Note: Descriptions are shown in the official language in which they were submitted.
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MULTI-LAYER ELECTROCHEMICAL CELL DEVICES
BACKGROUND OF THE INVENTION
s The present invention generally relates to bonded mufti-layer, flat-
plate electrochemical cell devices, such as rechargeable batteries and
supercapacitors. More specifically, the invention describes such devices
having persistent interfacial bonding between laminated planar electrode
and microporous separator members utilized in such electrochemical
z o devices wherein the bonding may be acheived at low-temperatures.
Widely deployed primary and secondary, rechargeable lithium-ion
battery cells are typical of electrochemical devices to which the present
invention is directed. Such cells comprise layers, or membranes, of
respective positive and negative electrode compositions assembled with a
coextensive interposed layer, or membrane, of electrically-insulating,
ion-transmissive separator material. This mufti-layer battery cell structure
is normally packaged with a mobile-ion electrolyte composition, usually in
fluid state and situated in part in the separator membrane, in order to
2 o ensure essential ionic conductivity between the electrode membranes
during charge and discharge cycles of the battery cell.
One type of separator for this purpose is a microporous polyolefin
membrane, either of single- or mufti-layer structure, described, for
2s example, in U.S. Patents 5,565,281 and 5,667,911. When employed as
rechargeable battery cell separators, these porous membranes not only
effectively retain within their porous structure the essential fluid cell
electrolyte compositions, but they also provide an additional advantage in
that they possess an automatic cell "shut-down" feature that prevents
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uncontrolled heat buildup within the battery cell which might otherwise
result, for instance during excessive cell recharging, in a dangerous
explosive condition. This built-in safety mechanism occurs because the
melting point range of the polyolefins utilized in the fabrication of the
s separator membranes is at the lower end of the danger zone of battery cell
heat buildup. Thus, in the event of a run-away cell heating episode, the
porous polyolefin separator membrane becomes heated to a point of
melting and its pore structure collapses, thereby interrupting the essential
ionic conductivity within the cell and terminating the electrochemical
z o reaction before a dangerous condition ensues.
The packaging of battery cell structures has heretofore regularly
taken the form of a metal "can", whether, for example, in elongated tubular
or flattened prismatic shape, which has commonly been relied upon to not
1 s only contain the electrolyte component, but also to impart the significant
stack pressure required to maintain close physical contact between the
individual cell electrodes and the interposed separator member. This
intimate contact, along with the composition of the electrolyte, is, as
previously noted, essential to efficient ion transmission between electrodes
2 o during operation of the battery cell.
More recently, however, the profusion and continued
miniaturization of electronic devices powered by Li-ion batteries and
similar energy storage cells has generated a demand for a greater number
2 s of cell package shapes and dimensions, e.g., relatively broad, yet thin,
lightweight packages having a significant degree of flexibility. For
example, numerous end-use applications make thin, flexible envelope-style
packages of polymer film more desirable than the prior rigid-walled high-
pressure can containers. However, these more flexible packages are
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decreasingly capable of achieving and maintaining the substantial physical
pressures required to ensure the noted essential intimate inter-layer contact
throughout the battery cell.
s In order to minimize the deleterious effect of degraded physical
stack pressure previously relied upon to establish the necessary contact
between cell layers, developers have progressed to the use of direct
laminated adhesive bonding between electrode and separator layers to
ensure their essential intimate contact. Typical of such innovations are
Zo battery cells utilizing polymer-based layer members, such as described in
U.S. Patents 5,456,000 and 5,460,904. In those fabrications, polymer
compositions, preferably of poly(vinylidene fluoride) copolymers, which
are compatible with efficient fluid electrolyte compositions are utilized in
the physical matrix of both the electrode and the separator members to not
is only promote essential ionic conductivity, but also to provide a common
composition component in those cell members which promotes strong
interfacial adhesion between them within a reasonably low laminating
temperature range. Such laminated, multilayer polymeric battery cells
operate effectively with stable, high-capacity performance even though
2 o packaged in flexible, lightweight polymeric film enclosures.
Although such laminated battery cells, and like energy storage
devices, have significantly advanced the art in miniaturized applications,
the use of substantially non-porous polymeric matrices and membranes in
2 s their fabrication has deprived these devices of the desirable shut-down
feature achieved when using the microporous polyolefin separator
membranes. However, the high surface energy exhibited by the polyolefin
membranes renders them highly abherent in nature and thus prevents their
strong, permanent adhesion to electrode layer compositions, particularly
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within a reasonable temperature range which does not lead to melting or
thermal collapse of the porous structure of the polyolefin membranes.
Some attempts have been made by electrochemical cell fabricators
to combine, by simple solution overcoating or extrusion, the shut-down
properties of porous separator membranes with the laminate adhesive
properties of polymer compositions, for example, as described in U.S.
Patents 5,837,015 and 5,853,916. However, it has generally been found
that the overcoating compositions significantly occlude or otherwise
1 o interfere with the porous structure of the polyolefin membranes and cause
a deleterious decrease in electrolyte mobility and ionic conductivity.
Further, the addition of substantial amounts of overcoating materials,
increases the proportion of non-reactive components in a cell, thereby
detracting from the specific capacity of any resulting energy storage
device.
As an alternative approach to enabling the incorporation of
microporous separator membranes into a laminated electrochemical cell
structure, an attempt to modify the surface of the polyolefin membrane by
2 o application of a minimal layer of polymer composition has been made.
The polymer composition would not be of such excessive thickness as to
occlude the porosity of the membrane, but rather would provide an
intermediate transition in compatibility to the matrix polymer of preferred
electrode cell layer compositions. Thus, for example, a thin layer from a
2 5 dilute solution of poly(vinylidene fluoride) copolymer is applied to the
microporous separator membrane when the membrane is intended to be
employed in the fabrication of a battery cell by thermal lamination with
electrodes comprising active compositions of a similar polymers. This
modification has proven to be insufficient in itself to enable satisfactory
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interfacial bonding between cell component layers at lamination
temperatures below the critical level which results in collapse of separator
porosity and its attendant loss of effective ionic conductivity and desirable
shut-down capability.
Therefore, there remains a need in the art to provide improved
bonded high-capacity, shut-down protected, electrochemical cells through
the use of surface-modified microporous separator membranes. There also
remains a need in the art for improved electrochemical cells which utilize
1 o surface-modified microporous separator membranes.
SUMMARY OF THE INVENTION
The present invention provides bonded high-capacity, shut-down
15 protected, electrochemical cells through the use of surface-modified
microporous separator membranes and also provides improvements in
surface-modified microporous separator membranes for use in such
electrochemical cells.
2 o More particularly, the present invention comprises electrochemical
cells which have been bonded at laminating temperatures which effect firm
interfacial bonding between electrode and separator layers, yet are
sufficiently low to avoid thermal collapse or other occlusion of the porous
structure of the separator membranes, through the use of surface-modified
2 s microporous polyolefin separator membranes. The present invention helps
prevent loss of essential ionic conductivity and maintains thermal
shut-down capability.
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In general, the present invention comprises initially applying to a
surface-modified separator membrane a dilute solution of a primary
plasticizer for the surface-modifying, polymeric membrane coating in a
volatile organic solvent, and removing the volatile solvent, such as by
evaporation in air, to deposit the plasticizer in the pores of the separator.
The cell is further processed by applying an electrode to each surface of the
surface-modified separator membrane; applying a moderate amount of heat
and pressure to the multi-layer assembly to affect bonding; and removing
any residual plasticizer from the assembly by heat and/or reduced pressure.
to
The treatment solution is preferably made up of about 10% to 30%
of the plasticizer, and more preferably about 15% to 20% plasticizer.
Useful plasticizers are moderately volatile and include alkylene carbonates,
dialkyl phthalates, dialkyl succinates, dialkyl adipates, dialkyl sebacates,
15 trialkyl phosphates, polyalkylene glycol ethers and mixtures thereof. The
organic solvent is selected to be significantly more volatile than the
plasticizer and to exhibit limited solvency toward the surface-modifying
polymer of the separator membrane. Lower alcohols, ketones, esters,
aliphatic hydrocarbons, halogenated solvents, chlorinated hydrocarbons,
2 o chlorinated fluorocarbons, and mixtures thereof are all useful. A
sufficient
amount of the plasticizer solution is applied to the membrane to ensure
some significant intake of the solution within the pores of the membrane.
The treatment solution may be applied by any appropriate method, such as
coating, immersion or spraying.
Electrode membranes may be in the form of highly densified
polymeric electrodes deposited on metal-foil current collectors, such as
those used in liquid-electrolyte Li-ion cells, and/or densified and non-
extracted and/or extracted plastic Li-ion electrodes such as those disclosed
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in U.S. Pat. Nos. 5,418,091; 5,429,891; 5,456,000; 5,460,904; 5,540,741;
5,571,634; 5,587,253; 5,607,485; wherein preferably at least one electrode
has a reticulated metal current collector in the form of an expanded-metal
grid, mesh, metallic non-woven material, etched foil or perforated foil.
Following application of the plasticizer/solvent solution, the
volatile solvent is removed, such as by evaporation, which results in the
deposition of the plasticizer superficially on the surface and in the pores of
the separator membrane. The coated separator membrane is thereafter
1 o assembled in the usual manner between positive and negative electrode
layers or membranes and the assemblage is laminated, e.g., between heated
pressure rollers, at a temperature and pressure which does not significantly
effect the porous structure; i.e. a temperature below the shutdown
temperature, of the separator membrane. For example, lamination may be
15 carried out between 70°C and 120°C, and preferably between
90°C and
110°C, and more preferably at about 100°C, and with a linear
load between
and 40 pounds per linear inch (lb/in) and more preferably between 20
and 30 lb/in. Advantageously, when processed in these temperature and
pressure ranges, the deposited plasticizer now resident in and about the
2 o porous separator membrane exhibits its solvency toward and softens the
surface-modifying polymer of the separator membrane, as well as the
contiguous surface of the compatible electrode matrix polymer, and a close
adhesive/ cohesive bond is formed between the electrode and separator
membrane interfaces.
A minor amount of plasticizer insufficient to disrupt the modifying
polymer layer may reside on the surface of the membrane at the outset of
the lamination operation, however, a greater amount is forced from the
pores of the separator membrane under the pressure of lamination and
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provides sufficient softening of the polymer interfaces to effect a deep
intermingling of the surface polymers of the electrode and separator
membranes. Subsequent to the lamination, and influenced by the slowly
dissipating heat of the laminating operation, the remaining plasticizer
volatilizes to promote a strong, unsoftened polymer bond at the electrode
and separator membrane interfaces.
In and alternative embodiment of the present invention, the
moderately volatile primary plasticizer is included in the electrode polymer
1 o matrix composition and is available from that source at the electrode and
separator membrane interface to act upon the polymer layer of the
separator membrane during the laminating operation.
BRIEF DESCRIPTION OF THE DRAWING
The present invention will be described with reference to the
accompanying drawing of which:
FIG. 1 is a cross-sectional view of an assemblage of
2 o electrochemical cell members according to one embodiment of the present
invention, including a surface-modified microporous separator member, in
the process of being laminated; and
FIG. 2 is an enlarged cross-sectional view of a segment of the
microporous separator member of FIG. l, depicting in greater detail an
embodiment of the present invention.
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DESCRIPTION OF THE INVENTION
As shown in FIG. 1, the fabrication of a laminated electrochemical
cell typically comprises assembling a separator membrane or layer member
s 16, between a first electrode member 12, and a second electrode member
18, of opposite polarity to that of the first electrode member 12, and
applying heat and pressure in the direction of the arrows to soften the
polymeric electrode and separator compositions and bring the member
interfaces into intimate bonding contact to form a unitary, bonded laminate
1 o cell structure. The respective electrodes 12, 18, are often first formed
as
individual subassemblies by coating or laminating electrode composition
layers 13, 17, upon respective conductive current collector members 1 l,
19, such as metallic foils or reticulated grids. It is preferred that at least
one collector member comprise a reticulated grid to facilitate later fluid
15 fabrication operations, e.g., solvent or evaporative removal of electrode
composition plasticizer and insertion of electrolyte solution.
In particular, the composite electrodes appropriate for use in
electrochemical cells according to the present invention may be fabricated
2 o by first dissolving a polymeric binder material in an appropriate solvent,
adding powdered positive or negative electrode material and an
electronically conductive additive, then homogenizing the components to
obtain a smooth, homogeneous paste, and casting such paste on a carrier
substrate, a metallic foil, or reticulated current collector by any number of
2 s methods, such as meter bar or doctor-blade casting, die extrusion, screen
printing, transfer coating, and the like. In another variation, a non-volatile
plasticizer of said polymeric binder may also be included in the casting
preparation as a processing aid. After the volatile casting solvent is
removed by evaporation, the electrode composition is mechanically
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compacted and bonded to the appropriate metallic collector by calendering,
pressing, or lamination at elevated pressure and temperature conditions.
In the present invention, the separator member 16, is a commercial
microporous polyolefin membrane, such as marketed by Celgard LLC
under the trademark, Celgard, which has been modified by the
manufacturer to add a surface coating of polymer, e.g., a poly(vinylidene
fluoride) copolymer, which forms a thin coating of such polymer in and
about the surfaces of the myriad pores of the membrane structure, as
1 o shown in FIG. 2. The separator membrane 16, comprises a body portion
22, of polyolefin structure having pores 24, dispersed throughout that
ultimately contain electrolyte and establish the essential ionic conductivity
within the electrochemical cell, while also providing the heat-collapsible
shut-down safety feature of the cell. The separator membrane 16, is
modified by providing a coated film 26, of modifying polymer selected to
have compatibility with the preferred polymeric matrix materials utilized
in the cell electrode membranes. This modification is intended by the
manufacturer to enhance the ability of the polyolefin membrane to adhere
to cell electrode layers, however, this modification has been found to be
2 o unsuitable in many applications to enable a firm interfacial bond with
electrode membranes by a process of thermal lamination at temperatures
which are sufficiently low to avoid collapse of the porous structure of the
separator membrane and ultimate disruption of the desirable battery cell
shut-down feature.
The present invention overcomes the shortcomings noted above. In
particular, in accordance with one embodiment of the present invention,
the modified membrane is treated with a dilute solution of about 10% to
30% of a moderately volatile plasticizer in an inorganic solver, wherein the
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plasticizes is a primary plasticizes for the modifying polymer of the
separator membrane. The treated membrane is then dried to remove the
organic solvent and deposit a layer 28, of the plasticizes on the surfaces of
the modifying polymer film 26. A microporous separator membrane
treated in this manner may then be assembled with any of numerous
common polymeric electrode layers or membranes, such as shown in FIG.
l, and laminated with heat and pressure in readily available commercial
devices.
1 o Because of the in situ plasticizing effect of locally-deposited
plasticizes in layer 28, a laminating temperature well below the normal
softening point of the separator polyolefin body will be sufficient to
establish the desired permanent bond between electrodes and separator
without endangering the porous structure of the separator membrane. The
15 moderate volatility of the deposited plasticizes enables its dissipation
from
the laminate bond site over time with a resulting strengthening of the
adhesive bond.
The effective concentration of plasticizes in the membrane-coating
2 o solution may be readily varied depending upon the specific membrane-
modifying and electrode matrix polymers in the cell fabrication in order to
deposit the minimal optimum amount of plasticizes sufficient to promote
the adhesive/cohesive softening of the contiguous surfaces of the
modifying polymer of the separator membrane and electrode matrix
2 s polymers at temperatures safely below the flow temperature of the
polyolefin body of the separator membrane. The selection of a particular
plasticizes solution composition is well within the normal abilities of cell
fabrication technicians.
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In the alternative embodiment of the present invention, wherein the
plasticizer is included in the electrode polymer matrix composition, the
optimum proportion of plasticizer to be incorporated in the electrode
matrix composition is also within the skill of the cell fabrication
s technician.
The following examples are illustrative of the processes used in
accordance with the present invention and provide guidance to the
selection of useful combinations of ingredients and compositions for
1 o effective practice of the present invention. However, other embodiments
will be clear to the skilled artisan and certainly within the ability of the
skilled cell fabrication technician.
EXAMPLE 1
1 s Preparation of Plastic Cathode
74 g of commercial-grade LiCoO~, 8 g of poly(vinylidene
fluoride)-hexafluoropropylene (PVdF-HFP) copolymer (Kynar
PowerFLEX LBG, Elf Atochem), 5 g of Super P conductive carbon
(MMM, Belgium),13 g of dibutyl phthalate (DBP, Aldrich), and 150 ml
2 o acetone were homogenized and heated in a hermetically closed vessel for 1
hour at 45°C. After additional homogenization in a laboratory blender,
the
resulting paste was cast on a polyester carrier film using a doctor blade
apparatus gapped at about 0.3 mm. The acetone was evaporated in a
stream of warm air and the resulting self supporting film was removed
2 s from the carrier. A section of the film was used as a positive electrode
membrane and was laminated with a similarly sized section of aluminum
expanded metal grid (MicroGrid, Delker Corp.) using a heated double-roll
laminator at a temperature of about 145°C. In an ancillary operation
often
employed to enhance the absorption of electrolyte solution, the DBP
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plasticizer was extracted from the electrode membrane with hexanes at
room temperature and the resulting positive electrode member was
air-dried at about 70°C.
In an alternative embodiment, two electrode films formed by the above
s process were laminated on opposite surfaces of the aluminum grid using
the laminating process described above, to create a positive electrode
structure having an embedded aluminum collector layer.
A further alternative positive electrode member useful with the present
invention and typical of such members comprising many current
1 o commercial battery cells was similarly prepared from a composition of 90
g of LiCo02, 5 g of poly(vinylidene fluoride) homopolymer (Kynar 741,
Elf Atochem), 5 g of Super P carbon, and 60 ml of N-methyl pyrrolidone.
The resulting paste was coated on 0.03 mm aluminum foil at about 0.3
mm, dried in heated air, and the resulting coated foil calendered to about
15 0.1 mm thickness to form a positive electrode member. This electrode
alternative provided substantially the same physical and electrochemical
results when substituted for the foregoing electrode member in the
following examples.
2 o EXAMPLE 2
Preparation of Plastic Anode
70 g of MCMB 25-28 microbead mesophase artificial graphite (Osaka Gas
Co., Japan), 8 g of PvdF-HFP copolymer (Kynar PowerFLEX LBG, Elf
Atochem), 4 g of Super P conductive carbon (MMM, Belgium), 18 g of
2 s DBP plasticizer, and 150 ml of acetone was processed as set forth in
Example 1. A section of the formed electrode membrane was laminated
with a similarly sized section of copper expanded metal grid (MicroGrid,
Delker Corp.) using a heated double-roll laminator at a temperature of
about 145°C. The DBP plasticizer was extracted in the manner of
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Example 1 and the resulting negative electrode member was air-dried at
about 70°C.
In an alternative embodiment, the copper grid may be embedded between
two electrode membranes or coated with an electrode paste in the same
s manner as described in Example 1.
EXAMPLE 3
Preparation of Coated Polyolefin Separator Membrane
A commercial three-layer, 25 ~m microporous polyolefin separator
1o membrane material which had been surface-modified by the manufacturer
(Celgard LLC) with a proprietary poly(vinylidene fluoride) copolymer
composition coating was treated according to an embodiment of the
present invention in the following manner to prepare an electrochemical
cell separator member. A section of separator membrane cut slightly larger
15 in lateral dimensions than electrode members of Examples 1 and 2 to
ensure complete electrical insulation between those members was
immersed for a few seconds in a 15% solution of propylene carbonate (PC)
in methanol and then removed to allow excess solution to drip from the
sample. The originally opaque membrane appeared translucent, indicating
z o impregnation of the solution into the pores of the membrane. The sample
was then allowed to air-dry for several minutes during which the methanol
vehicle evaporated, depositing the residual PC on the surfaces of the pores
of the membrane without compromising the porous membrane structure, as
was indicated by a reversion to membrane opacity approaching that of the
2 s original membrane.
EXAMPLE 4
Assembly of Battery Cell
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A functional laminated rechargeable electrochemical battery cell was
prepared be assembling the cell members of Examples 1-3 as depicted in
FIG. 1 and laminating the assemblage in a commercial heated
opposed-roller laminator device at about 100°C and 25 lb/in roll
pressure.
s The laminate was placed in a circulating air oven at about 70°C for 1
hour
to remove moisture and residual PC and then packaged in an hermetically
sealed mufti-layer foil/polymer envelope in a helium atmosphere with a
measure of activating 1 M solution of LiPF6 in an equipart mixture of
ethylene carbonate:dimethyl carbonate (EC:DMC). The cell was then
Zo connected to a battery cycler and tested under various conditions of
common usage employing a CCCV charging protocol (charge at a C/2 rate
to an upper cutoff voltage of 4.2 V followed by a 2 hour constant-voltage
holding period at 4.2 V) and a CC (C/5) constant-current discharge. The
battery cell exhibited highly responsive performance and a remarkably
is stable capacity over extended cycles. At the conclusion of the period of
cycle testing, the packaged battery cell was contacted with a heated platen
to quickly raise its temperature to about 160°C, a temperature in
excess of
the designed polyolefin softening shut-down temperature of the separator
membrane. The current output of the battery rapidly ceased at a cell
2 o temperature of about 135°C, indicating that microporous structure
of the
cell was sustained during the laminating operation.
EXAMPLE 5
Assembly of Battery Cell
2 s As a counter-example of the efficacy of the present invention, electrode
member samples prepared in the manner of Examples 1 and 2 were
assembled, laminated, and formed into a battery cell in the manner and
under the conditions of Example 4 with a section of the commercial
surface-modified microporous separator membrane employed in Example
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3, but lacking the plasticizer solution treatment of that example. The
lamination adhesion between the cell member layers was sufficient to
allow careful handling of the laminate cell structure during the final
packaging operation; however, it was apparent that the layers could be
readily separated at the interfaces without undue effort. Such inadequate
interfacial bonding, resulted in the performance of the battery cell
fluctuating significantly during charge/discharge cycling and cell capacity
diminishing noticeably over numerous cycles.
1 o EXAMPLE 6
Comparative Bond Strengthh
In an attempt to quantify the efficacy of the foregoing plasticizer treatment
in terms of comparative interfacial bond strengths developed during
lamination at sub-shut-down temperature, e.g., as between the laminates
s5 according to Examples 4 and 5, the laminate cell structures of those
examples were duplicated, but for the lack of laminating pressure in the
region of the trailing ends of the assemblages in order to provide
unadhered sections of individual cell member layers which would serve as
access tabs for the ensuing peel strength testing. Each of the cell samples
2 o was thereafter mounted in an Instron tensile strength test device such
that
individual electrode/separator membrane lamination couples were clamped
at their access tabs in the device. Each peel strength test was conducted at
room temperature under a constant applied strain rate of 200% per minute.
In response to the applied strain of the tests, the untreated sample
2 s according to Example 5 registered no substantial interfacial bond
strength,
rather both the positive electrode/separator and negative
electrode/separator interfaces readily separated without significant
disfigurement of either surface, thus indicating minimal bond strength
between those cell members.
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On the other hand, under identical peel test conditions, the interface
couples of the Example 4 sample prepared after treatment according to the
above-described embodiment of the present invention registered
substantial bond strength in the Instron device. This data was inconclusive
s in determining the electrode/separator interfacial bond strength, because in
each instance bond failure occurred not at that interface, but within the
body of the respective electrode composition layers. The
electrode/separator interfacial bond effected by the present invention thus
indeed exceeds the strength of the individual electrode composition layers.
FX A MPT F 7
Preparation of Electrodes
For the fabrication of a laminated battery cell according to another
embodiment of the present invention, positive and negative electrode
1 s members were prepared as in Examples 1 and 2 with the exceptions that
propylene carbonate (PC) was substituted for dibutyl phthalate (DBP) as
the polymer matrix plasticizer, and the ancillary plasticizer extraction
operation was not employed. The resulting electrode membranes
comprised about 15% PC plasticizer.
EXAMPLE 8
Assembly of Battery Cell
The electrode members of Example 7 were laminated with a
surface-modified separator membrane and further used to prepare a battery
2 s cell in the manner of Example 5. However, contrary to the results of tests
obtained with the laminated cell structure of Example 5, the present
structure performed substantially the same, as to both strong interfacial
laminate bonding and desirable electrochemical cell characteristics, as that
of Example 4.
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EXAMPLE 9
Assembly of Batter.
As an example of the comparative efficacy of plasticizer compounds in the
s present invention, electrode members of Examples 1 and 2 were prepared,
but not subjected to the ancillary extraction operation. Laminated cell
structures and battery cell samples were prepared with these electrode
members according to Example 8 and tests were conducted in like manner.
The test results were marginally satisfactory in substantially all aspects,
1 o evidencing the preferred performance of a plasticizer, such as PC, which
exhibits a more aggressive solvency, or plasticizing capability, with respect
to the surface-modifying polymer of the microporous separator membrane.
EXAMPLE 10
1 s Comparative Lamination Tests
Respective exemplary embodiments of the present invention were used to
fabricate a number of laminated battery cells in the manner of foregoing
Examples 4 and 8. The conditions of lamination were varied from about
80°C to 110°C and about 10 to 30 lb/in roller pressure with
substantially
2 o similar results in both separator interfacial bonding and electrochemical
cell performance.
EXAMPLE 11
Comparative Plasticizer Tests
2 J A number of battery cells were prepared in the manner of Example 4, i.e.
using the cell members of Examples 1-3, except that the separator
membrane materials were treated with solutions of PC in methanol varying
from about 10% to 30% PC. Test results, as in the previous example,
varied little within commercially acceptable ranges.
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Numerous additional laminated battery cells were considered
comprising various compositions of other outlined plasticizer solutes, such
as, butylene carbonate, dimethyl phthalate, diethyl phthalate, dipropyl
s phthalate, dibutyl phthalate, dimethyl ethers of diethylene glycol, dimethyl
ethers of triethylene glycol, dimethyl succinate, diethyl succinate, dibutyl
succinate, dimethyl adipate, diethyl adipate, dimethyl sebacate, and
mixtures thereof. Of those, the compositions comprising dimethyl ethers
of diethylene glycol, and dimethyl ethers of triethylene glycol, in addition
1 o to the exemplary propylene carbonate, would be particularly preferred due
to their more vigorous plasticizing capability.
In the microporous membrane-treating embodiment of the
invention, there may be employed, instead of the exemplary methanol, a
1 s number of other useful solvent vehicles, such as, acetone, methyl ethyl
ketone, ethanol, n-propanol, isopropanol, methyl acetate, ethyl acetate,
methyl propionate, dimethyl carbonate, methylene chloride, chloroform,
dichloroethane, trichloroethylene, higher-boiling chlorofluorocarbons, and
mixtures thereof. While such other components have been seen to provide
2 o substantially similar results in the preparation of microporous
membrane-treating compositions, their preferential selection may depend
on a number of ancillary considerations, such as, for example, desired
solvent evaporation time and speed of processing, maintenance of safe
environments, and robustness of processing equipment and conditions.
2 s For instance, while the use of acetone as a treatment solution vehicle
would promote more rapid evaporation and shorter processing lines, the
lower solvency of methanol would minimize a tendency toward affecting
the configuration or uniformity of the surface-modifying polymers of the
polyolefin separator membrane material, thus leading to a preference for
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the methanol solvent. This is also the case for other solvents of lesser
solvency, such as, ethanol, n-propanol, isopropanol, dichloroethane, and
trichloroethylene. Other considerations such as corrosiveness, commercial
availability, cost, toxicity, flammability, and reactivity in electrochemical
environs would similarly bear weight in selection of final components.
It is anticipated that other embodiments and variations of the
present invention will become readily apparent to the skilled artisan in the
light of the foregoing specification. Such embodiments and variations are
1 o intended to likewise be included within the scope of the invention as set
out in the appended claims.
