WO2013152030A1 - Battery with non-porous alkali metal ion conductive honeycomb structure separator - Google Patents

Battery with non-porous alkali metal ion conductive honeycomb structure separator Download PDF

Info

Publication number
WO2013152030A1
WO2013152030A1 PCT/US2013/035003 US2013035003W WO2013152030A1 WO 2013152030 A1 WO2013152030 A1 WO 2013152030A1 US 2013035003 W US2013035003 W US 2013035003W WO 2013152030 A1 WO2013152030 A1 WO 2013152030A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
cells
negative electrode
electrochemical
rechargeable battery
Prior art date
Application number
PCT/US2013/035003
Other languages
French (fr)
Inventor
Douglas COORS
John Howard Gordon
Original Assignee
Ceramatec, 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 Ceramatec, Inc. filed Critical Ceramatec, Inc.
Priority to EP13773140.2A priority Critical patent/EP2834866A4/en
Priority to JP2015503686A priority patent/JP2015515723A/en
Publication of WO2013152030A1 publication Critical patent/WO2013152030A1/en

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463Separators, membranes or diaphragms characterised by their shape
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/054Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562Solid materials
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/058Construction or manufacture
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46Separators, membranes or diaphragms characterised by their combination with electrodes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00Batteries for particular applications
    • H01M2220/30Batteries in portable systems, e.g. mobile phone, laptop
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates in general to batteries. More particularly, the present invention provides a battery having a non-porous alkali metal ion conductive honeycomb structure separator.
  • Batteries are known devices that are used to store and release electrical energy for a variety of uses. Our society has come to rely on batteries to power a myriad of devices, including computers, cell phones, portable music players, lighting devices, as well as many other electronic components. In order to produce electrical energy, batteries typically convert chemical energy directly into electrical energy. Generally, a single battery includes one or more galvanic cells, wherein each of the cells is made of two half-cells that are electrically isolated except through an external circuit. During discharge, electrochemical reduction occurs at the cell's positive electrode, while electrochemical oxidation occurs at the cell's negative electrode.
  • the positive electrode and the negative electrode in the cell do not physically touch each other, they are generally chemically connected by at least one (or more) ionically conductive and electrically insulative electrolyte(s), which can either be in a solid or a liquid state, or in combination.
  • an external circuit, or a load is connected to a terminal that is connected to the negative electrode and to a terminal that is connected to the positive electrode, the battery drives electrons through the external circuit, while ions migrate through the electrolyte.
  • Batteries can be classified in a variety of manners. For example, batteries that are completely discharged only once are often referred to as primary batteries or primary cells. In contrast, batteries that can be discharged and recharged more than once are often referred to as secondary batteries or secondary cells. The ability of a cell or battery to be charged and discharged multiple times depends on the Faradaic efficiency of each charge and discharge cycle.
  • Batteries comprised of honeycomb structure separators are known in the art.
  • Berkey, et al. in U.S. Pat. No. 6,010,543 and in U.S. Pat. No. 5,916,706 disclose cells arranged in a honeycomb pattern where the separator walls are porous.
  • Lyman in US Patent 5,567,544 discloses separator walls that wet with an electrolyte solution.
  • Stempin, et al. in U.S. Pat. No. 5,554,464 discloses a honeycomb structure with thin, porous, ceramic walls.
  • Kummer in U.S. Patent No. 4,160,068 disclose a honeycomb separator being formed of a material having a porosity in the range which permits ions of electrolyte to flow there through.
  • the honeycomb structure separator offers many advantages.
  • One advantage is providing a strong structure from thin membranes.
  • Another advantage is providing an efficient structure with a large separator surface area which can be fabricated at low cost.
  • the structure can provide a high ratio of separator area to electrode volume.
  • the present invention provides a rechargeable battery.
  • the battery includes a honeycomb separator which defines therein a plurality of cells separated from adjacent cells by thin, non-porous cell walls of the honeycomb separator. The cells extend in parallel, longitudinal directions.
  • the cell walls of the honeycomb separator comprise a substantially non-porous, alkali ion conductive ceramic membrane material.
  • the substantially non-porous, alkali ion conductive ceramic membrane material may comprise a NASICON (Na Super Ion CONducting) type membrane material.
  • the substantially non-porous, alkali ion conductive ceramic membrane material may comprise a LISICON (Li Super Ion CONducting) type membrane material.
  • Other examples of solid alkali ion conductive electrolyte membranes include beta alumina, sodium-conductive glasses, etc.
  • the honeycomb separator may be an extruded, ceramic material.
  • the battery includes a plurality of positive electrodes, each positive electrode being disposed in a respective positive electrode cell of the honeycomb separator.
  • the positive electrodes may be electrically coupled in a positive electrode grid.
  • Each positive electrode cell contains a positive electrode electrochemical material that undergoes electrochemical reduction during battery discharge and electrochemical oxidation during battery charge.
  • the battery further includes a plurality of negative electrodes, each negative electrode being disposed in a respective negative electrode cell of the honeycomb separator.
  • the negative electrodes may be electrically coupled in a negative electrode grid.
  • Each negative electrode cell contains a negative electrode electrochemical material that undergoes electrochemical oxidation during battery discharge and electrochemical reduction during battery charge.
  • the positive and negative electrodes are disposed in the cells of the honeycomb separator such that cells with positive electrodes are adjacent cells with negative electrodes in a checkerboard pattern.
  • the negative electrode electrochemical material may comprise an alkali metal.
  • alkali metals include sodium and lithium, and alloys thereof.
  • the negative electrode electrochemical material may comprise a molten alkali metal.
  • the negative electrode electrochemical material may comprise an alkali metal intercalation material.
  • the intercalation material in the negative electrode comprises alkali metal intercalated with carbon (e.g., graphite, mesoporous carbon, boron-doped diamond, carbon, and/or graphene).
  • the positive electrode electrochemical material may comprise elemental sulfur and at least one solvent selected to at least partially dissolve the elemental sulfur and M 2 S X , wherein M is an alkali metal.
  • the solvent includes an apolar solvent to dissolve the elemental sulfur and a polar solvent to dissolve the M 2 S X .
  • the solvent consists of at least one polar solvent to at least partially dissolve the elemental sulfur and the M 2 S X .
  • the positive electrode electrochemical material may comprise an alkali metal halide and corresponding halogen.
  • alkali metal iodide such as Nal and Lil, and iodine (I 2 )
  • I 2 iodine
  • alkali metal bromide such as NaBr and Ibr, and bromine (Br 2 ).
  • Figure 1 depicts an extruded honeycomb structure separator.
  • Figure 2 depicts a cross-sectional representation of a honeycomb structure separator affixed to an electronically insulative planar base material.
  • Figure 3 depicts a cross-sectional representation of a honeycomb structure separator as shown in Figure 2 in which current collectors are attached to alternating negative electrodes and positive electrodes.
  • Figure 4 depicts a top view of a honeycomb structure separator showing alternating negative electrodes and positive electrodes in adjacent cells forming a checkerboard pattern.
  • Figure 5A depicts a top view of a honeycomb structure separator as shown in Figure 4 with arrows indicating the flow of cations across the cell walls during battery discharge.
  • Figure 5B depicts a top view of a honeycomb structure separator as shown in Figure 4 with arrows indicating the flow of cations across the cell walls during battery charge.
  • Non-limiting examples of the non- porous membrane walls include an alkali ion conductive ceramic material such as NASICON-type material, LISICON-type material, and materials of the garnet structure which are ionically conductive.
  • Berkey, Lyman, Stempin and Kummer noted above all teach away from non-porous membranes.
  • the disclosed prior art systems require a porous honeycomb separator in the case of alkaline chemistries where over charging may lead to gas formation and passage of gas from one side of the membrane to the other to allow recombination is desirable. Otherwise, gases evolved from this reaction could result in an explosion or destruction of the cell.
  • porous membranes are not suitable for many rechargeable battery systems, including systems where dendrite formation during recharge may penetrate through the membrane pores, shorting the cell or the undesirable migration of constituents through a porous separator will result in irreversible loss of cell capacity.
  • non-porous honeycomb separator membranes so that certain rechargeable battery chemistries may be used.
  • the chemistries of the two electrode types are incompatible such as in the case where one of the electrodes is a molten alkali metal, and the opposite electrode is a material that will react with the metal, such as an aqueous electrolyte, then the porous membrane could result in decomposition of one of the electrode materials.
  • the presently disclosed invention captures the advantages of using non-porous membrane separators and advantages of configuring the separators into a honeycomb structure: (1) The unit cost per cell can be much lower with the honeycomb compared to the individual cell because there is less labor and handling of pieces per membrane area; and (2) The overall honeycomb structure is strong and can handle stresses with thin membranes that individual tubes would not.
  • Fabricating rechargeable batteries with a honeycomb structure separator is an effective way to produce a rechargeable battery having a high energy density at sufficiently low cost.
  • Fig. 1 is a non-limiting example of a honeycomb structure separator 20.
  • the honeycomb separator 20 defines a plurality of cells 25 separated from adjacent cells by thin, non-porous cell walls 30 of the honeycomb separator 20. The cells extend in parallel, longitudinal directions 35.
  • the cell walls 30 of the honeycomb separator 20 comprise a substantially non-porous, alkali ion conductive ceramic membrane material.
  • the honeycomb separator may be fabricated using known extrusion processes.
  • the honeycomb separator 20 is formed of a material that is substantially non- porous yet alkali-metal ion conductive.
  • the honeycomb material is resistant to attack by the materials forming the battery.
  • the honeycomb material comprises a NaSICON-type membrane (e.g., a NaSELECT® membrane, produced by Ceramatec, Inc., in Salt Lake City, Utah).
  • the honeycomb material is a LiSICON-type material, such as LiSICON-type materials produced by Ceramatec, Inc.
  • the honeycomb separator may be selective to the transport of alkali ions while being substantially impermeable to water and other electrolyte materials used in the battery.
  • the honeycomb separator structure may be fabricated using known ceramic extrusion processes.
  • the honeycomb structure separator 20 may be attached to an electronically insulative planar base material 40 to facilitate the construction of a multi-cell battery where the cell constituents and electrodes enter from the top.
  • a suitable material for the base is non-porous alumina which may be attached to the extruded membrane material using glass or epoxy bonding.
  • FIG. 5 A depicts a top view of a honeycomb structure separator as shown in Fig. 4 with arrows 80 indicating the flow of alkali metal cations, such as Na + or Li + , across the cell walls during battery discharge.
  • Fig 5B depicts a top view of a honeycomb structure separator as shown in Figure 4 with arrows 85 indicating the flow of alkali metal cations across the cell walls during battery charge.
  • the cations flow from positive electrode cells 65 across cell walls 30 into negative electrode cells 60.
  • the battery may include seals for sealing off the open ends of negative electrode cells 60 and the positive electrode cells 65 to make them fluid tight.
  • the battery may also include vents (not shown) to permit the escape of generated gases therefrom.
  • the battery includes electrically insulative material to electrically insulate the negative electrodes from the positive electrodes.
  • the positive electrode cells contain a positive electrode electrochemical material that undergoes electrochemical reduction during battery discharge and electrochemical oxidation during battery charge.
  • the negative electrode cells contain a negative electrode electrochemical material that undergoes electrochemical oxidation during battery discharge and electrochemical reduction during battery charge.
  • a housing may hold the honeycomb separator, the negative electrodes, the positive electrodes, the seals, the gas vents, the electrically insulative material, the positive and negative electrochemical materials in an assembled condition.
  • the negative electrode cells 60 can comprise any suitable alkali metal negative electrode 50 and/or associated current collector that allows the battery to function (e.g., be discharged and recharged) as intended.
  • the negative electrode may comprise the negative electrode electrochemical material that undergoes electrochemical oxidation during battery discharge and electrochemical reduction during battery charge.
  • suitable negative electrode materials include, but are not limited to, sodium or lithium that is substantially pure and a sodium or lithium alloy comprising any other suitable sodium or lithium-containing negative electrode material. In certain embodiments, however, the negative electrode comprises or consists of either an amount of sodium or an amount of lithium that is substantially pure.
  • the negative electrode 50 comprises an alkali metal intercalation material that allows alkali metal in the negative electrode to be oxidized to form alkali metal ions as the battery is discharged, and that also allows alkali metal ions to be reduced and to intercalate with the intercalation material as the cell is recharged.
  • the intercalation material also comprises a material that causes little to no increase in the resistance of the alkali metal conductive membrane material. In other words, in some embodiments, the intercalation material readily transports alkali metal ions therethrough and has little to no adverse effect on the rate at which alkali metal ions pass from the negative electrode cell to the positive electrode cell (and vice versa).
  • the intercalation material in the negative electrode comprises alkali metal intercalated with carbon (e.g., graphite, mesoporous carbon, boron-doped diamond, carbon, and/or graphene).
  • the negative electrode cell 60 may contain a non-aqueous negative electrolyte solution (or secondary electrolyte).
  • the non-aqueous negative electrolyte solution may comprise any suitable electrolyte that is capable of transporting alkali metal ions, that is chemically compatible with the materials of the negative electrode and the alkali metal ion conductive membrane, and that otherwise allows the cell to function as intended.
  • suitable negative electrolyte solutions comprise organic electrolytes and ionic liquids.
  • the negative electrolyte solution comprises an ionic liquid.
  • the positive electrode cell 65 can comprise any suitable positive electrode 55 and/or associated current collector that allows the battery to be charged and discharged as intended.
  • the positive electrode can comprise virtually any positive electrode material that has been successfully used in a sodium or lithium-based rechargeable battery system.
  • the positive electrode comprises one or more wires, strands of wires, pieces of felt, plates, tubes, meshes, pieces of foam, and/or one or more other suitable positive electrode configurations.
  • the positive electrode can comprise any suitable material that may undergo oxidation- reduction reactions during charge and discharge, in some non-limiting embodiments it comprises elemental sulfur (typically S 8 molecules in solid form).
  • the positive electrode cell may include at least one solvent selected to at least partially dissolve the elemental sulfur and M 2 S X (alkali metal monosulfide and/or polysulfide, where M is an alkali metal such as sodium or lithium).
  • the positive electrode 55 may comprise a nickel foam, nickel hydroxide (Ni(OH) 2 ), nickel oxyhydroxide (NiOOH), sulfur composites, sulfur halides (including sulfuric chloride), carbon, copper, copper iodide, platinum, and/or another suitable material. Furthermore, these materials may coexist or exist in combinations. Indeed, in some embodiments, the positive electrode comprises copper, platinum, or copper iodide.
  • the positive electrode cells 65 may contain a liquid positive electrode solution compatible with the positive electrode material such as liquid electrolyte solutions.
  • the positive electrode solution comprises an alkali metal compound
  • that compound can perform any suitable function, including, without limitation, helping the metal complex (discussed below) become soluble and protecting the alkali metal ion conductive electrolyte membrane from degradation by dissolution.
  • the alkali metal complex can comprise any suitable component, in some embodiments, it comprises an alkali ion and one or more halide ions and/or pseudo-halide ions.
  • one or more solvents may be selected to at least partially dissolve elemental sulfur and/or M 2 S X .
  • the solvents will also ideally have a relatively high boiling point. Because M 2 S X is polar, in certain embodiments, a polar solvent may be selected to at least partially dissolve the M 2 S X . Similarly, because elemental sulfur is apolar, an apolar solvent may be selected to at least partially dissolve the elemental sulfur. Nevertheless, in general, the solvents may include any single solvent or mixture of solvents that are effective to at least partially dissolve elemental sulfur and/or M 2 S X .
  • Tetraglyme (TG) a polar solvent which is useful for dissolving M 2 S X , also significantly partially dissolves sulfur.
  • tetraglyme by itself, or in combination with other polar solvents, may be used exclusively as the solvent or solvents in the positive electrode cell. This characteristic of tetraglyme (and possibly other polar solvents) is not believed to be disclosed in the prior art.
  • tetraglyme is liquid over a wide temperature range, from -30° C to 275° C at 1 atmosphere pressure. The solubility characteristics of tetraglyme are especially beneficial when used with the substantially non- porous membrane walls of the honeycomb separator.
  • solvents that may be used in the positive electrode cell may include tetrahydrafuran (THF) and/or dimethylanaline (DMA).
  • THF tetrahydrafuran
  • DMA dimethylanaline
  • THF tetrahydrafuran
  • DMA dimethylanaline

Abstract

The present invention provides a rechargeable battery. The battery includes a honeycomb separator (20) which defines therein a plurality of cells separated from adjacent cells by thin, non-porous cell walls (30) of a substantially non-porous, alkali ion conductive ceramic membrane material. The battery includes a plurality of positive electrodes (55), each positive electrode (55) being disposed in a respective positive electrode cell (65) of the honeycomb separator (20). Each positive electrode cell (65) contains a positive electrode electrochemical material that undergoes electrochemical reduction during battery discharge and electrochemical oxidation during battery charge. Negative electrodes (50) are disposed in respective negative electrode cells (60) of the honeycomb separator (20). Each negative electrode cell (60) contains a negative electrode electrochemical material that undergoes electrochemical oxidation during battery discharge and electrochemical reduction during battery charge. The positive (55) and negative (50) electrodes are disposed in the cells of the honeycomb separator (20) in a checkerboard pattern.

Description

BATTERY WITH NON-POROUS ALKALI METAL ION CONDUCTIVE HONEYCOMB
STRUCTURE SEPARATOR
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Patent Application No. 61/619,170, filed April 2, 2012, entitled HIGH POWER, LOW TOTAL ENERGY STORAGE BATTERY WITH HONEYCOMB SEPARATOR. This application is also a continuation-in-part of U.S. Patent App. No. 12/725,319, filed March 16, 2010, entitled SODIUM-SULFUR BATTERY WITH A SUBSTANTIALLY NON-POROUS MEMBRANE AND ENHANCED CATHODE UTILIZATION, which claims the benefit of U.S. Provisional Patent Application No. 61/160,621, filed March 16, 2009, titled SODIUM- SULFUR BATTERY WITH A SUBSTANTIALLY NON-POROUS MEMBRANE AND ENHANCED CATHODE UTILIZATION, which is a continuation of U.S. Patent App. No. 12/205,759, filed September 5, 2008, entitled LITHIUM- SULFUR BATTERY WITH A SUBSTANTIALLY NON-POROUS MEMBRANE AND ENHANCED CATHODE UTILIZATION, which claims the benefit of U.S. Provisional Patent Application No. 60/970,178, filed September 5, 2007, titled HIGH RATE LITHIUM- SULFUR BATTERY WITH NON-POROUS CERAMIC SEPARATOR. The foregoing applications are each incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates in general to batteries. More particularly, the present invention provides a battery having a non-porous alkali metal ion conductive honeycomb structure separator.
BACKGROUND OF THE INVENTION
[0003] Batteries are known devices that are used to store and release electrical energy for a variety of uses. Our society has come to rely on batteries to power a myriad of devices, including computers, cell phones, portable music players, lighting devices, as well as many other electronic components. In order to produce electrical energy, batteries typically convert chemical energy directly into electrical energy. Generally, a single battery includes one or more galvanic cells, wherein each of the cells is made of two half-cells that are electrically isolated except through an external circuit. During discharge, electrochemical reduction occurs at the cell's positive electrode, while electrochemical oxidation occurs at the cell's negative electrode. While the positive electrode and the negative electrode in the cell do not physically touch each other, they are generally chemically connected by at least one (or more) ionically conductive and electrically insulative electrolyte(s), which can either be in a solid or a liquid state, or in combination. When an external circuit, or a load, is connected to a terminal that is connected to the negative electrode and to a terminal that is connected to the positive electrode, the battery drives electrons through the external circuit, while ions migrate through the electrolyte.
[0004] Batteries can be classified in a variety of manners. For example, batteries that are completely discharged only once are often referred to as primary batteries or primary cells. In contrast, batteries that can be discharged and recharged more than once are often referred to as secondary batteries or secondary cells. The ability of a cell or battery to be charged and discharged multiple times depends on the Faradaic efficiency of each charge and discharge cycle.
[0005] Batteries comprised of honeycomb structure separators are known in the art. For example, Berkey, et al. in U.S. Pat. No. 6,010,543 and in U.S. Pat. No. 5,916,706 disclose cells arranged in a honeycomb pattern where the separator walls are porous. Lyman in US Patent 5,567,544 discloses separator walls that wet with an electrolyte solution. Stempin, et al. in U.S. Pat. No. 5,554,464 discloses a honeycomb structure with thin, porous, ceramic walls. Kummer in U.S. Patent No. 4,160,068 disclose a honeycomb separator being formed of a material having a porosity in the range which permits ions of electrolyte to flow there through.
[0006] The honeycomb structure separator offers many advantages. One advantage is providing a strong structure from thin membranes. Another advantage is providing an efficient structure with a large separator surface area which can be fabricated at low cost. Also the structure can provide a high ratio of separator area to electrode volume.
[0007] The prior art above recognizes the honeycomb separator structure, but in each case calls for a porous wall structure so that ions may conduct through the non-ceramic electrolyte contained in the pores.
[0008] There is an ongoing need for further advances in battery technology. It would be an improvement in the art to provide a battery having a non-porous alkali metal ion conductive honeycomb structure separator. BRIEF SUMMARY OF THE INVENTION
[0009] The present invention provides a rechargeable battery. The battery includes a honeycomb separator which defines therein a plurality of cells separated from adjacent cells by thin, non-porous cell walls of the honeycomb separator. The cells extend in parallel, longitudinal directions. The cell walls of the honeycomb separator comprise a substantially non-porous, alkali ion conductive ceramic membrane material. The substantially non-porous, alkali ion conductive ceramic membrane material may comprise a NASICON (Na Super Ion CONducting) type membrane material. The substantially non-porous, alkali ion conductive ceramic membrane material may comprise a LISICON (Li Super Ion CONducting) type membrane material. Other examples of solid alkali ion conductive electrolyte membranes include beta alumina, sodium-conductive glasses, etc. The honeycomb separator may be an extruded, ceramic material.
[0010] The battery includes a plurality of positive electrodes, each positive electrode being disposed in a respective positive electrode cell of the honeycomb separator. The positive electrodes may be electrically coupled in a positive electrode grid. Each positive electrode cell contains a positive electrode electrochemical material that undergoes electrochemical reduction during battery discharge and electrochemical oxidation during battery charge.
[0011] The battery further includes a plurality of negative electrodes, each negative electrode being disposed in a respective negative electrode cell of the honeycomb separator. The negative electrodes may be electrically coupled in a negative electrode grid. Each negative electrode cell contains a negative electrode electrochemical material that undergoes electrochemical oxidation during battery discharge and electrochemical reduction during battery charge.
[0012] The positive and negative electrodes are disposed in the cells of the honeycomb separator such that cells with positive electrodes are adjacent cells with negative electrodes in a checkerboard pattern.
[0013] In operation, the negative electrode electrochemical material may comprise an alkali metal. Non-limiting examples of alkali metals include sodium and lithium, and alloys thereof. In some embodiments, the negative electrode electrochemical material may comprise a molten alkali metal.
[0014] In operation, the negative electrode electrochemical material may comprise an alkali metal intercalation material. In some non-limiting embodiments, the intercalation material in the negative electrode comprises alkali metal intercalated with carbon (e.g., graphite, mesoporous carbon, boron-doped diamond, carbon, and/or graphene).
[0015] In operation, the positive electrode electrochemical material may comprise elemental sulfur and at least one solvent selected to at least partially dissolve the elemental sulfur and M2SX, wherein M is an alkali metal. In certain embodiments, the solvent includes an apolar solvent to dissolve the elemental sulfur and a polar solvent to dissolve the M2SX. In certain embodiments, the solvent consists of at least one polar solvent to at least partially dissolve the elemental sulfur and the M2SX.
[0016] In other embodiments, the positive electrode electrochemical material may comprise an alkali metal halide and corresponding halogen. Non-limiting examples include an alkali metal iodide, such as Nal and Lil, and iodine (I2), and an alkali metal bromide, such as NaBr and Ibr, and bromine (Br2).
[0017] These features and advantages of the present invention will become more fully apparent from the following description and appended claims, or may be learned by the practice of the invention as set forth hereinafter.
BRIEF DESCRIPTION OF THE SEVERAL DRAWINGS
[0018] In order that the manner in which the above-recited and other features and advantages of the invention are obtained and will be readily understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. Understanding that the drawings are not made to scale, depict only some representative embodiments of the invention, and are not therefore to be considered to be limiting of its scope, the invention will be described and explained with additional specificity and detail through the use of the accompanying drawings in which:
[0019] Figure 1 depicts an extruded honeycomb structure separator.
[0020] Figure 2 depicts a cross-sectional representation of a honeycomb structure separator affixed to an electronically insulative planar base material.
[0021] Figure 3 depicts a cross-sectional representation of a honeycomb structure separator as shown in Figure 2 in which current collectors are attached to alternating negative electrodes and positive electrodes.
[0022] Figure 4 depicts a top view of a honeycomb structure separator showing alternating negative electrodes and positive electrodes in adjacent cells forming a checkerboard pattern. [0023] Figure 5A depicts a top view of a honeycomb structure separator as shown in Figure 4 with arrows indicating the flow of cations across the cell walls during battery discharge.
[0024] Figure 5B depicts a top view of a honeycomb structure separator as shown in Figure 4 with arrows indicating the flow of cations across the cell walls during battery charge.
DETAILED DESCRIPTION OF THE INVENTION
[0025] Reference throughout this specification to "one embodiment," "an embodiment," or similar language means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases "in one embodiment," "in an embodiment," and similar language throughout this specification may, but do not necessarily, all refer to the same embodiment. Additionally, while the following description refers to several embodiments and examples of the various components and aspects of the described invention, all of the described embodiments and examples are to be considered, in all respects, as illustrative only and not as being limiting in any manner.
[0026] Furthermore, the described features, structures, or characteristics of the invention may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are provided, such as examples of suitable alkali metal negative electrodes, positive electrode materials, liquid positive electrolyte solutions, non- porous alkali metal ion conductive membrane, etc., to provide a thorough understanding of embodiments of the invention. One having ordinary skill in the relevant art will recognize, however, that the invention may be practiced without one or more of the specific details, or with other methods, components, materials, and so forth. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the invention.
[0027] As stated above, secondary cells can be discharged and recharged and this specification describes cell arrangements and methods for both states. Although the term "recharging" in its various forms implies a second charging, one of skill in the art will understand that discussions regarding recharging would be valid for, and applicable to, the first or initial charge, and vice versa. Thus, for the purposes of this specification, the terms "recharge," "recharged" and "rechargeable" shall be interchangeable with the terms "charge," "charged" and "chargeable" respectively. [0028] The present invention provides a rechargeable battery utilizing a non-porous membrane wall in a honeycomb structure separator. Non-limiting examples of the non- porous membrane walls include an alkali ion conductive ceramic material such as NASICON-type material, LISICON-type material, and materials of the garnet structure which are ionically conductive. Berkey, Lyman, Stempin and Kummer noted above all teach away from non-porous membranes. The disclosed prior art systems require a porous honeycomb separator in the case of alkaline chemistries where over charging may lead to gas formation and passage of gas from one side of the membrane to the other to allow recombination is desirable. Otherwise, gases evolved from this reaction could result in an explosion or destruction of the cell. Furthermore, porous membranes are not suitable for many rechargeable battery systems, including systems where dendrite formation during recharge may penetrate through the membrane pores, shorting the cell or the undesirable migration of constituents through a porous separator will result in irreversible loss of cell capacity.
[0029] It would be a significant advancement in the art to provide non-porous honeycomb separator membranes so that certain rechargeable battery chemistries may be used. For example, if the chemistries of the two electrode types are incompatible such as in the case where one of the electrodes is a molten alkali metal, and the opposite electrode is a material that will react with the metal, such as an aqueous electrolyte, then the porous membrane could result in decomposition of one of the electrode materials.
[0030] The presently disclosed invention captures the advantages of using non-porous membrane separators and advantages of configuring the separators into a honeycomb structure: (1) The unit cost per cell can be much lower with the honeycomb compared to the individual cell because there is less labor and handling of pieces per membrane area; and (2) The overall honeycomb structure is strong and can handle stresses with thin membranes that individual tubes would not.
[0031] Fabricating rechargeable batteries with a honeycomb structure separator is an effective way to produce a rechargeable battery having a high energy density at sufficiently low cost.
[0032] Fig. 1 is a non-limiting example of a honeycomb structure separator 20. The honeycomb separator 20 defines a plurality of cells 25 separated from adjacent cells by thin, non-porous cell walls 30 of the honeycomb separator 20. The cells extend in parallel, longitudinal directions 35. The cell walls 30 of the honeycomb separator 20 comprise a substantially non-porous, alkali ion conductive ceramic membrane material. The honeycomb separator may be fabricated using known extrusion processes.
[0033] The honeycomb separator 20 is formed of a material that is substantially non- porous yet alkali-metal ion conductive. The honeycomb material is resistant to attack by the materials forming the battery. Indeed, in some non-limiting implementations, the honeycomb material comprises a NaSICON-type membrane (e.g., a NaSELECT® membrane, produced by Ceramatec, Inc., in Salt Lake City, Utah). In another embodiment the honeycomb material is a LiSICON-type material, such as LiSICON-type materials produced by Ceramatec, Inc. The honeycomb separator may be selective to the transport of alkali ions while being substantially impermeable to water and other electrolyte materials used in the battery. The honeycomb separator structure may be fabricated using known ceramic extrusion processes.
[0034] As shown in Fig. 2, the honeycomb structure separator 20 may be attached to an electronically insulative planar base material 40 to facilitate the construction of a multi-cell battery where the cell constituents and electrodes enter from the top. A suitable material for the base is non-porous alumina which may be attached to the extruded membrane material using glass or epoxy bonding.
[0035] Current collectors can be attached effectively to alternating negative electrodes 50 and positive electrodes 55 as shown Fig. 3. Negative electrodes 50 are disposed in negative electrode cells 60. Positive electrodes 55 are disposed in positive electrode cells 65. Negative electrode cells 60 are preferably disposed adjacent negative electrode cells 65 in a checkerboard pattern, as shown in Fig. 4. Each of the cells with negative electrodes 50 may be electrically connected in a negative electrode grid 70. Each of the cells with positive electrodes 55 may be electrically connected in a positive electrode grid 75. Fig. 5 A depicts a top view of a honeycomb structure separator as shown in Fig. 4 with arrows 80 indicating the flow of alkali metal cations, such as Na+ or Li+, across the cell walls during battery discharge. The cations flow from negative electrode cells 60 across cell walls 30 into positive electrode cells 65. Fig 5B depicts a top view of a honeycomb structure separator as shown in Figure 4 with arrows 85 indicating the flow of alkali metal cations across the cell walls during battery charge. The cations flow from positive electrode cells 65 across cell walls 30 into negative electrode cells 60.
[0036] The battery may include seals for sealing off the open ends of negative electrode cells 60 and the positive electrode cells 65 to make them fluid tight. The battery may also include vents (not shown) to permit the escape of generated gases therefrom. In one embodiment, the battery includes electrically insulative material to electrically insulate the negative electrodes from the positive electrodes.
[0037] The positive electrode cells contain a positive electrode electrochemical material that undergoes electrochemical reduction during battery discharge and electrochemical oxidation during battery charge. The negative electrode cells contain a negative electrode electrochemical material that undergoes electrochemical oxidation during battery discharge and electrochemical reduction during battery charge. A housing may hold the honeycomb separator, the negative electrodes, the positive electrodes, the seals, the gas vents, the electrically insulative material, the positive and negative electrochemical materials in an assembled condition.
[0038] With respect to the negative electrode 50, the negative electrode cells 60 can comprise any suitable alkali metal negative electrode 50 and/or associated current collector that allows the battery to function (e.g., be discharged and recharged) as intended. In some non-limiting embodiments, the negative electrode may comprise the negative electrode electrochemical material that undergoes electrochemical oxidation during battery discharge and electrochemical reduction during battery charge. Some non-limiting examples of suitable negative electrode materials include, but are not limited to, sodium or lithium that is substantially pure and a sodium or lithium alloy comprising any other suitable sodium or lithium-containing negative electrode material. In certain embodiments, however, the negative electrode comprises or consists of either an amount of sodium or an amount of lithium that is substantially pure.
[0039] In some embodiments, the negative electrode 50 comprises an alkali metal intercalation material that allows alkali metal in the negative electrode to be oxidized to form alkali metal ions as the battery is discharged, and that also allows alkali metal ions to be reduced and to intercalate with the intercalation material as the cell is recharged. In some embodiments, the intercalation material also comprises a material that causes little to no increase in the resistance of the alkali metal conductive membrane material. In other words, in some embodiments, the intercalation material readily transports alkali metal ions therethrough and has little to no adverse effect on the rate at which alkali metal ions pass from the negative electrode cell to the positive electrode cell (and vice versa). In some embodiments, the intercalation material in the negative electrode comprises alkali metal intercalated with carbon (e.g., graphite, mesoporous carbon, boron-doped diamond, carbon, and/or graphene). [0040] For low temperature battery operation, the negative electrode cell 60 may contain a non-aqueous negative electrolyte solution (or secondary electrolyte). The non-aqueous negative electrolyte solution may comprise any suitable electrolyte that is capable of transporting alkali metal ions, that is chemically compatible with the materials of the negative electrode and the alkali metal ion conductive membrane, and that otherwise allows the cell to function as intended. Some non-limiting examples of suitable negative electrolyte solutions comprise organic electrolytes and ionic liquids. However, it is theorized that because certain ionic liquids have a higher ionic conductivity than the sodium ion conductive membrane and/or because some ionic liquids can act as a surfactant, such ionic liquids may impede dendrite formation on the negative electrode better than some organic electrolytes. Accordingly, in some non-limiting implementations, the negative electrolyte solution comprises an ionic liquid.
[0041] With respect to the positive electrode 55, the positive electrode cell 65 can comprise any suitable positive electrode 55 and/or associated current collector that allows the battery to be charged and discharged as intended. For instance, the positive electrode can comprise virtually any positive electrode material that has been successfully used in a sodium or lithium-based rechargeable battery system. In some embodiments, the positive electrode comprises one or more wires, strands of wires, pieces of felt, plates, tubes, meshes, pieces of foam, and/or one or more other suitable positive electrode configurations. Additionally, while the positive electrode can comprise any suitable material that may undergo oxidation- reduction reactions during charge and discharge, in some non-limiting embodiments it comprises elemental sulfur (typically S8 molecules in solid form). The positive electrode cell may include at least one solvent selected to at least partially dissolve the elemental sulfur and M2SX (alkali metal monosulfide and/or polysulfide, where M is an alkali metal such as sodium or lithium).
[0042] In other embodiments, the positive electrode 55 may comprise a nickel foam, nickel hydroxide (Ni(OH)2), nickel oxyhydroxide (NiOOH), sulfur composites, sulfur halides (including sulfuric chloride), carbon, copper, copper iodide, platinum, and/or another suitable material. Furthermore, these materials may coexist or exist in combinations. Indeed, in some embodiments, the positive electrode comprises copper, platinum, or copper iodide.
[0043] The positive electrode cells 65 may contain a liquid positive electrode solution compatible with the positive electrode material such as liquid electrolyte solutions. Where the positive electrode solution comprises an alkali metal compound, that compound can perform any suitable function, including, without limitation, helping the metal complex (discussed below) become soluble and protecting the alkali metal ion conductive electrolyte membrane from degradation by dissolution. While the alkali metal complex can comprise any suitable component, in some embodiments, it comprises an alkali ion and one or more halide ions and/or pseudo-halide ions.
[0044] In certain embodiments, one or more solvents may be selected to at least partially dissolve elemental sulfur and/or M2SX. The solvents will also ideally have a relatively high boiling point. Because M2SX is polar, in certain embodiments, a polar solvent may be selected to at least partially dissolve the M2SX. Similarly, because elemental sulfur is apolar, an apolar solvent may be selected to at least partially dissolve the elemental sulfur. Nevertheless, in general, the solvents may include any single solvent or mixture of solvents that are effective to at least partially dissolve elemental sulfur and/or M2SX.
[0045] Tetraglyme (TG), a polar solvent which is useful for dissolving M2SX, also significantly partially dissolves sulfur. Thus, tetraglyme by itself, or in combination with other polar solvents, may be used exclusively as the solvent or solvents in the positive electrode cell. This characteristic of tetraglyme (and possibly other polar solvents) is not believed to be disclosed in the prior art. In addition, tetraglyme is liquid over a wide temperature range, from -30° C to 275° C at 1 atmosphere pressure. The solubility characteristics of tetraglyme are especially beneficial when used with the substantially non- porous membrane walls of the honeycomb separator. Other solvents that may be used in the positive electrode cell may include tetrahydrafuran (THF) and/or dimethylanaline (DMA). DMA is apolar and has been found to be particularly effective at dissolving elemental sulfur, while also having a relatively high boiling point.
[0046] While specific embodiments and examples of the present invention have been illustrated and described, numerous modifications come to mind without significantly departing from the spirit of the invention, and the scope of protection is only limited by the scope of the accompanying claims.

Claims

CLAIMS:
1. A rechargeable battery comprising:
a honeycomb separator defining a plurality of cells separated from adjacent cells by thin, non-porous cell walls of the honeycomb separator, wherein the cells extend in parallel, longitudinal directions, wherein the cell walls of the honeycomb separator comprise a substantially non-porous, alkali ion conductive ceramic membrane material;
a plurality of positive electrodes, each positive electrode being disposed in a respective positive electrode cell of the honeycomb separator, the positive electrodes being electrically coupled in a positive electrode grid, each positive electrode cell contains a positive electrode electrochemical material that undergoes electrochemical reduction during battery discharge and electrochemical oxidation during battery charge;
a plurality of negative electrodes, each negative electrode being disposed in a respective negative electrode cell of the honeycomb separator, the negative electrodes being electrically coupled in a negative electrode grid, each negative electrode cell contains a negative electrode electrochemical material that undergoes electrochemical oxidation during battery discharge and electrochemical reduction during battery charge; and
wherein the positive and negative electrodes are disposed in the cells of the honeycomb separator such that the positive electrode cells are adjacent the negative electrode cells in a checkerboard pattern.
2. The rechargeable battery of claim 1, wherein the substantially non-porous, alkali ion conductive ceramic membrane is a NASICON-type membrane.
3. The rechargeable battery of claim 1, wherein the substantially non-porous, alkali ion conductive ceramic membrane is a LISICON-type membrane.
4. The rechargeable battery of claim 1, wherein the honeycomb separator is an extruded, ceramic material.
5. The rechargeable battery of claim 1, wherein the negative electrode electrochemical material comprises an alkali metal.
6. The rechargeable battery of claim 1, wherein the negative electrode electrochemical material comprises a molten alkali metal.
7. The rechargeable battery of claim 1, wherein the negative electrode electrochemical material comprises an alkali metal intercalation material.
8. The rechargeable battery of claim 1, wherein the alkali metal intercalation material comprises the alkali metal intercalated with carbon.
9. The rechargeable battery of claim 1, wherein the positive electrode electrochemical material comprises elemental sulfur and at least one solvent selected to at least partially dissolve the elemental sulfur and M2SX, wherein M is an alkali metal.
10. The rechargeable battery of claim 9, wherein the at least one solvent includes an apolar solvent to dissolve the elemental sulfur and a polar solvent to dissolve the M2SX.
11. The rechargeable battery of claim 9, wherein the at least one solvent consists of at least one polar solvent to at least partially dissolve the elemental sulfur and the M2SX.
12. The rechargeable battery of claim 1, wherein the positive electrode electrochemical material comprises an alkali metal halide and corresponding halogen.
13. The rechargeable battery of claim 1, wherein the positive electrode electrochemical material comprises an alkali metal iodide and iodine (I2).
14. The rechargeable battery of claim 1, wherein the positive electrode electrochemical material comprises an alkali metal bromide and bromine (Br2).
15. A rechargeable battery comprising:
an extruded ceramic honeycomb separator defining a plurality of cells separated from adjacent cells by thin, non-porous cell walls, wherein the cells extend in parallel, longitudinal directions, wherein the cell walls comprise a substantially non-porous, sodium ion conductive NASICON-type membrane material;
a plurality of positive electrodes, each positive electrode being disposed in a respective positive electrode cell of the honeycomb separator, the positive electrodes being electrically coupled in a positive electrode grid, each positive electrode cell contains a positive electrode electrochemical material that undergoes electrochemical reduction during battery discharge and electrochemical oxidation during battery charge;
a plurality of negative electrodes, each negative electrode being disposed in a respective negative electrode cell of the honeycomb separator, the negative electrodes being electrically coupled in a negative electrode grid, each negative electrode cell contains a negative electrode electrochemical material comprising sodium that undergoes
electrochemical oxidation during battery discharge and electrochemical reduction during battery charge; and
wherein the positive and negative electrodes are disposed in the cells of the honeycomb separator such that the positive electrode cells are adjacent the negative electrode cells in a checkerboard pattern.
16. The rechargeable battery of claim 15, wherein the positive electrode electrochemical material comprises elemental sulfur and at least one solvent selected to at least partially dissolve the elemental sulfur and Na2Sx.
17. The rechargeable battery of claim 15, wherein the positive electrode electrochemical material comprises a sodium halide and corresponding halogen.
18. A rechargeable battery comprising:
an extruded ceramic honeycomb separator defining a plurality of cells separated from adjacent cells by thin, non-porous cell walls, wherein the cells extend in parallel, longitudinal directions, wherein the cell walls comprise a substantially non-porous, lithium ion conductive LISICON-type membrane material;
a plurality of positive electrodes, each positive electrode being disposed in a respective positive electrode cell of the honeycomb separator, the positive electrodes being electrically coupled in a positive electrode grid, each positive electrode cell contains a positive electrode electrochemical material that undergoes electrochemical reduction during battery discharge and electrochemical oxidation during battery charge;
a plurality of negative electrodes, each negative electrode being disposed in a respective negative electrode cell of the honeycomb separator, the negative electrodes being electrically coupled in a negative electrode grid, each negative electrode cell contains a negative electrode electrochemical material comprising lithium that undergoes
electrochemical oxidation during battery discharge and electrochemical reduction during battery charge; and
wherein the positive and negative electrodes are disposed in the cells of the honeycomb separator such that the positive electrode cells are adjacent the negative electrode cells in a checkerboard pattern.
19. The rechargeable battery of claim 18, wherein the positive electrode electrochemical material comprises elemental sulfur and at least one solvent selected to at least partially dissolve the elemental sulfur and Li2Sx.
20. The rechargeable battery of claim 18, wherein the positive electrode electrochemical material comprises a lithium halide and corresponding halogen.
PCT/US2013/035003 2012-04-02 2013-04-02 Battery with non-porous alkali metal ion conductive honeycomb structure separator WO2013152030A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP13773140.2A EP2834866A4 (en) 2012-04-02 2013-04-02 Battery with non-porous alkali metal ion conductive honeycomb structure separator
JP2015503686A JP2015515723A (en) 2012-04-02 2013-04-02 Batteries having non-polar alkali metal ion conducting honeycomb structure separator

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261619170P 2012-04-02 2012-04-02
US61/619,170 2012-04-02

Publications (1)

Publication Number Publication Date
WO2013152030A1 true WO2013152030A1 (en) 2013-10-10

Family

ID=49300991

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2013/035003 WO2013152030A1 (en) 2012-04-02 2013-04-02 Battery with non-porous alkali metal ion conductive honeycomb structure separator

Country Status (3)

Country Link
EP (1) EP2834866A4 (en)
JP (1) JP2015515723A (en)
WO (1) WO2013152030A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016142087A1 (en) * 2015-03-11 2016-09-15 Robert Bosch Gmbh Separator for a battery cell
JP2016201199A (en) * 2015-04-08 2016-12-01 日本碍子株式会社 Secondary battery using hydroxide ion conductivity ceramics separator
CN107864687A (en) * 2015-06-18 2018-03-30 南加利福尼亚大学 Mixing the conductive membranes of lithium ion improves lithium-sulfur cell and the performance of other energy storage devices
US10230088B1 (en) 2015-01-30 2019-03-12 Johnson Controls Technology Company Battery electrode assembly, separator and method of making same
US10847833B2 (en) 2015-05-21 2020-11-24 Sion Power Corporation Glass-ceramic electrolytes for lithium-sulfur batteries

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6631568B2 (en) * 2017-03-13 2020-01-15 株式会社豊田中央研究所 Secondary battery and method of manufacturing the same
WO2018168286A1 (en) * 2017-03-13 2018-09-20 株式会社豊田中央研究所 Secondary battery and method for producing same
JP7081516B2 (en) * 2019-01-31 2022-06-07 トヨタ自動車株式会社 Secondary battery
US20230261259A1 (en) * 2020-06-29 2023-08-17 Tohoku University Electrolyte, secondary cell, and composite material
JP7327302B2 (en) 2020-07-06 2023-08-16 トヨタ自動車株式会社 BATTERY AND MANUFACTURING METHOD THEREOF

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4160068A (en) * 1978-11-21 1979-07-03 Ford Motor Company Storage battery
US20060141346A1 (en) * 2004-11-23 2006-06-29 Gordon John H Solid electrolyte thermoelectrochemical system
WO2008027050A1 (en) * 2006-08-29 2008-03-06 Tsang Floris Y Lithium battery
US20090061288A1 (en) * 2007-09-05 2009-03-05 John Howard Gordon Lithium-sulfur battery with a substantially non-pourous membrane and enhanced cathode utilization
US20090134842A1 (en) * 2007-11-26 2009-05-28 Joshi Ashok V Nickel-Metal Hydride Battery Using Alkali Ion Conducting Separator
US20100239893A1 (en) * 2007-09-05 2010-09-23 John Howard Gordon Sodium-sulfur battery with a substantially non-porous membrane and enhanced cathode utilization

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0769822A1 (en) * 1995-10-11 1997-04-23 Corning Incorporated Honeycomb battery structure
US6428935B1 (en) * 1998-11-10 2002-08-06 Matsushita Electric Industrial Co., Ltd. Lithium secondary battery
FR2880197B1 (en) * 2004-12-23 2007-02-02 Commissariat Energie Atomique ELECTROLYTE STRUCTURE FOR MICROBATTERY
WO2007075867A2 (en) * 2005-12-19 2007-07-05 Polyplus Battery Company Composite solid electrolyte for protection of active metal anodes
US20090189567A1 (en) * 2008-01-30 2009-07-30 Joshi Ashok V Zinc Anode Battery Using Alkali Ion Conducting Separator

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4160068A (en) * 1978-11-21 1979-07-03 Ford Motor Company Storage battery
US20060141346A1 (en) * 2004-11-23 2006-06-29 Gordon John H Solid electrolyte thermoelectrochemical system
WO2008027050A1 (en) * 2006-08-29 2008-03-06 Tsang Floris Y Lithium battery
US20090061288A1 (en) * 2007-09-05 2009-03-05 John Howard Gordon Lithium-sulfur battery with a substantially non-pourous membrane and enhanced cathode utilization
US20100239893A1 (en) * 2007-09-05 2010-09-23 John Howard Gordon Sodium-sulfur battery with a substantially non-porous membrane and enhanced cathode utilization
US20090134842A1 (en) * 2007-11-26 2009-05-28 Joshi Ashok V Nickel-Metal Hydride Battery Using Alkali Ion Conducting Separator

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2834866A4 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10230088B1 (en) 2015-01-30 2019-03-12 Johnson Controls Technology Company Battery electrode assembly, separator and method of making same
WO2016142087A1 (en) * 2015-03-11 2016-09-15 Robert Bosch Gmbh Separator for a battery cell
JP2016201199A (en) * 2015-04-08 2016-12-01 日本碍子株式会社 Secondary battery using hydroxide ion conductivity ceramics separator
US10847833B2 (en) 2015-05-21 2020-11-24 Sion Power Corporation Glass-ceramic electrolytes for lithium-sulfur batteries
CN107864687A (en) * 2015-06-18 2018-03-30 南加利福尼亚大学 Mixing the conductive membranes of lithium ion improves lithium-sulfur cell and the performance of other energy storage devices
EP3311441A4 (en) * 2015-06-18 2019-06-26 University of Southern California Lithium-ion mixed conductor membrane improves the performance of lithium-sulfur battery and other energy storage devices
US11114688B2 (en) 2015-06-18 2021-09-07 University Of Southern California Lithium-ion mixed conductor membrane improves the performance of lithium-sulfur battery and other energy storage devices

Also Published As

Publication number Publication date
EP2834866A4 (en) 2016-01-20
EP2834866A1 (en) 2015-02-11
JP2015515723A (en) 2015-05-28

Similar Documents

Publication Publication Date Title
US20130244085A1 (en) Battery with non-porous alkali metal ion conductive honeycomb structure separator
WO2013152030A1 (en) Battery with non-porous alkali metal ion conductive honeycomb structure separator
Besenhard Handbook of battery materials
US8968902B2 (en) Low temperature molten sodium secondary cell with sodium ion conductive electrolyte membrane
EP2893590B1 (en) Sodium-halogen secondary cell
JP6570995B2 (en) All-solid metal-metal battery
US10056651B2 (en) Low temperature secondary cell with sodium intercalation electrode
US10020543B2 (en) Low temperature battery with molten sodium-FSA electrolyte
US9748544B2 (en) Separator for alkali metal ion battery
CA2902908C (en) Low temperature battery with molten sodium-fsa electrolyte
JP2016122650A5 (en)
WO2017160529A1 (en) Alkali-metal batteries with a dendrite-free anode interfacing an organic liquid electrolyte
EP2973838B1 (en) Low temperature secondary cell with sodium intercalation electrode
EP3050153B1 (en) Intermediate temperature sodium-metal halide battery
WO2022052119A1 (en) Composite solid-state electrolyte, battery, and electronic device
US10854929B2 (en) Sodium-halogen secondary cell
US20140030571A1 (en) Battery charge transfer mechanisms
KR102213399B1 (en) Battery charge transfer mechanisms
EP3227951B1 (en) Sodium-halogen secondary cell
WO2018094464A1 (en) Lithium-sulfur energy storage cell and hybrid cell having capacitive energy storage and discharge capability

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13773140

Country of ref document: EP

Kind code of ref document: A1

REEP Request for entry into the european phase

Ref document number: 2013773140

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2013773140

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2015503686

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE