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WO1998026466A1 - Electrolyte polymere polybenzimidazol sublime et cellule electrochimique dans laquelle il est utilise - Google Patents

Electrolyte polymere polybenzimidazol sublime et cellule electrochimique dans laquelle il est utilise Download PDF

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Publication number
WO1998026466A1
WO1998026466A1 PCT/US1997/022175 US9722175W WO9826466A1 WO 1998026466 A1 WO1998026466 A1 WO 1998026466A1 US 9722175 W US9722175 W US 9722175W WO 9826466 A1 WO9826466 A1 WO 9826466A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrochemical cell
electrodes
electrochemical
electrolyte
polybenzimidazole
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US1997/022175
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English (en)
Inventor
Changming Li
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Motorola Solutions Inc
Original Assignee
Motorola 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 Motorola Inc filed Critical Motorola Inc
Publication of WO1998026466A1 publication Critical patent/WO1998026466A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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

Definitions

  • This invention relates in general to electrochemical cells, and more particularly to electrochemical cells having a polymer electrolyte comprising a polymeric matrix or support structure and an electrolyte active species dispersed therein.
  • aqueous liquid electrolytes have problems associated with sealing, packaging, and electrolyte leakage, all of which are well known in the industry.
  • Solid polymer electrolytes were developed by numerous different companies in an effort to address the problems associated with liquid aqueous electrolytes. Each of these different types of solid polymer electrolyte systems have met with varying degrees of success, typically owing to the fact that ionic conductivity is generally not as good as that found in a liquid aqueous system. Solid polymer electrolytes alleviate the problems experienced with respect to packaging and electrolyte leakage.
  • the mechanical strength of thin films of PVA based polymer electrolytes also needs further improvement for eliminating shorts during the assembly process.
  • the frequency response of certain polymer electrolyte based electrochemical capacitor devices is relatively narrow in comparison to dielectric capacitors. This performance differential may be partially improved by developing polymer electrolytes which have higher ionic conductivity.
  • a second polymer electrolyte which has received some interest is polybenzimidazole (“PBI”), as is disclosed in, for example, commonly assigned, co-pending patent application serial no. 08/693,780, filed July 22, 1996 in the name of Li, et al, the disclosure of which is incorporated herein by reference. While PBI has demonstrated very acceptable characteristics with respect to electrochemical performance, it has not, heretofore, demonstrated the very high thermal stability, and chemical resistance found in other types of materials, notably perfluorinated membranes such as Nafion.
  • FIG. 1 is a schematic representation of an electrochemical charge storage device in accordance with the instant invention
  • FIG. 2 is a schematic representation of a second electrochemical charge storage device in accordance with the instant invention.
  • an energy storage device such as an electrochemical charge storage device fabricated from a pair of electrode assemblies 10 and 11, which may be the anode and the cathode of the device.
  • the electrochemical charge storage device may be an electrochemical capacitor or an electrochemical battery cell.
  • the electrochemical capacitor is preferably an electrochemical capacitor characterized by an oxidation/reduction charge storage mechanism.
  • Each electrode assembly 10 and 11 includes an electrode 13 which electrodes may either be fabricated from the same or different materials. In the instance in which the electrodes are fabricated of the same material, they are referred to as "symmetric electrodes". Conversely, if they are made from different materials, they are referred to as "asymmetric electrodes".
  • the electrodes may be each made from one or more materials selected from the group consisting of ruthenium, iridium, platinum, cobalt, tungsten, vanadium, iron, nickel, molybdenum, silver, zinc, lead, manganese, alloys thereof, nitrides thereof, carbides thereof, sulfides thereof, oxides thereof, and combinations thereof.
  • said electrodes may be fabricated of conducting polymers.
  • Each electrode assembly may further include a current collector 12 which is electrically conducting.
  • the current collector 12 is preferably chemically inert in the polymer electrolyte 15 described hereinbelow.
  • a housing or gasket 14 may be employed to house the electrode and the electrolyte, but is optional.
  • the electrolyte 15 is sandwiched between the electrodes and is in the form of a film, such as a polymer, and may also serve as a separator between the two electrodes. This structure thus affords free and unobstructed movement to the ions in the electrolyte.
  • the combination electrolyte /separator prevents contact between the opposing electrodes since such a condition would result in a short circuit and malfunction of the electrochemical cell.
  • FIG. 2 there is illustrated therein a second electrochemical device, such as an electrochemical capacitor, which may be adapted to employ an electrolyte material such as that disclosed hereinbelow.
  • the device of FIG. 2 is a bipolar electrochemical capacitor device which includes a seven capacitor subassemblies 44, 46, 48, 50, 52, 54, and 55, which may be arranged in stacked configuration. As each subassembly is essentially identical, only one, assembly 44 will be described in detail.
  • Capacitor subassembly 44 includes a first layer 30 which is a bipolar metal substrate or foil.
  • the bipolar metal foil is fabricated to be both the substrate upon which active electrode materials are deposited, as well as a current collector for the charge generated by the materials.
  • layer 30 may be fabricated of a number of different materials selected from the group consisting of carbon, aluminum, tin, indium, titanium, copper, nickel, brass, stainless steel, silver, titanium /tantalum alloys, alloys thereof, and combinations thereof.
  • Layer 30 includes first and second major surfaces upon which are deposited layers of electrode active material 32 and 34.
  • the electrode active materials may be fabricated of symmetric or asymmetric materials such as those described hereinabove with respect to FIG. 1.
  • a completed single cell bipolar device 44 comprises a bipolar metal foil, with electrodes disposed on either side of said foil and a layer of electrolyte material disposed on at least one of said electrodes.
  • a plurality of such single subassemblies may be arranged in stacked configuration. Accordingly, seven such devices , 44, 46, 48, 50, 52, 54, and 55 may be arranged in stacked configuration in order to increase the voltage output therefrom. It is to be understood that the number of cells arranged in stacked configuration may be varied.
  • Disposed adjacent the outer most cells 44 and 55 are end plates 56 and
  • electrolyte material 58 adapted to collect current generated by the stacked subassemblies.
  • the electrolyte material described hereinbelow may be readily adapted for use in capacitors, electrochemical battery cells, fuel cells, electrochemical sensors, and any other type of electrochemical cell requiring an electrolyte material for providing ionic conductivity.
  • the electrolyte materials described herein may be fabricated by providing a polybenzimidazole ("PBI") polymeric material which has been sulfonated.
  • the PBI material is subjected to a sulfur containing acidic species at temperatures sufficient to induce sulfonation of the PBI material.
  • the PBI material may be provided in any number of different forms, but is preferably provided in a form selecting from the group consisting of powders, films, fibers, particles, fabric, powders, and combinations thereof.
  • the sulfur containing acidic species is selected from the group consisting of H2SO4, H2SO3, H2O + SO2, H2O + SO3, and combinations thereof.
  • the sulfur containing acidic species is H2SO4.
  • the sulfur containing acidic species is typically provided in molar concentrations of between 0.01 and 7.6, and preferably 5.0.
  • the ratio of sulfur containing acidic species to polymeric material is between about 2:1 and 40:1, and preferably between 10:1 and 30:1.
  • the PBI material and sulfur containing acidic species are heated to temperatures of between 30 and 95°C, and preferably heated to temperatures of between 50 and 80°C.
  • an electrochemical capacitor was fabricated using a commercially available, non-woven sulfonated PBI material sandwiched between a pair of Ru ⁇ 2 electrodes deposited on Ti substrates, as are well known in the art. Cyclic voltammogram (“CV") and conductivity measurements were run on this device to measure its performance as an electrochemical capacitor. As originally tested, the solid electrolyte film was dry and demonstrated an unacceptably high equivalent series resistance (“ESR"). The device was the "wetted” by exposing it to steam for 1 minute. The CV results illustrated a device having low ESR and high conductivity.
  • ESR equivalent series resistance
  • Conductivity was specifically measured for this film, and was 2.8x10"3 Ohms " ! per centimeter (" " V m"). With additional steaming of up to four minutes, conductivity increased to 6x10 ⁇ 2 -1/cm. This compares very favorably to Nafion which, after steaming in sulfuric acid for 8 hours demonstrates conductivity of 2xl0"3 -1/cm.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

L'invention concerne une cellule électrochimique dotée de première (10) et seconde (11) électrodes entre lesquelles est placé un électrolyte polymère solide (15). L'électrolyte polymère solide est de préférence fabriqué au moyen d'un matériau polymère polybenzimidazol qui est exposé à du soufre contenant des espèces acides, à une température suffisante pour que la sulfonation du polybenzimidazol soit provoquée. Les cellules électrochimiques fabriquées au moyen de ces systèmes présentent des caractéristiques de fonctionnement nettement meilleures que celles de la technique antérieure.
PCT/US1997/022175 1996-12-09 1997-11-26 Electrolyte polymere polybenzimidazol sublime et cellule electrochimique dans laquelle il est utilise Ceased WO1998026466A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US76191696A 1996-12-09 1996-12-09
US08/761,916 1996-12-09

Publications (1)

Publication Number Publication Date
WO1998026466A1 true WO1998026466A1 (fr) 1998-06-18

Family

ID=25063603

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/022175 Ceased WO1998026466A1 (fr) 1996-12-09 1997-11-26 Electrolyte polymere polybenzimidazol sublime et cellule electrochimique dans laquelle il est utilise

Country Status (1)

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WO (1) WO1998026466A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114540876A (zh) * 2022-04-12 2022-05-27 河南工业大学 用于析氧反应的磺化聚苯并咪唑基电催化剂及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J. ELECTROCHEMICAL SOCIETY, Vol. 142, No. 7, July 1995, WAINRIGHT et al., "Acid-Doped Polybenzimidazoles; A New Polymer Electrolyte", page 121. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114540876A (zh) * 2022-04-12 2022-05-27 河南工业大学 用于析氧反应的磺化聚苯并咪唑基电催化剂及其制备方法
CN114540876B (zh) * 2022-04-12 2023-08-11 河南工业大学 用于析氧反应的磺化聚苯并咪唑基电催化剂及其制备方法

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