WO1997041608A1 - Electrochemical cell - Google Patents

Electrochemical cell Download PDF

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Publication number
WO1997041608A1
WO1997041608A1 PCT/US1997/007005 US9707005W WO9741608A1 WO 1997041608 A1 WO1997041608 A1 WO 1997041608A1 US 9707005 W US9707005 W US 9707005W WO 9741608 A1 WO9741608 A1 WO 9741608A1
Authority
WO
WIPO (PCT)
Prior art keywords
cathode
current collector
pellet
electrochemical cell
cell according
Prior art date
Application number
PCT/US1997/007005
Other languages
French (fr)
Inventor
Walter C. Sunderland
Anthony W. Rorvick
Donald R. Merritt
Craig L. Schmidt
David P. Haas
Original Assignee
Medtronic, 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 Medtronic, Inc. filed Critical Medtronic, Inc.
Priority to DE69709643T priority Critical patent/DE69709643T2/en
Priority to EP97925415A priority patent/EP0910872B1/en
Publication of WO1997041608A1 publication Critical patent/WO1997041608A1/en

Links

Classifications

    • 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/76—Containers for holding the active material, e.g. tubes, capsules
    • H01M4/762—Porous or perforated metallic containers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/191—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/533—Electrode connections inside a battery casing characterised by the shape of the leads or tabs
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N1/00—Electrotherapy; Circuits therefor
    • A61N1/18—Applying electric currents by contact electrodes
    • A61N1/32—Applying electric currents by contact electrodes alternating or intermittent currents
    • A61N1/36—Applying electric currents by contact electrodes alternating or intermittent currents for stimulation
    • A61N1/372—Arrangements in connection with the implantation of stimulators
    • A61N1/375—Constructional arrangements, e.g. casings
    • A61N1/3758—Packaging of the components within the casing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
    • H01M50/609—Arrangements or processes for filling with liquid, e.g. electrolytes
    • H01M50/627—Filling ports
    • H01M50/636—Closing or sealing filling ports, e.g. using lids
    • 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
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H01M6/12—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with flat electrodes
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making

Definitions

  • This invention relates to an electrochemical cell, a current
  • the invention relates to a hermetically sealed cell having a reactive
  • the electrochemical cell may be
  • a known method of making a cathode pellet is to
  • PTFE polytetrafluroethylene
  • cathode current collector and the cathode material.
  • cathode material One known
  • the volume of the cathode typically expands as the
  • cathode is discharged. This expansion of the cathode can cause
  • a cathode assembly which includes a support ring into
  • an object of the present invention to provide an
  • the cathode assembly includes a ring-shaped current
  • the cathode current collector circumferentially
  • the cathode is comprised of a
  • the housing may
  • the cathode current collector in one aspect of the invention, the cathode current collector
  • the cathode pellet can be a ring having an open top portion exposing the top surface of the cathode pellet and an open bottom portion exposing the
  • cathode material to maximize cathode capacity in the cell.
  • collector can have a non-circular shape such as a D-shape in
  • the reinforcement can be, for example, a
  • flange would be provided at the top portion or the bottom portion
  • the flange extends inwardly
  • the cell is provided with an insulator material which electrically separates the cathode material from the metal housing.
  • a connector tab can extend outwardly from the cathode
  • collector allows for construction of the electrochemical cell by a
  • the current collector is formed and placed into a circumferentially fitting die where the cathode material can
  • cathode current collector The combined cathode current
  • collector and cathode material can then be placed as a unit into
  • current collector ring can be provided with an outward bend to
  • This method is particularly useful when assembling a cell with a pocket-like, D-shaped housing
  • collector allows for the use of an alternative connection to a
  • FIG. 1 shows a cross-sectional, elevational view of the cell.
  • FIG. 2 shows a cross-sectional, side view of the cell along line 2-
  • FIG. 3 shows an elevational view of the non-circular ring current
  • FIG. 4 shows a cross-sectional view, along line 4-4, of the
  • FIG. 1 a cell 1 according to the invention is shown
  • the housing cover 15 is placed in the open
  • housing body 10 end of housing body 10 and is hermetically sealed to the housing
  • the housing cover 15 has an opening 20 to allow a
  • the housing cover 15 also has a fill
  • housing cover 15 is welded to the housing body 10. After the cell 1 is
  • the cell 1 can include an organic solvent in combination with an
  • the organic solvent can be, for example, diethyl
  • low viscosity cosolvents such as tetrahydrofuran (THF)
  • THF tetrahydrofuran
  • DME dimethoxyethane
  • DMI dimethyl isoxazole
  • the ionizing solute can be a simple or double
  • LiBF 4 LiAsF ⁇ , LiPF ⁇ , LiCI0 4 ,
  • FIG. 2 shows various elements contained within the housing
  • An anode layer 40 of an active metal is pressed onto a thin
  • anode current collector 45 comprised of a conducting metal such as
  • materials can include, for example, aluminum, the alkali metals,
  • alkaline earth metals and alloys of alkali metals or alkaline earth are alkaline earth metals and alloys of alkali metals or alkaline earth
  • materials are lithium, sodium, potassium, calcium and alloys thereof.
  • a cathode assembly including a cathode pellet 55 and
  • cathode current collector 60 is spaced apart from the anode layer
  • separator 50 which is comprised of a porous or a microporous
  • separator 50 completely surrounds and seals the anode 40 and
  • the reactive cathode material is a which
  • Manganese dioxide is one such material.
  • manganese dioxide including vanadium oxide (V2O5), silver
  • vanadium oxide (Ag2V 4 On) carbon monoflouride, C0O2, Ni ⁇ 2, and
  • the cathode pellet 55 may include binders and conductivity
  • binders may comprise between
  • cathode pellet 55 while the conductive material may comprise
  • cathode materials used to make the cathode pellet 55 are in finely
  • a lining material 65 such as polyethylene, electrically insulates
  • the lining material 65 can be provided in a thin, molded pocket-shaped item or a porous or microporous material which fits
  • the cathode current collector 60 has a
  • the cathode current collector 60 is comprised of a wall 80
  • flange 65 is to provide a reinforcing means which will retain the
  • the reinforcing means may also include
  • the current collector 60 preferably has a uniform width, as
  • the cathode current collector 60 comprising an electrically
  • the rectangular tab can then be bent perpendicularly to create the electrical connector tab 75 of the
  • the cathode current collector 60 is
  • the manganese dioxide For example, Mn ⁇ 2, CF X , V2O5, and a silver
  • vanadium oxide e.g. Ag2V 4 On
  • Ag2V 4 On vanadium oxide
  • FIG. 4 provides ⁇ cross-section ⁇ l view of the cathode current
  • collector 60 including the wall 80 with rim portion 70 and inward
  • the connector tab 75 has a flat surface 85 which is
  • One end of the conductor may be
  • cathode current collector The electrical connections can be made

Abstract

An electrochemical cell has a cathode material formed into a pellet shape which expands as the cell is discharged. A cathode current collector circumferentially surrounds the cathode pellet and is in contact with the peripheral edge of the cathode pellet to prevent peripheral cathode expansion. The peripheral cathode current collector maintains a stable cell impedance during cell discharge.

Description

ELECTROCHEMICAL CELL
BACKGROUND OF THE INVENTION
This invention relates to an electrochemical cell, a current
collector for the cell and a method for cell construction. In particular,
the invention relates to a hermetically sealed cell having a reactive
cathode and a lithium anode. The electrochemical cell may be
used to power body implantable medical devices such as heart
pacemakers.
In constructing an electrochemical cell for use in implantable
medical devices, a known method of making a cathode pellet is to
compress a mixture of powdered metal oxide, a conductive matrix
such as graphite or carbon black and a binding material such as
polytetrafluroethylene (PTFE). In such a cell, it is essential for uniform
discharge of the cell to maintain good contact between the
cathode current collector and the cathode material. One known
way of providing such contact is to imbed the current collector inside the cathode powder mixture and then compress the mixture into a
pellet.
A drawback of imbedding the current collector in the cathode
material is that the volume of the cathode typically expands as the
cathode is discharged. This expansion of the cathode can cause
degradation of the contact between the cathode and the current
collector, causing changes in overall cell impedance as the cell is
discharged. During latter stages of discharge, contact degradation
may cause such an increase in impedance that it causes a
significant decrease in cell capacity. Since high reliability in a
surgically implanted medical device is essential, an unexpected
reduction in cell capacity means that the device must be surgically
removed and replaced much earlier than usual.
It should be understood that not all cells with imbedded
current collectors will undergo a dramatic impedance increase that
requires replacement of the cell. However, even without the
problem of early cell replacement, the variability of cell impedance
complicates the use of the cell. Powering critical implantable
medical devices such as pacemakers, neurostimulators and drug
infusing pumps, requires compactness and efficiency of circuit design. If the cells used are too variable in their output, the device
would need to be larger and less efficient since the circuits must
either increase in complexity to compensate for the output variability
or must include capacitors which can provide additional energy
storage.
Of course, it is known to provide cathodes without imbedded
current collectors. For example, U.S. Patent 3,440,1 10 issued to Arbter
discloses a cathode assembly which includes a support ring into
which a cathode material is pressed. This cathode assembly is then
pressed into intimate contact with the bottom of the cell housing so
that the housing itself can contact the cathode material and act as
a current collector. However, in a high reliability electrochemical cell
for use in critical medical device applications, reliance on this
contact between the cathode and the case can still raise a concern
about undesirable impedance variations.
It is, therefore, an object of the present invention to provide an
electrochemical cell in which a cathode material which is subject to
swelling during discharge has a current collector which will obviate
cell impedance variability. SUMMARY OF THE INVENTION
We have discovered an electrochemical cell having a metal
housing and an anode and cathode within the metal housing in
which the cathode assembly includes a ring-shaped current
collector into which the cathode material is pressed. The cathode
is formed into a pellet shape with a flat top surface, a flat bottom
surface and a peripheral edge extending between the top and
bottom surfaces. The cathode current collector circumferentially
surrounds the cathode pellet and is in contact with the peripheral
edge of the cathode pellet. Since the cathode is comprised of a
material which expands as the cell is discharged, the expansion of
the cathode material against the confining ring-shaped current
collector will serve as a stable connection between the current
collector and the cathode material. The current collector is then
electrically connected to the metal housing to allow current flow
between the current collector and housing. The housing may
therefore be used as one terminal of the cell.
In one aspect of the invention, the cathode current collector
can be a ring having an open top portion exposing the top surface of the cathode pellet and an open bottom portion exposing the
bottom surface of the cathode pellet. Since neither the top nor
bottom portions of the cathode pellet are confined by the current
collector, the expansion of the cathode material during discharge
may be distributed more evenly on both sides of the ring. Also,
another advantage for the open ring shape is that it allows the
entire thickness of the cathode assembly to be filled with reactive
cathode material to maximize cathode capacity in the cell.
In yet another aspect of the invention, the cathode current
collector can have a non-circular shape such as a D-shape in
which the ring is reinforced in order to maintain its shape during
cathode discharge. The reinforcement can be, for example, a
flange extending around the ring or placed selectively at portions
of the ring which are susceptible to deformation. Typically, the
flange would be provided at the top portion or the bottom portion
of the current collector ring. Preferably, the flange extends inwardly
around the ring to assist in the retention of the cathode pellet but
still exposing the center portion of the cathode pellet.
In yet another aspect of the invention, the metal housing of the
cell is provided with an insulator material which electrically separates the cathode material from the metal housing. The ring-
shaped current collector then provides the connection to the
housing. A connector tab can extend outwardly from the cathode
current collector to a location remote from the cathode material
where it can be attached to the metal housing by welding or some
other means for providing electrical contact.
In yet another aspect of the invention, the ring-shaped current
collector allows for construction of the electrochemical cell by a
convenient method. The current collector is formed and placed into a circumferentially fitting die where the cathode material can
be pressed into a self-supporting pellet which is retained within the
cathode current collector. The combined cathode current
collector and cathode material can then be placed as a unit into
the metal housing of the cell and electrically connected to a
portion of the metal housing. Also, a portion of the flange of the
current collector ring can be provided with an outward bend to
provide a tab to secure the current collector to the metal housing
at a portion of the housing that is not insulated. This would also
have the effect of making a stable electrical connection between
the current collector and the housing. This method is particularly useful when assembling a cell with a pocket-like, D-shaped housing
since the current collector assembly can be readily inserted into the
pocket of the housing and secured to the housing by welding at the
pocket opening.
In yet another aspect of the invention, the cathode current
collector allows for the use of an alternative connection to a
feedthrough pin which would allow the metal housing of the cell to
be used as a negative terminal for the cell (i.e. connecting the
anode to the metal housing and the cathode to a feedthrough pin)
or for the housing to be neutral with respect to the terminals of the
cell (i.e. the anode and cathode each connected to a feedthrough
pin) .
BRIEF DESCRIPTION OF DRAWINGS
The invention will be further described with reference to the
accompanying drawings, in which:
FIG. 1 shows a cross-sectional, elevational view of the cell.
FIG. 2 shows a cross-sectional, side view of the cell along line 2-
2 of FIG. 1. FIG. 3 shows an elevational view of the non-circular ring current
collector of FIG. 1.
FIG. 4 shows a cross-sectional view, along line 4-4, of the
current collector of FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1 , a cell 1 according to the invention is shown,
including a metal housing in two parts, a D-shaped cell housing body
10 and a housing cover 15, both comprised of a metal such as
stainless steel or titanium. The housing cover 15 is placed in the open
end of housing body 10 and is hermetically sealed to the housing
body 10 with a laser weld around the entire edge of the housing
cover 15. The housing cover 15 has an opening 20 to allow a
conducting pin 25 to be externalized through a feedthrough with a
glass seal 28 which insulates the pin 25 from the housing cover 15 and
hermetically seals the opening 20. The housing cover 15 also has a fill
port 30 which allows filling of the cell 1 with an electrolyte after the
housing cover 15 is welded to the housing body 10. After the cell 1 is
charged with a liquid electrolyte, a disc 35 is welded into the fill port 30 to provide α hermetic seal. The liquid electrolyte charged into
the cell 1 can include an organic solvent in combination with an
ionizing solute. The organic solvent can be, for example, diethyl
carbonate, dimethylcarbonate, butylene carbonate,
3-methyl-2-oxazolidone, sulfolane, tetrahydrofuran, methyl-substituted
tetrahydrofuran, 1 ,3-dioxolane, propylene carbonate (PC), ethylene
carbonate, gamma -butyrolactone, ethylene glycol sulfite,
dimethylsulfite, dimethyl sulfoxide or mixtures thereof and also, for
example, low viscosity cosolvents such as tetrahydrofuran (THF),
methyl-substituted tetrahydrofuran (Met-THF), dioxolane (DIOX),
dimethoxyethane (DME), dimethyl isoxazole (DMI), diethyl
carbonate(DEC), ethylene glycol sulfite (EGS), dioxane, dimethyl
sulfite (DMS) or the like. The ionizing solute can be a simple or double
salt or mixtures thereof, for example, LiBF4, LiAsFό, LiPFό, LiCI04,
LiN(SOCl2)3, or UC(Sθ2CF3)2, which will produce an ionically
conductive solution when dissolved in one or more solvents.
FIG. 2 shows various elements contained within the housing
body 10. An anode layer 40 of an active metal is pressed onto a thin
anode current collector 45 comprised of a conducting metal such as
stainless steel, nickel or titanium. One end of the pin 25 is attached by welding to the anode current collector 45. Active metal anode
materials can include, for example, aluminum, the alkali metals,
alkaline earth metals and alloys of alkali metals or alkaline earth
metals with each other and other metals. The preferred anode
materials are lithium, sodium, potassium, calcium and alloys thereof.
A cathode assembly, including a cathode pellet 55 and
cathode current collector 60 is spaced apart from the anode layer
40 by separator 50 which is comprised of a porous or a microporous
material, preferably polypropylene or polyethylene. The
separator 50 completely surrounds and seals the anode 40 and
anode current collector 45. The reactive cathode material is a which
will swell upon discharge. Manganese dioxide is one such material.
Other suitable cathode materials could be used instead of
manganese dioxide, including vanadium oxide (V2O5), silver
vanadium oxide (Ag2V4On) carbon monoflouride, C0O2, Niθ2, and
TiS2. The cathode pellet 55 may include binders and conductivity
enhancers in addition to the reactive cathode material. Binders
which may be typically employed in the cathode of the present
invention are polytetrafluoroethylene, ethylene/propylene
copolymers and the like. Representative of the conductive materials which may be employed as a conductivity enhancer are graphite,
carbon and the like. In a cathode pellet 55 having manganese
dioxide as the reactive component, binders may comprise between
about 1 and about 10 weight percent, preferably between about 1
and about 5 weight percent, of the cathode mix used to make the
cathode pellet 55 while the conductive material may comprise
between about 1 and about 12 weight percent, preferably between
about 3 and about 10 weight percent, of the cathode mix. The solid
cathode materials used to make the cathode pellet 55 are in finely
divided form so they can be intimately mixed. The cathode mixture
may then be pressed into the cathode current collector 60 such that
a self supporting cathode pellet 55 is formed within the current
collector with peripheral edges of the cathode pellet 55 pressed into
intimate contact with the current collector 60. The intimate contact
of the current collector 60 around the cathode pellet 55 has the
effect of confining the cathode pellet 55 from expanding in diameter
as the cathode pellet 55 expands in volume during cell discharge.
A lining material 65, such as polyethylene, electrically insulates
the anode 40 and cathode pellet 55 from the interior of the housing
body 10. The lining material 65 can be provided in a thin, molded pocket-shaped item or a porous or microporous material which fits
closely within the housing body 10. The cathode current collector 60
is electrically connected to the housing body 10 at connector tab 75
which is welded to the housing cover 15.
Referring now to FIG. 3, the cathode current collector 60 has a
generally D-shaped outline that is partly semicircular and partly
polygonal. The cathode current collector 60 is comprised of a wall 80
with a rim portion 70 and an flange portion 65. The purpose of the
flange 65 is to provide a reinforcing means which will retain the
shape of the cathode current collector 60 as the cathode pellet
expands. Accordingly, the reinforcing means may also include
internal or external flanges or a thickened portion of the cathode
current collector 60 or other known means for retaining a shape. As
in FIG 3, the current collector 60 preferably has a uniform width, as
measured from the rim portion 70 to the inward flange 65.
The cathode current collector 60, comprising an electrically
conductive material such as stainless steel or titanium, can be
formed by stamping a metal sheet into a cup, cutting excess steel or
titanium sheet around the cup but leaving a rectangular tab on a
straight edge of the cup. An aperture can then be punched out at the bottom of the cup forming the inward flange 65 portion of the
curent collector 60. The rectangular tab can then be bent perpendicularly to create the electrical connector tab 75 of the
current collector 60.
After the cathode current collector 60 is formed, a collector-
cathode assembly is made. The cathode current collector 60 is
placed in a closely fitting die fixture such that the die maintains the
shape of the cathode current collector 60 as the collector-cathode
assembly is made. A measured amount of cathode mixture
comprising powdered manganese dioxide, an inert binding material
such as PTFE and conductivity enhancer such as graphite or carbon
black is placed into the die inside the current collector. The cathode
mixture is compressed in a press within the cathode current collector
60 to form a self-supporting cathode pellet 55 having opposite, flat
surfaces exposed. It will be appreciated by those skilled in the art
that other active cathode materials which cause the cathode pellet
55 to expand as the cell is discharged could be used in in place of
the manganese dioxide. For example, Mnθ2, CFX, V2O5, and a silver
vanadium oxide (e.g. Ag2V4On) could be used alone or in
combination as active cathode materials in the present invention. FIG. 4 provides α cross-sectionαl view of the cathode current
collector 60, including the wall 80 with rim portion 70 and inward
flange portion 65. The connector tab 75 has a flat surface 85 which is
electrically connected to the housing cover 15.
As an alternative embodiment of the invention, the connector
tab 75 on the cathode current collector 60 can be electrically
connected to the housing 10 or the cover 15 via a separate,
intervening conductor. One end of the conductor may be
electrically connected to the housing cover 15. The other end of the
conductor is electrically connected to the connector tab 75 of the
cathode current collector. The electrical connections can be made
by welding.
In yet another embodiment of the invention, a case negative
version of the cell (i.e. with the case at the anode potential) can be
easily made by connecting the anode current collector 45 to the
metal housing cover 15 by a tab similar to the connector tab 75 on
the cathode current collector 60 and the anode curent collector to
the conducting pin 25. Also, a case neutral version of the cell (i.e.
with the case at neither the anode or cathode potential) can be
made by adding a second conductive pin to the feedthrough or adding a second feedthrough so that each of the current collectors
45, 60 can be connected to a separate conductor pins passing
through the metal housing.
It will be appreciated by those skilled in the art that while the
invention has been described above in connection with particular
embodiments and examples, the invention is not necessarily so
limited and that numerous other embodiments, examples, uses,
modifications and departures from the embodiments, examples and
uses may be made without departing from the inventive concepts.

Claims

We claim:
1 . An electrochemical cell comprising:
(a) a metal housing;
(b) an anode;
(c) a cathode in operative relation to the anode, the cathode
comprised of a material which expands as the cell is discharged,
the cathode formed into a pellet shape having a flat top
surface, a flat bottom surface and a peripheral edge extending
between the top and bottom surfaces;
(d) a cathode current collector circumferentially surrounding
said cathode pellet and in contact with the peripheral edge of
the cathode pellet; and
(e) means for electrically connecting the cathode current
collector to the metal housing.
2. An electrochemical cell according to claim 1 wherein the
cathode current collector is a non-circular ring having an open top
portion exposing the top surface of the cathode pellet and an
open bottom portion exposing the bottom surface of the cathode pellet, and reinforcement means for retaining the non-circular
shape of the current collector.
3. An electrochemical cell according to claim 2 wherein said
reinforcement means comprises a flange at the top portion or
bottom portion of the current collector.
4. An electrochemical cell according to claim 3 wherein the flange
is inwardly extending and forming an exposure of a portion of the
cathode pellet.
5. An electrochemical cell according to claim 1 wherein said
means for electrically connecting includes a connector tab
extending outward from contact with the cathode current
collector.
6. An electrochemical cell according to claim 5 wherein the
means for electrically connecting includes a weld extending
between the connector tab and the metal housing.
7. An electrochemical cell according to claim 1 wherein the
cathode material includes a metal oxide powder as an active
cathode material.
8. An electrochemical cell comprising:
(a) a metal housing;
(b) an anode;
(c) a cathode in operative relation to the anode, the cathode
comprised of a powder as an active cathode material the
cathode formed into a pellet shape having a flat top surface, a
flat bottom surface and a peripheral edge extending between
the top and bottom surfaces;
(d) a cathode current collector circumferentially surrounding
said cathode pellet and in contact with the peripheral edge of
the cathode pellet, wherein the cathode current collector has
an open top portion exposing the top surface of the cathode
pellet and σn open bottom portion exposing the bottom surface
of the cathode pellet;
(e) an insulator member insulating the metal housing from
contact with the cathode pellet; and (f) means for electrically connecting the cathode current
collector to the metal housing.
9. An electrochemical cell according to claim 8 wherein the
cathode current collector includes reinforcement means for
maintaining the shape of the cathode current collector
10. An electrochemical cell according to claim 9 wherein said
reinforcement means comprises a flange on the current collector.
1 1 . An electrochemical cell according to claim 10 wherein the
flange is inwardly extending and forming an exposure of a portion
of the cathode pellet.
12. An electrochemical cell according to claim 8 wherein said
means for electrically connecting includes a connector tab
extending outward from contact with the cathode current
collector.
13. An electrochemical cell according to claim 12 wherein the
means for electrically connecting includes a conductor weld
extending between the connector tab and the metal housing.
14. A method for constructing an electrochemical cell comprising
the steps of:
(a) forming a metal current collector in a closed ring shape;
(b) forming a metal housing;
(c) placing the formed current collector into a circumferentially
fitting die;
(d) placing an amount of a powdered cathode material into
the die and current collector;
(e) pressing the cathode material into a self-supporting pellet
shape such that the current collector circumferentially surrounds
the pellet in a cathode assembly;
(f) placing the cathode assembly into the housing; and
(g) electrically connecting the cathode current collector to the
metal housing.
15. The method according to claim 14 wherein the metal current
collector is formed by the steps of:
(a) stamping a metal sheet into a cup shape; and
(b) punching an aperture centrally in said cup shape to leave
an upstanding edge and inwardly directed flange.
16. The method according to claim 15 further comprising the step
of bending a portion of said upstanding edge outwardly to form a
connector tab.
17. The method according to claim 14 further comprising the step
of placing an insulator member into the metal housing to insulate
the metal housing from contact with the cathode pellet.
18. An electrochemical cell comprising:
(a) a metal housing;
(b) an anode;
(c) a cathode in operative relation to the anode, the cathode
comprised of a material which expands as the cell is discharged,
the cathode formed into a pellet shape having a flat top surface, a flat bottom surface and a peripheral edge extending
between the top and bottom surfaces;
(d) a cathode current collector circumferentially surrounding
said cathode pellet and in contact with the peripheral edge of
the cathode pellet;
(e) a feedthrough with an insulated, electrically conductive pin
extending through a portion of the metal housing; and
(f) means for electrically connecting the cathode current
collector to the feedthrough pin.
19. An electrochemical cell according to claim 18 wherein the
cathode current collector is a non-circular ring having an open top
portion exposing the top surface of the cathode pellet and an
open bottom portion exposing the bottom surface of the cathode
pellet, and reinforcement means for retaining the non-circular
shape of the current collector.
20. An electrochemical cell according to claim 19 wherein said
reinforcement means comprises a flange at the top portion or
bottom portion of the current collector.
21 . An electrochemical cell according to claim 20 wherein the
flange is inwardly extending and forming an exposure of a portion
of the cathode pellet.
22. An electrochemical cell according to claim 18 wherein said
means for electrically connecting includes a connector tab
extending outward from contact with the cathode current
collector.
23. An electrochemical cell according to claim 22 wherein the
means for electrically connecting includes a weld extending
between the connector tab and the feedthrough pin.
24. An electrochemical cell according to claim 18 wherein the
cathode material is a powder.
25. An electrochemical cell comprising:
(a) a metal housing;
(b) an anode; (c) α cathode in operative relation to the anode, the cathode
comprised of a powder, the cathode formed into a pellet shape
having a flat top surface, a flat bottom surface and a peripheral
edge extending between the top and bottom surfaces;
(d) a cathode current collector circumferentially surrounding
said cathode pellet and in contact with the peripheral edge of
the cathode pellet, wherein the cathode current collector has
an open top portion exposing the top surface of the cathode
pellet and an open bottom portion exposing the bottom surface
of the cathode pellet;
(e) an insulator member insulating the metal housing from
contact with the cathode pellet;
(f) a feedthrough with an insulated, electrically conductive pin
extending through a portion of the metal housing; and
(g) means for electrically connecting the cathode current
collector to the feedthrough pin.
26. An electrochemical cell according to claim 25 wherein the
cathode current collector includes reinforcement means for
maintaining the shape of the cathode current collector
27. An electrochemical cell according to claim 26 wherein said
reinforcement means comprises a flange on the current collector.
28. An electrochemical cell according to claim 27 wherein the
flange is inwardly extending and forming an exposure of a portion
of the cathode pellet.
29. An electrochemical cell according to claim 25 wherein said
means for electrically connecting includes a connector tab
extending outward from contact with the cathode current
collector.
30. An electrochemical cell according to claim 29 wherein the
means for electrically connecting includes a weld extending
between the connector tab and the feedthrough pin.
31. A method for constructing an electrochemical cell comprising
the steps of:
(a) forming a metal current collector in a closed ring shape; (b) forming α metal housing having a conductive feedthrough
pin extending therethrough;
(c) placing the formed current collector into a circumferentially
fitting die;
(d) placing an amount of a powdered cathode material into
the die and current collector;
(e) pressing the cathode material into a self-supporting pellet
shape such that the current collector circumferentially surrounds
the pellet in a cathode assembly;
(f) placing the cathode assembly into the housing; and
(g) electrically connecting the cathode current collector to the
feedthrough pin.
32. The method according to claim 31 wherein the metal current
collector is formed by the steps of:
(a) stamping a metal sheet into a cup shape; and
(b) punching an aperture centrally in said cup shape to leave
an upstanding edge and inwardly directed flange.
33. The method according to claim 32 further comprising the step
of bending a portion of said upstanding edge outwardly to form a
connector tab.
34. The method according to claim 31 further comprising the step
of placing an insulator member into the metal housing to insulate
the metal housing from contact with the cathode pellet.
35. An electrochemical cell comprising:
(a) a titanium housing;
(b) a lithium anode;
(c) a cathode in operative relation to the anode, the cathode
comprised of silver vanadium oxide cathode material, the
cathode formed into a pellet shape;
(d) a cathode current collector circumferentially surrounding
said cathode pellet; and
(e) means for electrically connecting the cathode current
collector to the titanium housing.
36. An electrochemical cell according to claim 35 wherein the
cathode current collector is a non-circular ring having an open top
portion exposing the top surface of the cathode pellet and an
open bottom portion exposing the bottom surface of the cathode
pellet, and reinforcement means for retaining the non-circular
shape of the current collector.
37. An electrochemical cell according to claim 36 wherein said
reinforcement means comprises a flange at the top portion or
bottom portion of the current collector.
38. An electrochemical cell according to claim 37 wherein the
flange is inwardly extending and forming an exposure of a portion
of the cathode pellet.
39. An electrochemical cell according to claim 35 wherein said
means for electrically connecting includes a connector tab
extending outward from contact with the cathode current
collector.
40. An electrochemical cell according to claim 39 wherein the
means for electrically connecting includes a weld extending
between the connector tab and the metal housing.
41. An electrochemical cell according to claim 35 further
comprising an electrolyte having an aprotic organic solvent and a
solute selected from the group consisting of UCF3SO3, Li(Sθ3)(CF3)3,
UBF4, LiAsFό, LiPFό, LiCI04, imide and methide.
PCT/US1997/007005 1996-04-26 1997-04-25 Electrochemical cell WO1997041608A1 (en)

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Also Published As

Publication number Publication date
DE69709643D1 (en) 2002-02-21
EP0910872B1 (en) 2002-01-16
EP0910872A1 (en) 1999-04-28
US6132896A (en) 2000-10-17
DE69709643T2 (en) 2002-08-14
US5716729A (en) 1998-02-10

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