WO2002097941A2 - High-energy, rechargeable electrochemical cells - Google Patents

High-energy, rechargeable electrochemical cells Download PDF

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Publication number
WO2002097941A2
WO2002097941A2 PCT/IL2002/000420 IL0200420W WO02097941A2 WO 2002097941 A2 WO2002097941 A2 WO 2002097941A2 IL 0200420 W IL0200420 W IL 0200420W WO 02097941 A2 WO02097941 A2 WO 02097941A2
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Prior art keywords
aluminum
aqueous electrolyte
magnesium
group
electrolyte
Prior art date
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PCT/IL2002/000420
Other languages
French (fr)
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WO2002097941A3 (en
Inventor
Doron Aurbach
Orit Chasid
Yossi Gofer
Chaim Gizbar
Original Assignee
Bar-Ilan University
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Publication date
Application filed by Bar-Ilan University filed Critical Bar-Ilan University
Priority to KR20037015707A priority Critical patent/KR20040006005A/en
Priority to EP02735937A priority patent/EP1399999A2/en
Priority to JP2003501020A priority patent/JP2005505099A/en
Priority to HU0500522A priority patent/HUP0500522A2/en
Priority to IL15909202A priority patent/IL159092A0/en
Priority to MXPA03011001A priority patent/MXPA03011001A/en
Priority to CA002449241A priority patent/CA2449241A1/en
Priority to BR0210240-4A priority patent/BR0210240A/en
Priority to EA200301326A priority patent/EA200301326A1/en
Priority to TW091113893A priority patent/TW546864B/en
Publication of WO2002097941A2 publication Critical patent/WO2002097941A2/en
Publication of WO2002097941A3 publication Critical patent/WO2002097941A3/en

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    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G28/00—Compounds of arsenic
    • C01G28/007—Halides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G30/00—Compounds of antimony
    • C01G30/006—Halides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/006—Compounds containing, besides molybdenum, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/061—Aluminium compounds with C-aluminium linkage
    • C07F5/064—Aluminium compounds with C-aluminium linkage compounds with an Al-Halogen linkage
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
    • 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

  • the present invention relates to electrochemical cells utilizing a non-
  • Such cells usually consist of a transition metal oxide or
  • chalcogenide cathode-active material an anode-active alkali metal or alkali
  • a rechargeable cell is capable of charging and discharging
  • a liquid cathode can be used, allowing
  • Liquid cathodes are also advantageous in that
  • cathode requires protective, insulating films on the anode.
  • a solid cathode must be insoluble in the electrolyte, and must be able to
  • a prime example of a solid cathode of this variety is an
  • Intercalation cathode Intercalation cathode. Intercalation chemistry focuses on the insertion of ions
  • a group of intercalation materials of particular importance is called
  • Chevrel-phase materials also known as Chevrel compounds. Chevrel
  • n is usually about 8.
  • the unique crystal structure of Chevrel-phase materials allows the insertion of one or more metal ions in a reversible, partially
  • metal and x may vary from 0 (no intercalated metal) to 4 or less, depending on
  • electrochemical cells must be paired with a suitable anode-active material
  • electrolytes are known to perform well with a particular anode-cathode couple
  • organometallic alkali metal salts in organic solvents as the electrolyte system.
  • organic radicals selected from the following groups: alkyl, aryl, alkenyl,
  • M* represents an alkali metal ion.
  • active metal salt complexes having the formula ZMR n X i; wherein Z is a metal
  • the Rs are specified haloorganic radicals
  • the Xs are selected from various halides, alkyls, aryls, alkaryls and aralkyls.
  • lithium is specified to be an alkali metal, with lithium being the preferred embodiment.
  • M is
  • alkali metal anodes are much more readily ionized than are alkaline earth metal
  • Alkali metals are highly lithium
  • Alkali metals are also highly flammable, and fire due to reaction of
  • Lithium is poisonous and compounds thereof are known for their
  • alkali metals requires specialized facilities, such as dry rooms, specialized
  • magnesium metal and aluminum metal are easy to manufacture.
  • the metals are reactive, but undergo rapid passivation of the surface,
  • electrochemical cell having an intercalation cathode, an alkaline earth anode,
  • R1-R4 are radicals selected from the
  • alkyl alkyl, aryl, alkaryl, aralkyl, alkenyl, cycloalkyl, allyl,
  • M represents an alkaline earth metal such as
  • radicals can be inertly substituted with substituents that have
  • composition with respect to effectiveness in an electrochemical cell such as
  • M is lithium, sodium, potassium, or magnesium
  • c is 1 or 2
  • n is an integer from 1 to 6.
  • electrochemical cells having an alkaline earth anode such as magnesium.
  • electrolyte is M' +m (ZR n X q-n ) m in which: M' is selected from the group
  • Z is selected from the group consisting of aluminum, boron, phosphorus, antimony and arsenic; R represents
  • radicals selected from the following groups: alkyl, alkenyl, aryl, phenyl, benzyl,
  • the ions of Mg, Ca, and Al are small and multivalent, such that the
  • electrolyte is strongly dependent on the solvent structure and polarity.
  • liquid electrolyte systems is tetrahydrofuran (THF).
  • THF tetrahydrofuran
  • inventive electrolyte system will be soluble and compatible in such way that the complex will not segregate or react with the polymer matrix and the
  • Grignard reagents may be of scientific interest, they cannot be applied to
  • the present invention is a new type of solid gel electrolyte for use in
  • the properties of the solid gel electrolyte include high
  • electrolyte including: (a) at least one polymer compound; (b) at least one
  • M' is selected from the group consisting of magnesium, calcium, and
  • Z is selected from the group consisting of aluminum, boron,
  • R represents radicals selected from the
  • follo ⁇ ving groups alkyl, alkenyl, aryl, phenyl, benzyl, and amido;
  • X is a
  • non-aqueous electrolyte is incorporated into an electrochemical cell further
  • electrolyte including: (a) at least one organic solvent, and (b) at least one
  • electrolytically active salt represented by the formula:
  • M' (ZR n X q-n ) m in which: M' is selected from the group consisting of magnesium, calcium, and
  • Z is selected from the group consisting of aluminum, boron,
  • R represents radicals selected from the
  • alkyl alkenyl, aryl, phenyl, benzyl, and amido
  • X is a
  • aqueous electrolyte is incorporated into an electrochemical cell further
  • Z is aluminum
  • M' is magnesium
  • M' is calcium
  • the electrolytically active salt is Mg[butylAlCl 3 ] 2 .
  • the electrolytically active salt is Mg[butylethylAlCl 2 ] 2 -
  • M' is selected from the group consisting of magnesium and
  • the organic solvent contains tetraglyme.
  • the organic solvent contains tetrahydrofuran.
  • the polymer compound serves as a matrix.
  • the polymer compound is selected from the group consisting of
  • M' is selected from the group consisting of magnesium and
  • the intercalation cathode is a Chevrel-phase intercalation
  • the metal anode is magnesium.
  • the polymer compound is selected from the group consisting of
  • the solvent is selected from the group consisting of THF and
  • the present invention successfully addresses the shortcomings of the
  • FIG. 1 is a graph displaying typical cyclic voltammogram of solid gel
  • electrolyte containing a matrix of Mg(AlCl 2 B ⁇ £t) 2 salt and tetraglyme in
  • PVdF poly(vinylidene fluoride)
  • FIG. 2 is a graph of the voltage patterns of an electrochemical cell
  • PVdF poly(vinylidene fluoride)
  • the present invention is a new type of solid gel electrolyte for use in
  • the properties of the solid gel electrolyte include high
  • Alkali metals are very inexpensive relative to alkali metals. Alkali metals are very inexpensive relative to alkali metals. Alkali metals are very inexpensive relative to alkali metals. Alkali metals are very inexpensive relative to alkali metals. Alkali metals are very inexpensive relative to alkali metals. Alkali metals are very inexpensive relative to alkali metals. Alkali metals are very inexpensive relative to alkali metals. Alkali metals.
  • Lithium in particular is poisonous, and lithium compounds are
  • the surface such that for all practical purposes, the metals are highly stable.
  • a polymeric matrix in conjunction with a polar organic solvent can dissolve the
  • cation M' is selected from the group consisting of magnesium, calcium, and
  • the cation M' is magnesium.
  • Z is selected from the group consisting of aluminum, boron, phosphorus,
  • R represents at least one type of radical selected from the
  • alkyl alkenyl, aryl, phenyl, benzyl, and amido
  • X is a
  • radical “R” refers to at least one type of radical selected from the following
  • alkyl alkenyl, aryl, phenyl, benzyl, and amido.
  • electrolytically active salts having different R groups are Mg[butylethylAlCl 2 ] 2,
  • PEO polyethylene oxide
  • PVdF poly(vinylidene fluoride)
  • PVC poly(vinylchloride)
  • Bu refers to a butyl group
  • Et refers to
  • THF tetrahydrofuran
  • cathode pair is 2.2 volts, such that the cell can be operated in a stable, reversible
  • electrolyte not only as an independent entity, but also as a unit within a system
  • appropriate battery includes the solid gel electrolyte according to the present invention, a magnesium metal anode and a magnesium insertion compound
  • compound cathode is a magnesium-Chevrel intercalation cathode of the form
  • the solid electrolyte composition of the present invention includes a
  • organometallic salts of the form M'(ZR n X q-n ) m , as described above.
  • Organometallic salts of this form may be combined with compatible non-polar organic radicals,
  • organometallic salts or with compatible organometallic salts of other forms.
  • PEO poly(propylene oxide)
  • PPO poly(propylene oxide)
  • PVdF polyfvinylidene fluoride
  • HFP poly(hexafluoropropylene)
  • PVC poly(vinylchloride)
  • PMMA poly(acrylonitrile)
  • PAN poly(acrylonitrile)
  • PEEK poly(acrylonitrile)
  • MEEP metal-oxide
  • transition metal oxides include transition metal oxides,
  • the transition metal oxides include V 2 0 5 , TiS 2 , MoS 2 , ZrS 2 , Co 3 0 4 , Mn0 2 ,
  • Mn 2 0 4 Mn 2 0 4
  • chalcogenides include Chevrel-phase compounds.
  • a magnesium-Chevrel intercalation cathode for use in conjunction with
  • the temperature was raised at a rate of 400°C/h to 450°C.
  • the temperature was
  • the copper molybdenum s ⁇ lfide powder was mixed with Teflon-loaded
  • the composite electrode formed was dried under vacuum af room
  • the electrode was subsequently subjected to either chemical or
  • FIG. 1 is a graph displaying typical
  • magnesium organo-halo-aluminates salt and tetraglyme solvent magnesium organo-halo-aluminates salt and tetraglyme solvent.
  • FIG. 1 shows the potentiodynamic behavior of Mg(AlCl 2 BuEt) 2
  • An electrochemical cell was prepared consisting of a Chevrel-phase
  • the solid gel electrolyte was prepared from 0.25 Molar
  • the anode was a disc
  • the battery was encased in a stainless steel "coin type" cell configuration
  • the cell was cycled on a standard charger-discharger with
  • the battery was subjected to continuous cycling over 3 months.
  • a solid gel electrolyte according to the present invention was prepared

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

A solid, gel type non-aqueous electrolyte for use in an electrochemical cell, the electrolyte including: (a) at least one polymer compound; (b) at least one organic solvent, and (c) at least one electrolytically active salt represented by the formula: M'(ZRnXq-n)m, in which: M' is selected from the group consisting of magnesium, calcium, and aluminum; Z is selected from the group consisting of aluminum, boron, phosphorous, antimony and arsenic; R represents radicals selected from the following groups: alkyl, alkenyl, aryl, phenyl, benzyl, and amido: X is a halogen (I, Br, Cl, F); m = 2-3; n = 0-5 and q = 6 for Z = phosphorous, antimony, and arsenic, and n = 0-3 and q = 4 for Z = aluminum and boron, wherein the polymer compound, organic solvent, and electrolytically active salt interact to form a non-aqueous electrolyte having a solid, gel type structure. The solid, gel type non-aqueous electrolyte is preferably incorporated into an electrochemical cell further including a metal anode and an intercalation cathode.

Description

HIGH-ENERGY, RECHARGEABLE ELECTROCHEMICAL CELLS
FIELD AND BACKGROUND OF THE INVENTION
The present invention relates to electrochemical cells utilizing a non-
aqueous gel polymer electrolyte with an intercalation cathode, and more
particularly, to electrochemical cells utilizing a non-aqueous gel polymer
electrolytic system, an intercalation cathode and a magnesium anode.
Rechargeable, high energy density electrochemical cells of various kinds
are known. Such cells usually consist of a transition metal oxide or
chalcogenide cathode-active material, an anode-active alkali metal or alkali
metal intercalation compound, and an electrolyte solution containing a
dissolved alkali-based salt in an aprotic organic or inorganic solvent, or
polymer electrolyte.
Theoretically, a rechargeable cell is capable of charging and discharging
indefinitely, however, in practice such performance is unattainable. The degradation mechanisms of the various anodes, cathodes and electrolytes are
complex and are known to those skilled in the art.
Two basic types of cathodes are appropriate for a battery system that is
rechargeable at ambient temperatures. A liquid cathode can be used, allowing
reactions to take place with facility. Liquid cathodes are also advantageous in
that thin films or crusts forming on the surface of the cathode tend to crack,
such that the cathode activity remains high over the course of the cycling. The
mobility of the cathodic material is a liability, however, in that contact with the
anode short-circuits the cell. Thus, an electrochemical cell with a liquid
cathode requires protective, insulating films on the anode.
A solid cathode must be insoluble in the electrolyte, and must be able to
absorb and desorb a charge-compensating ion in a substantially reversible and
fast manner. A prime example of a solid cathode of this variety is an
intercalation cathode. Intercalation chemistry focuses on the insertion of ions
or neutral molecules into an inorganic or organic matrix. In a typical
intercalation cathode, cations dissolved in the electrolyte solution are inserted
into the inorganic matrix structure.
A group of intercalation materials of particular importance is called
Chevrel-phase materials, also known as Chevrel compounds. Chevrel
compounds contain an invariant portion consisting of molybdenum and a
chalcogen - sulfur, selenium, tellurium, or mixtures thereof. The invariant
portion is generally of the formula Mo6Tn, where T represents the chalcogen
and n is usually about 8. The unique crystal structure of Chevrel-phase materials allows the insertion of one or more metal ions in a reversible, partially
reversible, or irreversible manner. The stoichiometry of the intercalation
compound can be represented as MxMo6Tn, where M represents the intercalated
metal and x may vary from 0 (no intercalated metal) to 4 or less, depending on
the properties of the particular metal.
The intercalation of metal ions into the Chevrel compound releases
energy. Since the process is partially or fully reversible, these compounds are
particularly suitable as electrodes in electrochemical cells. For example,
lithium, the predominant intercalation ion, can be removed from the Chevrel
compound by the application of electrical energy. The energy is released as
electrical energy upon reintercalation.
The cathode-active material in the high energy density, rechargeable
electrochemical cells must be paired with a suitable anode-active material,
which is most commonly made of an active metal such as alkali metals.
However, the performance of a particular anode-cathode couple is strongly
influenced by the nature of the electrolyte system. Certain non-aqueous
electrolytes are known to perform well with a particular anode-cathode couple
and be ineffective or significantly less effective with other anode-cathode
couples, either because the electrolyte solution's components are not stable or
because the solutions components degrades during cycling active electrodes.
As a result, much of the prior art relates to the cathode-active material, the
anode-active material and the electrolyte not only as independent entities, but
also as units within an appropriate battery system. U.S. Patent No. 4,104,4δO to Klemann et al., discloses reversible
batteries with an alkali metal anode, a chalcogenide cathode, and
organometallic alkali metal salts in organic solvents as the electrolyte system.
Non- aqueous electrolyte systems containing alkali metal salts of boron or
aluminum anions based which also contain organic groups are disclosed.
Organoborate salts of alkali metals represented by the formula
Rl
M+ R4— B— R2
R3
are disclosed in U.S. Patent No. 4,511,642 to Higashi et al., wherein R1-R4 are
organic radicals selected from the following groups: alkyl, aryl, alkenyl,
cycloalkyl, allyl, heterocyclic, and cyano, and M* represents an alkali metal ion.
U.S. Patent No. 4,139,681 describes cells containing electrolytically
active metal salt complexes having the formula ZMRnXi; wherein Z is a metal
from a group containing aluminum, the Rs are specified haloorganic radicals,
the Xs are selected from various halides, alkyls, aryls, alkaryls and aralkyls. M
is specified to be an alkali metal, with lithium being the preferred embodiment.
U.S. Patent No. 4,542,081 to Armand et al., describes solutions for the
constitution of solid electrolyte materials of electrochemical generators. The
compound is of the formula
(R-C≡C)4 Z~, M" in which Z is a trivalent element capable of entering into 4-coordination, such
as aluminum, and R represents groups which are non-proton donors. M is
specified to be an alkali metal.
The prior art described above, including U.S. Patent Nos. 4,104,4S"€^
4,511,642, 4,139,681 and 4,542,081, specifies that M is an alkali metal The
use of an alkaline earth metal anode such as magnesium would appear
disadvantageous relative to the use of an alkali metal such as lithium because
alkali metal anodes are much more readily ionized than are alkaline earth metal
anodes. In addition, on recharge the cell must be capable of re-depositing the
anode metal that was dissolved during discharge, in a relatively pure state, and
without the formation of deposits on the electrodes.
However, there are numerous disadvantages to alkali batteries. Alkali
metals, and lithium in particular, are expensive. Alkali metals are highly
reactive. Alkali metals are also highly flammable, and fire due to reaction of
alkali metal with oxygen or other active material is extremely difficult to
extinguish. Lithium is poisonous and compounds thereof are known for their
severe physiological effects, even in minute quantities. As a result, the use of
alkali metals requires specialized facilities, such as dry rooms, specialized
equipment and specialized procedures.
In contradistinction, magnesium metal and aluminum metal are easy to
process. The metals are reactive, but undergo rapid passivation of the surface,
such that the metals exhibit highly stable behavior. Both magnesium and
aluminum are inexpensive relative to the alkali metals. U.S. Patent No. 4,894,302 to Hoffman et al., discloses an
electrochemical cell having an intercalation cathode, an alkaline earth anode,
and a non-aqueous liquid electrolyte containing an organic solvent and an
electrolytically active, organometallic alkaline earth metal salt represented by
the formula
Rl
Tvl +2 R4— Z— R2
R3
wherein Z is boron or aluminum; R1-R4 are radicals selected from the
following groups: alkyl, aryl, alkaryl, aralkyl, alkenyl, cycloalkyl, allyl,
heterocyclic alkyl, and cyano; and M represents an alkaline earth metal such as
magnesium. The radicals can be inertly substituted with substituents that have
no detrimental effect upon the electrolytic properties of the electrolyte
composition with respect to effectiveness in an electrochemical cell, such as
halogenated or partially halogenated derivatives of the above groups. While
exhaustive care is taken to disclose a broad range of organic radicals and
halogenated organic radicals, bonding the metallic species of the anion (Z) to
another inorganic species is not considered.
U.S. Patent No. 5,491,039 describes a solid, single-phase electrolyte
containing a solid polymeric matrix and an organometallic ion salt represented
by the formula
Mc(ZRn) wherein Z is boron, aluminum or titanium; Rn are various subsituted or
unsυbsituted organic radicals; M is lithium, sodium, potassium, or magnesium,
c is 1 or 2, and n is an integer from 1 to 6. As in U.S. Patent No. 4,894,302, a
broad range of organic radicals including halogenated organic radicals is
disclosed, but the bonding of the metallic species of the anion (Z) to another
inorganic species is not reported. In all cases, metallic species Z is bonded to a
carbon atom. More specifically, the bonding of the metallic species of the
anion (Z) directly to a halogen is not disclosed. It must be emphasized that this
is of particular significance in light of the fact that U.S. Patent No. 5,491,039
teaches an extremely broad range of radicals that may be appropriate for
attaching to the metallic species of the anion.
Both U.S. Patent No. 5,491,039 and U.S. Patent No. 4,894,302 disclose
electrochemical cells having an alkaline earth anode such as magnesium. For
commercial application, however, such magnesium batteries must be essentially
rechargeable and must have a reasonable shelf life. Sustaining a voltage of 1.5
volts is problematic or impossible with the usual intercalation cathodes and
electrolytes according to prior art. Magnesium batteries operating at 1.5 volts
are particularly prone to electrolyte decomposition and to
encrustation/passivation of both electrode surfaces.
In our co-pending parent application, Serial No. 09/419,940, a new type
of electrolyte for electrochemical cell was disclosed. The general formula of the
electrolyte is M'+m (ZRnXq-n)m in which: M' is selected from the group
consisting of magnesium, calcium, and aluminum; Z is selected from the group consisting of aluminum, boron, phosphorus, antimony and arsenic; R represents
radicals selected from the following groups: alkyl, alkenyl, aryl, phenyl, benzyl,
and a ido; X is a halogen (I, Br, Cl, F); m = 1-3; and n = 0-5 and q = 6 in the
case of Z = phosphorus, antimony and arsenic, and n = 0-3 and q = 4 in the
case of Z = aluminum and boron. The above-mentioned co-pending application
disclosed the compatibility of this electrolyte type with Mg and a magnesium-
Chevrel intercalation cathode of the form
CuxMgyMo6S8
to provide the basis for the production of a viable, rechargeable magnesium
battery with a nominal voltage exceeding 1.5 volts.
Special interest is currently being focused on the use of solid polymeric
electrolytes in advanced battery systems. The substitute of liquid electrolyte
with solid gel polymeric electrolyte provides advantages in terms of safety,
design flexibility and simplicity of production equipment and process operation.
Gels based on Li, Na and K ions are well known in academic literature
and some of them have seen some extent of commercial implementation. By
sharp contrast, very little work has been performed on gels based on Mg, Ca
and Al ions. The relative paucity of work on Mg, Ca and Al gels may be
attributed to several physical properties. The lattice energy of salts of Mg, Ca
and Al is usually very high relative to those of salts of the alkali metals. Hence,
it is extremely difficult to identify a polymer matrix that is polar enough to
effectively cause ionic dissociation of these salts. It must be emphasized that
the solubility of most of these salts is very low, even in water and in other high dielectric mediums, such that the possibility of finding a polymeric medium that
can dissolve them with reasonable ionic dissociation appears remote. In
addition, the ions of Mg, Ca, and Al are small and multivalent, such that the
ions are characterized by extremely high charge densities, which tend to
severely restrict ion mobility in solution. The transference number of such ions
is expected to be less than 0.5 and the electrical conductivity of the solutions of
such ions appear to be insufficient for the inventive electrolyte systems.
It must be further emphasized that the liquid electrolyte taught by our
above-referenced co-pending parent application is based on a delicate
equilibrium state in the solution. The electrochemical reactivity of the
electrolyte is strongly dependent on the solvent structure and polarity. For
example, the most extensively tested ethereal solvent in the above-referenced
liquid electrolyte systems is tetrahydrofuran (THF). The use of very similar
ether such as 2Me-THF, which differs from THF only by the addition of a
single methyl group, was investigated. This seemingly minor difference has
only a small effect on the polarity of the solvent, but in the inventive electrolyte
system, such a difference was enough to cause a segregation of the complex salt
and a loss in electrochemical reactivity. This example manifestly demonstrates
that which is l nown on purely theoretical grounds, namely, that the solvent
medium critically influences the structure and reactivity of the electrolyte
complex salt.
Therefore, it would be surprising to find a polymer matrix in which the
inventive electrolyte system will be soluble and compatible in such way that the complex will not segregate or react with the polymer matrix and the
electrochemical reactivity will maintain.
Prior to the liquid electrolyte system taught by our above-referenced co-
pending parent application, the only known type of electrolyte system in which
magnesium could be electrochemically deposited and dissolved reversibly was
a Grignard reagent in an ethereal solution. For example, Liebenow
(Electrochimica Acta, Vol 43, Nos. 10-1 1 , pp. 1253-1256, 1998) prepared a gel
polymer based on ethyl magnesium bromide in tetrahydrofuran solution with
polyethylene oxide as the polymeric matrix and demonstrated the ability of the
system to reduce and oxidize magnesium. However, while gel polymers based
on Grignard reagents may be of scientific interest, they cannot be applied to
commercial battery technologies. The extremely poor anodic stability of gel
polymers based on Grignard reagents precludes their use in such solid gel
electrolytes. Moreover, the Grignard reagents are extremely flammable,
corrosive and dangerous reduction materials.
Thus, there is a widely recognized need for, and it would be highly
advantageous to have, a solid polymeric non-aqueous electrolyte that allows the
production of an all solid, practical, rechargeable battery which would be more
safe, clean, efficient and economical than rechargeable batteries known
heretofore. It would be of further advantage if such an electrolyte would be
based on magnesium, calcium, or aluminum, which are inexpensive and
abundant raw materials. SUMMARY OF THE INVENTION
The present invention is a new type of solid gel electrolyte for use in
electrochemical cells. The properties of the solid gel electrolyte include high
conductivity and an electrochemical window that can exceed 2.2V vs.
Mg/Mg+2. The use of the electrolyte in an appropriate cell promotes the
substantially reversible deposition of the metal and a reversible intercalation
process at the cathode material.
According to the teachings of the present invention there is provided a
solid, gel type non-aqueous electrolyte for use in an electrochemical cell, the
electrolyte including: (a) at least one polymer compound; (b) at least one
organic solvent, and (c) at least one electrolytically active salt represented by
the formula:
M'(ZRnXq-n)m
in which: M' is selected from the group consisting of magnesium, calcium, and
aluminum; Z is selected from the group consisting of aluminum, boron,
phosphorus, antimony and arsenic; R represents radicals selected from the
folloλving groups: alkyl, alkenyl, aryl, phenyl, benzyl, and amido; X is a
halogen (I, Br, Cl, F); m = 2-3; n = 0-5 and q = 6 for Z = phosphorus,
antimony, and arsenic, and n = 0-3 and q = 4 for Z = aluminum and boron,
wherein the polymer compound, organic solvent, and electrolytically active salt
interact to form a non-aqueous electrolyte having a solid, gel type structure. According to another aspect of the present invention, the solid, gel type
non-aqueous electrolyte is incorporated into an electrochemical cell further
including a metal anode and an intercalation cathode.
According to yet another aspect of the present invention, there is
provided a non-aqueous electrolyte for use in an electrochemical cell, the
electrolyte including: (a) at least one organic solvent, and (b) at least one
electrolytically active salt represented by the formula:
M'(ZRnXq-n)m in which: M' is selected from the group consisting of magnesium, calcium, and
aluminum; Z is selected from the group consisting of aluminum, boron,
phosphorus, antimony and arsenic; R represents radicals selected from the
following groups: alkyl, alkenyl, aryl, phenyl, benzyl, and amido; X is a
halogen (I, Br, Cl, F); = 2-3; n = 0-5 and q = 6 for Z = phosphorus,
antimony, and arsenic, and n = 0-3 and q = 4 for Z = aluminum and boron.
According to yet another aspect of the present invention, the non-
aqueous electrolyte is incorporated into an electrochemical cell further
including a metal anode and an intercalation cathode.
According to further features in preferred embodiments of the invention
described below, Z is aluminum.
According to further features in preferred embodiments of the invention
described below, M' is magnesium. According to further features in preferred embodiments of the invention
described below, M' is calcium.
According to further features in preferred embodiments of the invention
described below, the electrolytically active salt is Mg[butylAlCl3]2.
According to further features in preferred embodiments of the invention
described below, the electrolytically active salt is Mg[butylethylAlCl2]2-
According to further features in preferred embodiments of the invention
described below, M' is selected from the group consisting of magnesium and
calcium, Z is aluminum, R represents at least one type of alkyl radical, and m is
2.
According to further features in preferred embodiments of the invention
described below, the organic solvent contains tetraglyme.
According to further features in preferred embodiments of the invention
described below, the organic solvent contains tetrahydrofuran.
According to further features in preferred embodiments of the invention
described beloλv, the polymer compound serves as a matrix.
According to further features in preferred embodiments of the invention
described below, the polymer compound is selected from the group consisting
ofPVdF. PEO, and PVC. According to further features in preferred embodiments of the invention
described below, M' is selected from the group consisting of magnesium and
calcium, Z is aluminum, R is at least one type of alkyl radical, and m is 2.
According to further features in preferred embodiments of the invention
described below, the intercalation cathode is a Chevrel-phase intercalation
cathode.
According to further features in preferred embodiments of the invention
described below, the Chevrel-phase intercalation cathode is represented by the
formula
Cu MgyMo6S8
wherein 1 > x > 0 and 2 > y > 0.
According to further features in preferred embodiments of the invention
described below, the metal anode is magnesium.
According to further features in preferred embodiments of the invention
described below, the polymer compound is selected from the group consisting
ofPVdF, PEO and PVC.
According to further features in preferred embodiments of the invention
described below, the solvent is selected from the group consisting of THF and
tetraglyme.
The present invention successfully addresses the shortcomings of the
presently known solid gel electrolytes and provides the basis for the production of a viable, rechargeable battery based on magnesium, calcium, and aluminum,
and having a nominal voltage exceeding 1.5 volts.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is herein described, by way of example only, with
reference to the accompanying drawings, wherein:
FIG. 1 is a graph displaying typical cyclic voltammogram of solid gel
electrolyte containing a matrix of Mg(AlCl2Bυ£t)2 salt and tetraglyme in
poly(vinylidene fluoride) (PVdF) using a gold electrode, according to the
present invention;
FIG. 2 is a graph of the voltage patterns of an electrochemical cell
consisting of a Chevrel-phase cathode, magnesium metal anode, and a solid gel
electrolyte containing a matrix of Mg(AlCl2BuEt)2 salt and tetraglyme in
poly(vinylidene fluoride) (PVdF), according to the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is a new type of solid gel electrolyte for use in
electrochemical cells. The properties of the solid gel electrolyte include high
conductivity and an electrochemical window that can exceed 2.2V vs.
Mg/Mg+2. The use of the solid gel electrolyte in an appropriate cell promotes the substantially reversible deposition of magnesium metal on the anode current
collector and the reversible intercalation of magnesium in the cathode material.
Although alkali metals are readily ionized, the use of other metal anodes,
such as magnesium or aluminum has decided advantages. Magnesium and
aluminum are very inexpensive relative to alkali metals. Alkali metals are
highly reactive and highly flammable, and alkali fire is extremely difficult to
extinguish. Lithium in particular is poisonous, and lithium compounds are
known for their severe physiological effects, even in minute quantities. As a
result, the use of alkali metals requires specialized facilities, such as dry rooms,
specialized equipment and specialized procedures.
Magnesium and aluminum are reactive, but undergo rapid passivation of
the surface, such that for all practical purposes, the metals are highly stable.
Magnesium and aluminum are available and inexpensive, non-toxic, non-
hazardous, and easy to work with, and as such, are highly desirable raw
materials for electrochemical cells and for electrolytic solutions and solid gel
electrolytes in particular.
Although primary electrochemical cells based on magnesium are known,
such cells are non-rechargeable and are used solely for military applications.
Sustaining a voltage of 1.5 volts is problematic or impossible with the usual
intercalation cathodes and electrolytes according to prior art. Magnesium
batteries operating at 1.5 volts are particularly prone to electrolyte
decomposition and to encrustation/passivation of the electrode surface. We have discovered that despite the known difficulties delineated above,
a polymeric matrix in conjunction with a polar organic solvent, can dissolve the
inventive electrolyte of the form:
M' (ZRnXq-n)m This mixture creates a polymeric gel that exhibits sufficient conductivity at
room temperature and that electrochemically deposits and dissolves the cation
M' with high reversibility, despite all the limitations discussed above. The
cation M' is selected from the group consisting of magnesium, calcium, and
aluminum. More preferably, the cation M' is magnesium.
Z is selected from the group consisting of aluminum, boron, phosphorus,
antimony and arsenic; R represents at least one type of radical selected from the
following groups: alkyl, alkenyl, aryl, phenyl, benzyl, and amido; X is a
halogen (I, Br, Cl, F); m = 2-3; and n = 0-5 and q = 6 in the case of Z =
phosphorus, antimony and arsenic, and n = 0-3 and q = 4 in the case of Z =
aluminum and boron.
As used herein in the specification and in the claims section that follows,
the radical "R" refers to at least one type of radical selected from the following
groups: alkyl, alkenyl, aryl, phenyl, benzyl, and amido. Examples of
electrolytically active salts having different R groups are Mg[butylethylAlCl2]2,
Mg[benzylethylmethylAlCl]2) and Ca[butylphenylAlCl2]2.
As used herein in the specification and in the claims section that follows,
"PEO" refers to polyethylene oxide; "PVdF" refers to poly(vinylidene fluoride); "PVC" refers to poly(vinylchloride); "Bu" refers to a butyl group; "Et" refers to
an ethyl group, and "THF" refers to tetrahydrofuran.
As described above, the electrochemical window of a cell with a solid
gel electrolyte according to the present invention and an appropriate anode-
cathode pair is 2.2 volts, such that the cell can be operated in a stable, reversible
fashion at 1.5 volts without decomposition of the solid gel electrolyte and
encrustation of the electrodes.
In a preferred embodiment of the invention, the solid gel electrolyte
according to the invention functions in an electrochemical cell with a metal
anode and an intercalation cathode.
Certain non-aqueous electrolytes are known to perform well λvith a
particular anode-cathode couple and be ineffective or significantly less
effective with other anode-cathode couples, either because the electrolyte is not
inert or because it degrades during cycling. It is relevant, therefore, to treat the
electrolyte, not only as an independent entity, but also as a unit within a system
containing an appropriate anode-cathode pair.
Hence, according to further features in preferred embodiments of the
invention described below, the solid gel electrolyte according to the present
invention is incorporated into specific electrochemical cells containing an
appropriate anode-cathode pair.
While various metals are suitable as anodes for the solid gel electrolytic
system, including magnesium, lithium, aluminum and calcium, a particularly
appropriate battery includes the solid gel electrolyte according to the present invention, a magnesium metal anode and a magnesium insertion compound
cathode.
In yet another preferred embodiment, the magnesium insertion-
compound cathode is a magnesium-Chevrel intercalation cathode of the form
CuxMgvMo6S8
wherein x = 0-1 and y = 0-2 .
The principles and operation of an electrolytic cell with an improved
electrolyte according to the present invention may be better understood with the
description provided hereinbelow and with reference to the drawings and the
accompanying description provided in the Examples.
The solid electrolyte composition of the present invention includes a
polymer compound, an organic solvent and electrochemically-active
organometallic salts of the form M'(ZRnXq-n)m, as described above.
Organometallic salts of this form may be combined with compatible non-
organometallic salts or with compatible organometallic salts of other forms.
Many types of polymer compounds can be use as matrix compound to
form the solid gel electrolyte of the present invention, including poly(ethylene
oxide) (PEO), poly(propylene oxide) (PPO), polyfvinylidene fluoride) (PVdF),
poly(hexafluoropropylene) (HFP), poly(vinylchloride) (PVC), poly(methyl
metacrylate) (PMMA), poly(acrylonitrile) (PAN), (PEEK), (MEEP) and
mixtures thereof. Intercalation cathodes used in conjunction with the solid gel electrolyte
according to the present invention include transition metal oxides,
chalcogenides and halogenides and combinations thereof. More specifically,
the transition metal oxides include V205, TiS2, MoS2, ZrS2, Co304, Mn02,
Mn204, and the chalcogenides include Chevrel-phase compounds.
EXAMPLE 1
A magnesium-Chevrel intercalation cathode for use in conjunction with
the solid gel electrolyte according to the present invention was synthesized
according to the procedure developed by Goecke and Schδlhorn, (E. Goecke,
R. Schόlhorn, G. Aselmann and W. Muller-Warmuth) published in Inorg.
Chem. 26, 1805 (1987). Elemental sulfur, molybdenum and copper of high
purity were added in a stoichiometric ratio of 4:3:1. After intimate mixing and
pressing into pellets, the mixture was sealed in a quartz ampoule under a
vacuum of 10"5 Torr. The ampoule was placed in a furnace, and the
temperature was raised at a rate of 400°C/h to 450°C. The temperature was
maintained at 450°C for 24 hours. Again, the temperature was raised at a rate
of 400°C h to 700°C and was maintained at 700°C for 24 hours. The
temperature was then raised at a rate of 120°C/h to 1050°C and was maintained
at 1050°C for 48 hours. After cooling to room temperature at a rate of 120°C/h, the ampoule was broken open. The copper molybdenum sυlfide (Cu2Mo6S8)
obtained was milled into fine powder using mortar and pestle.
The copper molybdenum sυlfide powder was mixed with Teflon-loaded
carbon black (CB). The resulting paste was spread on stainless steel mesh and
pressed. The composite electrode formed was dried under vacuum af room
temperature for 24 hours.
The electrode was subsequently subjected to either chemical or
electrochemical pretreatment in which some of the copper ions in the host
matrix (Cu2Mo6S8) were deinserted. The electrochemical deintercalation of
copper was performed in a non-aqueous medium, a IM solution of Mg(C10 )2
in acetonitrile. The deinsertion was performed by a galvanostatic charging
process in which the upper limit of the potential was controlled. A chemical
deintercalation of the copper was carried out by a direct reaction of Cu2Mo6Sg
with aqueous acidic solution containing FeCl3 as an oxidizer.
After thorough washing in acetonitrile and subsequent drying of the
electrode, charging-discharging cycles were conducted in a IM solution of
Mg(C104)2 in acetonitrile at various scan rates between -1.6V and 0.01 V,
relative to the Ag/Ag+1 reference electrode. A pronounced electrochemical
redox activity was observed, with a main oxidation peak at -1.219 V vs.
Ag/Ag+ and a corresponding main reduction peak at -1.41 V vs. Ag/Ag+. The
charge associated with the intercalation-deintercalation process was 71mAh/g
and 72mAh/g, respectively, which correspond to y = 1.09-1.12 in the formula
Cu0.ι3MgvMo6S8 The chemical and electrochemical reversibility of the intercalation
process was demonstrated over multiple cycles.
EXAMPLE 2
Referring now to the drawings, FIG. 1 is a graph displaying typical
cyclic voltammogram of an electrochemical cell including using a gold
electrode, a solid gel electrolyte containing a PVdF matrix with an ether-
magnesium organo-halo-aluminates salt and tetraglyme solvent.
FIG. 1 shows the potentiodynamic behavior of Mg(AlCl2BuEt)2
obtained with tetraglyme in a PVdF matrix using a gold working electrode. The
peak at -0.8V is due to the deposition of magnesium metal, and the peak at
around 0.7V is attributed to the subsequent electrochemical dissolution of the
magnesium metal. The electrochemical window obtained with this system
exceeds 2.2V. It is clearly evident from the cyclic voltammogram that the
process of magnesium deposition and dissolution is fully reversible.
EXAMPLE 3
An electrochemical cell was prepared consisting of a Chevrel-phase
cathode, a magnesium metal anode, and a solid gel electrolyte containing PVdF,
Mg(AlCl2BuEt)2 salt and tetraglyme. The cathode, weighing 74.3 mg, was
made from a mixture of copper-leached Chevrel-phase material containing 10 weight-% carbon black and 10 weight-% PVdF as a binder, spread on stainless
steel mesh. The solid gel electrolyte was prepared from 0.25 Molar
Mg(AlCl2BuEt)2 salt and tetraglyme in a PVdF matrix. The anode was a disc
of pure magnesium metal, with a diameter of 16 mm and a thickness of 0.2 mm.
The battery was encased in a stainless steel "coin type" cell configuration
without a separator. The cell was cycled on a standard charger-discharger with
a current density of 23.3 milliamperes/gram. The potential limits for the
cycling λvere between 0.5V at the fully discharged state and 1.8V for the fully
charged state.
The battery was subjected to continuous cycling over 3 months. The
good cyclability of the battery is clearly evident from FIG. 2, in which several
cycles are represented. The battery performance remains strong over the entire
length of the experiment. The measured charge density obtained in each
discharge is 61 mAh per gram of the cathode material.
EXAMPLE 4
A solid gel electrolyte according to the present invention was prepared
as follows: commercial, reagent-grade MgBu2, was dissolved in heptane.
Commercial, reagent-grade AlEtCl2 was added drop wise to the MgBu2 solution
according to the molar ratio. The mixture was stirred for 48 hours under an
inert gas, and Mg(BuEtAlCl2)2 was crystallized out of solution. The solvent
was removed by evacuation. Ether solvents were added very slowly to the organomagnesiυm salt to produce a saturated solution (around 0.5M). A
commercially available PVdF powder for gel polymer application was added to
the above solution and the mixture was stirred and heated until a one phase
polymeric gel was formed.
It Λvill be appreciated that the above descriptions are intended only to
serve as examples, and that many other embodiments are possible within the
spirit and the scope of the present invention.

Claims

WHAT IS CLAIMED IS:
1. A solid, gel type non-aqueous electrolyte for use in an
electrochemical cell, the electrolyte comprising:
(a) at least one polymer compound
(b) at least one organic solvent and
(c) at least one electrolytically active salt represented by the formula:
M'(ZRnXq-n)m in which:
M' is selected from the group consisting of magnesium, calcium, and aluminum;
Z is selected from the group consisting of aluminum, boron, phosphorus, antimony and arsenic;
R represents radicals selected from the following groups: alkyl, alkenyl, aryl, phenyl, benzyl, and amido;
X is a halogen (I, Br, Cl, F); m = 2-3; n = 0-5 and q = 6 for Z = phosphorus, antimony, and arsenic, and n = 0-3 and q = 4 for Z = aluminum and boron.
wherein said polymer compound, said organic solvent, and said electrolytically
active salt interact to form a non-aqueous electrolyte having a solid, gel type
structure.
2. The non-aqueous electrolyte of claim 1, wherein Z is aluminum.
3. The non-aqueous electrolyte of claim 2, wherein M' is
magnesium.
4. The non-aqueous electrolyte of claim 2, wherein M' is calcium.
5. The non-aqueous electrolyte of claim 1, wherein said
electrolytically active salt is Mg[butylAlCl3]2.
6. The non-aqueous electrolyte of claim 1 , wherein said
electrolytically active salt is Mg[butylethylAlCl2]2
7. The solid gel non-aqueous electrolyte of claim 1, wherein M' is
selected from the group consisting of magnesium and calcium, Z is aluminum,
R represents at least one type of alkyl radical, and m is 2.
8. The solid gel non-aqueous electrolyte of claim 6, wherein said
organic solvent contains tetraglyme.
9. The solid gel non-aqueous electrolyte of claim 6, wherein said
organic solvent contains tetrahydrofuran.
10. The solid gel non-aqueous electrolyte of claim 1, wherein said
polymer compound serves as a matrix.
11. The solid gel non-aqueous electrolyte of claim 1, wherein said
polymer compound is selected from the group consisting of PVdF, PEO and
PVC.
12. An electrochemical cell comprising:
(a) a metal anode;
(b) an intercalation cathode; and
(c) a solid gel non-aqueous electrolyte including:
i) at least one polymer compound
ii) at least one organic solvent and
iii) at least one electrolytically active salt represented by the
formula:
M'(ZRnXq-n)m in which:
M' is selected from the group consisting of magnesium, calcium, and aluminum;
Z is selected from the group consisting of aluminum, boron, phosphorus, antimony and arsenic;
R represents radicals selected from the following groups: alkyl, alkenyl, aryl, phenyl, benzyl, and amido;
X is a halogen (I, Br, Cl, F); m = 2-3; n = 0-5 and q = 6 for Z = phosphorus, antimony, and arsenic, and n = 0-3 and q = 4 for Z = aluminum and boron.
13. The electrochemical cell of claim 12, wherein M' in said solid
gel electrolyte is selected from the group consisting of magnesium and calcium,
Z is aluminum, R is at least one type of alkyl radical, and m is 2.
14. The electrochemical cell of claim 12, wherein said intercalation
cathode is a Chevrel-phase intercalation cathode.
15. The electrochemical cell of claim 14, wherein said Chevrel-phase
intercalation cathode is represented by the formula
CuxMgyMo6S8
wherein 1 > x > 0 and 2 > y > 0.
16. The electrochemical cell of claim 12, wherein said metal anode is
magnesium.
17. The electrochemical cell of claim 12, wherein said polymer
compound is selected from the group consisting of PVdF, PEO and PVC.
18. The electrochemical cell of claim 12, wherein said solvent is
selected from the group consisting of THF and tetraglyme.
19. A non-aqueous electrolyte for use in an electrochemical cell, the
electrolyte comprising:
(a) at least one organic solvent, and
(b) at least one electrolytically active salt represented by the formula:
■ M'(ZRnXq-n)m in which:
M' is selected from the group consisting of magnesium, calcium, and aluminum;
Z is selected from the group consisting of aluminum, boron, phosphorus, antimony and arsenic;
R represents radicals selected from the following groups: alkyl, alkenyl, aryl, phenyl, benzyl, and amido;
X is a halogen (I, Br, Cl, F); m = 2-3; n = 0-5 and q = 6 for Z = phosphorus, antimony, and arsenic, and n = 0-3 and q = 4 for Z = aluminum and boron.
20. The non-aqueous electrolyte of claim 19, wherein Z is aluminum.
21. The non-aqueous electrolyte of claim 19, wherein M' is
magnesium.
22. The non-aqueous electrolyte of claim 19, wherein M' is calcium.
23. The non-aqueous electrolyte of claim 19, wherein said
electrolytically active salt is Mg[butylAlCl3]2.
24. The non-aqueous electrolyte of claim 19, wherein said
electrolytically active salt is Mg[butylethylAlCl2]2.
25. The non-aqueous electrolyte of claim 19, wherein M' is selected
from the group consisting of magnesium and calcium, Z is aluminum, R
represents at least one type of alkyl radical, and m is 2.
26. The non-aqueous electrolyte of claim 25, wherein said organic
solvent contains tetraglyme.
27. An electrochemical cell comprising:
(a) a metal anode;
(b) an intercalation cathode; and
(c) a non-aqueous electrolyte including:
(i) at least one organic solvent and
(ii) at least one electrolytically active salt represented by the formula:
M'(ZRnXq-n)m in which:
M' is selected from the group consisting of magnesium, calcium, and aluminum;
Z is selected from the group consisting of aluminum, boron, phosphorus, antimony and arsenic;
R represents radicals selected from the following groups: alkyl, alkenyl, aryl, phenyl, benzyl, and amido;
X is a halogen (I, Br, Cl, F); m = 2-3; n = 0-5 and q = 6 for Z = phosphorus, antimony, and arsenic, and n = 0-3 and q = 4 for Z = aluminum and boron.
PCT/IL2002/000420 2001-06-01 2002-05-29 High-energy, rechargeable electrochemical cells WO2002097941A2 (en)

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