stack with other like units, in a manner similar to those example embodiments as described above.
  • the sealing unit 100 includes a solid electrolyte 102 which includes a wave shape or wave shape surface area.
  • the sealing unit 100 includes a cell wall 104 in the form of a shell or sealing ring which is sealed around the solid electrolyte 102, for example, using a glass seal 106.
  • the cell wall 104 may be formed of electrical and/or ionic insulating material.
  • An anode compartment 110 can contain a simplex or multiplex carbon felt, as described above.
  • the solid electrolyte 102 may include a three-dimensional dome shape, including an apex 108.
  • the solid electrolyte 102 further includes a wave shape or surface area.
  • the wave shape proceeds angularly around the three-dimensional dome shape, with respect to the apex 108.
  • the wave shape may also be periodic, as shown.
  • the wave shape may also have either a constant amplitude (as shown) or have varying amplitudes.
  • the wave shape extends radially outward from the apex 108 of the solid electrolyte 102, similar to a ripple caused by a stone in a puddle.
  • the wave shape of the solid electrolyte 102 increases the amount of electric contact surface area exposed to the cathode material (not shown), and therefore assists in increased power production and distribution during cell cycling.
  • the wave shape yields a larger surface area and can provide lower ionic resistance.
  • the solid electrolyte 102 includes a relatively high angular frequency (low period) when compared to the main curvature of the three-dimensional dome shape. Accordingly, the main curvature primarily provides the structural integrity of the solid electrolyte 102 during cell charge-discharge cycling, especially when the anode compartment 110 ( Figure 7C) or concave side has relatively low pressure.
  • the wave shape of the solid electrolyte 102 may be fluted (as shown), zig-zag, sinusoidal, rippled, corrugated, triangular-wave, etc.
  • suitable materials for the solid electrolyte include sodium beta-alumina, sodium beta"-alumina, and NaSICON and/or conductive glass.
  • suitable materials for the separating member include nickel, nickel-plated steel, and/or chromized steel.
  • suitable materials for the cathode material include NaCI/Fe-Ni, and sulfur materials.
  • example embodiments have been described as being cylindrically symmetrical, it can be appreciated that other cross-sectional shapes may be used in other example embodiments, for example rounded-cornered square or rectangle. Accordingly, reference to "radial” herein can likewise apply to any transverse axis or direction, as would be understood in the art.
  • Example embodiments described herein may simplify the cell design, reduce the number of components to a functional minimum, to apply simplified and reliable ceramic to ceramic, ceramic to metal, and metal to metal joining processes, and to improve the safety of the cell by eliminating voltage carrying parts on the outside of the cell.
  • Example embodiments may provide a strong robust cell assembly that is capable of withstanding the stresses of battery operation and of cell charge-discharge cycling.
  • Example embodiments may further provide for a substantially increased electrolyte/electrode interfacial surface area in a bipolar cell configuration .
  • each cell of the cell stack is formed from sealed and/or interlocking insulating outer cell walls with no exposed metal parts.
  • cell performance may be improved by the use of sharply arched solid electrolyte and bipolar separator plates that result in high surface areas in relation to the volume enclosed.
  • cell reliability may be provided by the use of a mechanically strong design for the solid electrolyte assembly that withstands the varying electrode pressures during charge- discharge cycling.
  • the described cell is orientation agnostic, i .e., it can operate similarly in horizontal or vertical orientations.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne une cellule électrochimique modulaire destinée à être assemblée axialement avec une cellule électrochimique correspondante pour former un empilage, qui comprend un élément conducteur de séparation, un matériau de cathode, un électrolyte solide, et une paroi de cellule scellée autour de l'électrolyte solide. La paroi de cellule est conçue pour se joindre axialement, au niveau d'une interface, à une paroi de cellule correspondante de la cellule électrochimique correspondante dans l'empilage, la paroi de cellule et la paroi de cellule correspondante étant dimensionnées pour entourer collectivement un périmètre entier de l'interface. L'électrolyte solide peut être formé pour avoir une forme de dôme qui possède un rayon basal et une hauteur dimensionnée pour être au moins égale au rayon basal.
PCT/CA2010/001355 2010-09-08 2010-09-08 Cellule électrochimique bipolaire WO2012031346A1 (fr)

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PCT/CA2010/001355 WO2012031346A1 (fr) 2010-09-08 2010-09-08 Cellule électrochimique bipolaire

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US20150017490A1 (en) * 2013-07-09 2015-01-15 Material and Systems Research, Inc. Planar alkali metal-beta battery
DE102015105611A1 (de) 2015-04-13 2016-10-13 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Hochtemperaturakkumulator mit wenigstens einer planaren Zelle
WO2016202556A1 (fr) * 2015-06-17 2016-12-22 Robert Bosch Gmbh Cellule apte à être empilée et module de batterie la comprenant
DE102016105608A1 (de) * 2016-03-24 2017-09-28 Battery Consult Gmbh Elektrochemische Energiespeichervorrichtung
WO2019081367A1 (fr) * 2017-10-23 2019-05-02 Iontech Systems Ag Batterie aux ions alcalins sur la base d'allotropes sélectionnés du soufre et ses procédés de fabrication
WO2023100172A1 (fr) * 2021-12-05 2023-06-08 Frederic Derfler Électrolyseur

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GB726008A (en) * 1952-04-25 1955-03-16 Pertrix Union Gmbh Improvements in or relating to galvanic stack batteries
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150017490A1 (en) * 2013-07-09 2015-01-15 Material and Systems Research, Inc. Planar alkali metal-beta battery
DE102015105611A1 (de) 2015-04-13 2016-10-13 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Hochtemperaturakkumulator mit wenigstens einer planaren Zelle
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WO2016202556A1 (fr) * 2015-06-17 2016-12-22 Robert Bosch Gmbh Cellule apte à être empilée et module de batterie la comprenant
DE102016105608A1 (de) * 2016-03-24 2017-09-28 Battery Consult Gmbh Elektrochemische Energiespeichervorrichtung
WO2019081367A1 (fr) * 2017-10-23 2019-05-02 Iontech Systems Ag Batterie aux ions alcalins sur la base d'allotropes sélectionnés du soufre et ses procédés de fabrication
CN111433950A (zh) * 2017-10-23 2020-07-17 昂泰克系统公司 基于所选择的硫同素异形体的碱离子硫电池及其制造方法
WO2023100172A1 (fr) * 2021-12-05 2023-06-08 Frederic Derfler Électrolyseur

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