U.S. patent application number 13/690551 was filed with the patent office on 2013-04-11 for electrochemical cells with improved separator and electrolyte.
This patent application is currently assigned to THE GILLETTE COMPANY. The applicant listed for this patent is THE GILLETTE COMPANY. Invention is credited to Fred Joseph Berkowitz, Nikolai Nikolaevich Issaev, Eric Navok, Michael Pozin, Michael Dean Sliger.
Application Number | 20130089792 13/690551 |
Document ID | / |
Family ID | 43528343 |
Filed Date | 2013-04-11 |
United States Patent
Application |
20130089792 |
Kind Code |
A1 |
Issaev; Nikolai Nikolaevich ;
et al. |
April 11, 2013 |
ELECTROCHEMICAL CELLS WITH IMPROVED SEPARATOR AND ELECTROLYTE
Abstract
An electrochemical cell is described. The electrochemical cell
includes an anode, a cathode, a separator between said anode and
said cathode, and an electrolyte. The electrolyte includes a salt
dissolved in an organic solvent. The separator in combination with
the electrolyte has an area specific resistance less than 2
ohm-cm.sup.2. The electrochemical cell has an interfacial anode to
cathode ratio of less than about 1.1.
Inventors: |
Issaev; Nikolai Nikolaevich;
(Woodbridge, CT) ; Pozin; Michael; (Brookfield,
CT) ; Sliger; Michael Dean; (New Milford, CT)
; Navok; Eric; (Stamford, CT) ; Berkowitz; Fred
Joseph; (Milford, CT) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
THE GILLETTE COMPANY; |
Boston |
MA |
US |
|
|
Assignee: |
THE GILLETTE COMPANY
Boston
MA
|
Family ID: |
43528343 |
Appl. No.: |
13/690551 |
Filed: |
November 30, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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12624670 |
Nov 24, 2009 |
8349493 |
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13690551 |
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Current U.S.
Class: |
429/328 ;
429/218.1; 429/219; 429/220; 429/221; 429/231.1; 429/231.5;
429/231.7; 429/246; 429/327; 429/330; 429/337; 429/341 |
Current CPC
Class: |
Y02E 60/10 20130101;
H01M 2/14 20130101; H01M 10/056 20130101; H01M 2010/4292 20130101;
H01M 2300/004 20130101; H01M 10/0569 20130101; H01M 4/581 20130101;
H01M 4/5815 20130101; H01M 6/164 20130101; H01M 4/136 20130101;
H01M 10/0525 20130101; H01M 10/052 20130101; H01M 4/06 20130101;
H01M 4/382 20130101 |
Class at
Publication: |
429/328 ;
429/246; 429/341; 429/337; 429/330; 429/327; 429/231.7; 429/220;
429/221; 429/219; 429/218.1; 429/231.5; 429/231.1 |
International
Class: |
H01M 10/056 20060101
H01M010/056; H01M 2/14 20060101 H01M002/14; H01M 10/0525 20060101
H01M010/0525; H01M 4/06 20060101 H01M004/06; H01M 6/16 20060101
H01M006/16; H01M 4/136 20060101 H01M004/136 |
Claims
1. An electrochemical cell comprising an anode, a cathode, a
separator between said anode and said cathode, and an electrolyte,
said electrolyte comprising a salt dissolved in an organic solvent,
and said separator in combination with said electrolyte has an area
specific resistance less than 2 ohm-cm.sup.2, and said
electrochemical cell has an interfacial anode to cathode ratio of
less than about 1.2.
2. The electrochemical cell of claim 1 wherein the separator has a
pore size between about 0.005 to about 5 micron.
3. The electrochemical cell of claim 1 wherein the separator has a
tortuosity less than about 2.5.
4. The electrochemical cell of claim 1 wherein the separator has a
porosity between about 30% and about 70%.
5. The electrochemical cell of claim 1 wherein the electrolyte
comprises a plurality of salts dissolved in an organic solvent.
6. The electrochemical cell of claim 1 wherein the organic solvent
comprises an ether-based solvent.
7. The electrochemical cell of claim 6 wherein the ether-based
solvent is selected from the group consisting of dimethoxyethane,
ethyl glyme, diglyme, dimethoxypropane, triglyme, and
dioxolane.
8. The electrochemical cell of claim 1 further comprising at least
one co-solvent included in the electrolyte solvent.
9. The electrochemical cell of claim 8 wherein the co-solvent is
present in an amount less than 25 weight percent based on the
weight of the solvent of the electrolyte solution and wherein the
co-solvent is selected from the group consisting of
3,5-dimethylisoxazole, 3-methyl-2-oxazolidone, propylene carbonate,
ethylene carbonate, butylene carbonate and sulfolane.
10. The electrochemical cell of claim 1 wherein the anode is
selected from the group consisting of carbon and graphite.
11. The electrochemical cell of claim 1 wherein the separator is
wetted by the electrolyte.
12. The electrochemical cell of claim 1 wherein the interfacial
anode to cathode ratio is between about 0.80 and about 1.05.
13. The electrochemical cell of claim 18 wherein the interfacial
anode to cathode ratio is between about 0.90 and about 1.0.
14. The electrochemical cell of claim 1 wherein the separator has a
thickness from about 8 to about 30 micrometers.
15. The electrochemical cell of claim 1 wherein the cathode is
selected from the group consisting of fluorinated carbon
(CF.sub.x).sub.n wherein x varies between about 0.5 and about 1.2
and n is greater than or equal to 1; (C.sub.2F).sub.n wherein n is
greater than or equal to 1; copper sulfide (CuS); copper oxide
(CuO); iron sulfide (FeS); iron disulfide (FeS.sub.2); silver oxide
(AgO, Ag.sub.2O); sulfur (S); cobalt oxide; vanadium pentoxide
(V.sub.2O.sub.5); molybdenum trioxide (MoO.sub.3); molybdenum
disulfide (MoS.sub.2); titanium disulfide (TiS.sub.2); transition
metal polysulfide; lithiated metal oxide; lithiated metal sulfide;
lithiated manganese oxide; Li.sub.xTiS.sub.2; LiFePO.sub.4;
LiFeNbPO.sub.4; and mixtures thereof.
Description
FIELD OF THE INVENTION
[0001] The invention relates to an electrochemical cell and more
particularly to an electrochemical cell including an improved
separator and electrolyte combination and cell design.
BACKGROUND OF THE INVENTION
[0002] The development of high energy battery systems requires the
compatibility of an electrolyte possessing desirable
electrochemical properties with highly reactive, high energy
density anode and cathode materials, such as lithium, sodium,
FeS.sub.2 and the like.
[0003] While the theoretical energy, i.e. the electrical energy
potentially available from a selected anode-cathode couple is
relatively easy to calculate, there is a need to choose an
electrolyte for such couple that permits the actual energy produced
by an assembled battery to approach the theoretical energy. The
problem usually encountered is that it is practically impossible to
predict in advance how well, if at all, an electrolyte will
function with a selected couple. Although a cell must be considered
as a unit having three parts, a cathode, an anode and an
electrolyte, and it is to be understood that the parts of one cell
are not predictably interchangeable with parts of another cell to
produce an efficient and workable cell. It has been realized that
the separator, in conjunction with the electrolyte, can play an
important part in the performance characteristics of a cell.
[0004] Many electrochemical systems can function in various
environments when they are freshly produced. However, when cell
systems are stored for long periods of time at high temperatures,
their impedance characteristics can become altered to render the
electrochemical systems unsuitable for some consumer applications.
A specific high rate application of a cell is its use in cameras.
Although cells can function under normal conditions, many cells may
exhibit high voltage drop under high drain rates as exemplified in
flash cameras.
[0005] There exists a need to provide an electrolyte solution and
separator combination for use in an electrochemical cell and cell
design to provide lower overall cell impedance to substantially
increase cell performance.
SUMMARY OF THE INVENTION
[0006] One aspect of the invention features an electrochemical
cell. The electrochemical cell comprises an anode, a cathode, a
separator between the anode and cathode, and an electrolyte. The
cathode comprises iron disulfide. The electrolyte comprises a salt
dissolved in an organic solvent. The separator in combination with
the electrolyte has an area specific resistance less than 2
ohm-cm.sup.2. The electrochemical cell has an interfacial anode to
cathode ratio of less than about 1.1.
[0007] In some implementations, the separator may have a pore size
between about 0.005 to about 5 micron. The separator may have a
tortuosity less than about 2.5. The separator may have a porosity
between about 30% and about 70%. The electrolyte may comprise a
plurality of salts dissolved in an organic solvent. The organic
solvent may comprise an ether-based solvent. The organic solvent
may be a mixture of a cyclic ether-based solvent and an acyclic
ether-based solvent. The cyclic ether-based solvent may be
dioxolane. The weight ratio of the acyclic ether-based solvent to
the dioxolane may be from 1:99 to 45:55. The weight ratio of the
acyclic ether-based solvent to the dioxolane may further be from
10:90 to 40:60. The acyclic ether-based solvent may be selected
from the group consisting of dimethoxyethane, ethyl glyme, diglyme,
dimethoxypropane, and triglyme. The acyclic ether-based solvent may
be 1,2-dimethoxyethane. At least one co-solvent may be included in
the electrolyte solvent. The co-solvent may be present in an amount
less than 25 weight percent based on the weight of the solvent(s)
of the electrolyte solution. The co-solvent may be selected from
the group consisting of 3,5-dimethylisoxazole,
3-methyl-2-oxazolidone, propylene carbonate, ethylene carbonate,
butylene carbonate and sulfolane. The anode may comprise lithium.
The separator may be wetted by the electrolyte. The separator may
have a thickness from about 8 to about 30 micrometers.
[0008] The electrochemical cell may have an anode to cathode ratio
between about 0.80 and about 0.90 and about 1.0 and about 1.05.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] While the specification concludes with claims particularly
pointing out and distinctly claiming the subject matter which is
regarded as forming the present invention, it is believed that the
invention will be better understood from the following description
taken in conjunction with the accompanying drawings.
[0010] FIG. 1 is a pictorial view of a cylindrical Li/FeS.sub.2
cell.
DETAILED DESCRIPTION OF THE INVENTION
[0011] Referring to FIG. 1, a primary electrochemical cell 10
includes an anode 12 that comprises lithium in electrical contact
with a negative lead 14, a cathode 16 that comprises iron disulfide
in electrical contact with a positive lead 18, a separator 20, and
an electrolyte. Anode 12 and cathode 16, with separator 20 disposed
therebetween, may be rolled into an assembly typically referred to
as a jelly roll. Anode 12, cathode 16, separator 20, and the
electrolyte are contained within a housing 22. Electrochemical cell
10 further includes a cap 24 and an annular insulating gasket 26.
The cell 10 may include a safety valve 28. The cathode 16
preferably comprises a blend of iron disulfide, conductive carbon
particles, and binder.
[0012] The electrolyte comprises a salt dissolved in an organic
solvent. A salt may comprise one salt or may comprise a plurality
of salts. The organic solvent may comprise an ether-based solvent.
The organic solvent may comprise a mixture of ether-based solvents.
The organic solvent may comprise a mixture of a cyclic ether-based
solvent and an acyclic ether-based solvent. The cyclic ether-based
solvent may comprise a dioxolane. As used herein the term dioxolane
shall mean 1,3-dioxolane (DIOX), alkyl-substituted dioxolanes or
mixtures thereof. Examples of alkyl-substituted dioxolanes are
4-methyl-1,3-dioxolane or 2,2-dimethyl-1,3-dioxolane. A preferred
dioxolane for use in this invention is 1,3-dioxolane. Typical
acyclic ether-based solvents suitable for use in this invention are
dimethoxyethane, 1,2-dimethoxyethane (DME), ethyl glyme, diglyme,
dimethoxypropane, and triglyme. The organic solvent may comprise an
organic carbonate. The organic solvent may comprise a mixture of
organic carbonates. Examples of organic carbonates include ethylene
carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DC),
ethyl methyl dicarbonate (EMC), diethyl carbonate (DEC), and
vinylene carbonate (VC).
[0013] For some applications, at least one optional co-solvent may
be used such as 3,5-dimethylisoxazole (DMI), 3-methyl-2-oxazolidone
(3Me2Ox), propylene carbonate (PC), ethylene carbonate (EC),
butylene carbonate (BC), tetrahydrofuran (THF), diethyl carbonate
(DEC), ethylene glycol sulfite (EGS), dioxane, dimethyl sulfite
(DMS), gamma butyrolactone (GBL), or the like. The preferred
co-solvents for use in this invention are 3,5-dimethylisoxazole,
3-methyl-2-oxazolidone and propylene carbonate. For most
applications the addition of the optional co-solvent should be
limited to 25 weight percent or less based on the total weight of
the solvent for the electrolyte, preferably less than 20 weight
percent.
[0014] The preferred weight ratio of the acyclic ether-based
solvent to dioxolane is from 1:99 to 45:55, more preferably from
10:90 to 40:60 and one of the most preferred is about 29:71. The
most preferred electrolyte is 29.0 weight percent DME, 70.8 weight
percent DIOX, 0.2 weight percent DMI, and 0.1 weight percent of
LiTFS along with 1.0 moles LiI per liter of solution.
[0015] It has been found that in addition to the electrolyte a low
resistance separator allows for optimal high rate cell performance.
A desired separator material for use in high rate lithium cells
comprises microporous extruded or cast films (membranes). The
separator may have a thickness from about 8 to 30 micrometers
(microns). The microporous membrane separator may have a pore size
range from about 0.005 to about 5 microns and preferably from about
0.005 to about 0.3 microns, a porosity range from about 30 to about
70 percent, preferably from about 35 to about 65 percent, an area
specific resistance measured in combination with the electrolyte of
less than 2 ohm-cm.sup.2, and a tortuosity of less than about
2.5.
[0016] The pore size of the separator may be above a minimum value
which enables the nonhindered migration of a solvated ion. A
solvated lithium ion may be on the order of 10 Angstroms or 0.001
micron. Since it may be common for organic electrolyte systems to
form ion pairs and for at least a monolayer of an electrolyte
solvent to line the pore walls of the separator, a minimum pore
diameter of 0.005 micron enables the nonimpeded passage of an ion
through a pore. As the pore size increases, however, nonporous
areas need to also increase in order to provide mechanical
strength. The result of increasing these nonporous areas may be
blockage of a substantial portion of the separator impeding ion
migration. As a result, a large number of moderate size pores may
be preferred to a few very large pores. Another way of viewing this
effect is that the distance between pores may be as important as
the pore diameter. Typically, in separators of submicron size, the
distance between pores should also be less than a micron. In
addition, it is also a function of the separator to form a physical
barrier to the passage of electrode particles through the separator
which could result in an electrical short between the anode and
cathode. Such particles can be as small as a few microns, thus also
limiting the upper desired pore diameter. Consequently the pore
size may preferably be in the submicron range or the pores should
be sufficiently tortuous to provide a physical barrier to the
passage of electrode particles through the separator.
[0017] Methods for determining pore size of a porous material are
liquid displacement and air flow measurements. These measurements
can be performed using a commercial instrument such as the Coulter
II Porometer. The Coulter II Porometer determines the pressure
required to overcome the surface tension of a liquid within a
wetted pore. The smaller the pore, the greater the pressure
required. By comparing the pressure profile of a wetted membrane to
a dry membrane, a pore diameter distribution can be determined.
Pore diameters represent mean pore flow diameters, that is, half of
the flow passes through pores larger than this value and half flows
through pores smaller than this diameter.
[0018] A minimum porosity of 35% may typically be utilized to
provide moderate ion transport. Porosities greater than 70%
typically may result in insufficient tensile strength for
processing into an electrochemical cell and the need for thicker
than desired separators. Preferred separator porosities may be
between about 35% and about 65%.
[0019] Area specific resistance is a measured combination separator
and electrolyte property which is influenced by other properties
such as pore size, number of pores, porosity, tortuosity and
wettability. The area specific resistance value may be the best
parameter which can be correlated to electrochemical cell rate
capability. In the case of lithium cells having organic
electrolytes and solid cathodes it has been found that the most
preferred area specific resistance value for high rate performance
should be less than 2 ohm-cm.sup.2. Separator and electrolyte area
specific resistance above 2 ohm-cm.sup.2 hinders the rate
performance capability of the cell.
[0020] Tortuosity in its simplest definition is the ratio of actual
pore length, i.e., how far an ion has to travel to pass through a
separator, to the separator thickness. However this definition
assumes that mass transport through a pore is affected only by
distance and does not take other hindrances to mass transport into
account. Such hindrances include: pore bottle necks or pore
restrictions, noninterconnected pores or dead ends, inhibited ion
flow as ions collide with pore side walls at channel bends. Since
no model accurately describes the tortuosity of a separator and
since the tortuosity of each separator is different, the best
indication of separator tortuosity is that estimated from the
measured resistance value in electrolyte. The most common method of
determining the effective tortuosity of a separator is based on the
separator porosity and the ratio of specific conductivity of the
separator to that of the electrolyte. Thus,
R separator R solution = Tortuosity 2 Porosity ##EQU00001##
where R.sub.separator is the area specific resistance in
ohms-cm.sup.2 of the separator, R.sub.solution is the area specific
resistance in ohms-cm.sup.2 of the electrolyte and porosity in
volume fraction. Although this equation assumes all pores have
identical tortuosities, it is accurate for defining the separator
of this invention. It has been found that the best high rate
separators exhibit tortuosities of less than 2.5 and preferably
less than 2.0. A study of commercial separators suggest that high
tortuosity may not be so much a result of actual tortuous paths but
rather a result of regions of pore blockage. That is, many
separators display layered regions of high and low porosity. If the
regions of low porosity limit ion transport, the result is a higher
resistance value which is reflected in a higher tortuosity value.
F. L. Tye described in the Journal of Power Sources Vol. 9 (1983),
89-100, a theoretical calculation of the contribution that pores of
varying tortuosities have on overall separator conductivity. Based
on this treatment, if a separator contained 50% of its pores at a
tortuosity of 1.5 and 50% of its pores at a tortuosity of 4, 88% of
the conductivity is a result of the pores at a tortuosity of 1.5.
This theoretical treatment of pore structure and separator
conductivity supports the observations of measured separator
resistances. However in reality, a measured resistance and
estimated tortuosity do not provide any insight as to whether all
the pores have equal tortuosity or if only a small portion of the
current is being carried through a few pores of low tortuosity.
Different cell performances would be expected based on the
distribution of pore tortuosities.
[0021] Another category of separators produced from microfibers,
such as by melt blown nonwoven film technology, may also be useful.
Such films typically possess pores of several microns in diameter
but displaying less tortuous paths.
[0022] Preferably the separator comprises a material that is
wettable or wetted by the electrolyte. A material is said to be
wetted by a liquid when the contact angle between the liquid and
the surface is less than 90.degree. or when the liquid will tend to
spread spontaneously across the surface; both conditions normally
coexist.
[0023] Material for anode 12 may comprise aluminum (Al), lithium
(Li), sodium (Na), potassium (K), calcium (Ca), magnesium (Mg) and
their alloys and metal-intercalated carbon or graphite material
such as lithiated carbon. Of these metals, lithium is preferred
because, in addition to being a ductile, soft metal that can easily
formed into a jelly roll and used in the assembly of a cell, it
possesses the highest energy-to-weight ratio of the group of
suitable anode metals.
[0024] Material for cathode 14 may comprise fluorinated carbon
represented by the formula (CF.sub.x).sub.n wherein x varies
between about 0.5 and about 1.2 and (C.sub.2F).sub.n wherein in
both cathodes the n refers to the number of monomer units which can
vary widely, copper sulfide (CuS), copper oxide (CuO), lead dioxide
(PbO.sub.2), iron sulfides (FeS, FeS.sub.2), copper chloride
(CuCl.sub.2), silver chloride (AgCl), silver oxide (AgO,
Ag.sub.2O), sulfur (S), bismuth trioxide (Bi.sub.2O.sub.3), copper
bismuth oxide (CuBi.sub.2O.sub.4), cobalt oxides, vanadium
pentoxide (V.sub.2O.sub.5), tungsten trioxide (WO.sub.3),
molybdenum trioxide (MoO.sub.3), molybdenum disulfide (MoS.sub.2),
titanium disulfide (TiS.sub.2), transition metal polysulfides,
lithiated metal oxides and sulfides, such as lithiated cobalt
and/or nickel oxides, lithiated manganese oxides,
Li.sub.xTiS.sub.2, Li.sub.xFeS.sub.2, Li.sub.4Ti.sub.5O.sub.12,
LiFePO.sub.4, LiFeNbPO.sub.4 and mixtures thereof.
[0025] The jelly roll assembly comprising anode 12 and cathode 16
with separator 20 therebetween may be prepared by spirally winding
flat electrodes with separator material. Anode 12 may be prepared
from a solid sheet of lithium metal as the anode active material,
e.g., a continuous sheet of lithium metal or lithium alloy, such as
a lithium-aluminum alloy. Cathode 16 may comprise a cathode active
material, such as iron disulfide (FeS.sub.2), coated onto metallic
substrate, such as a sheet, grid, or screen comprising aluminum or
stainless steel. Separator 20 comprises electrolyte permeable
material, such as microporous polypropylene or polyethylene.
[0026] To fabricate a jelly roll assembly, separator 20 may be
inserted on each side of the anode 12. The first (top) separator
sheet can be designated the outer separator sheet and the second
sheet can be designated the inner separator sheet. The cathode 16
may then placed against the inner separator sheet to form the flat
electrode assembly. The anode and cathode may be aligned in any
arrangement, but generally the smaller, in surface area, of the
electrodes is aligned so that its total surface area has an
opposing electrode with separator therebetween. The flat electrode
assembly may be spirally wound to form an electrode spiral
assembly, or jelly roll assembly. The winding can be accomplished
using a mandrel to grip an extended separator edge of the flat
electrode assembly and then spirally winding the flat electrode
assembly to form the wound electrode assembly. The winding may
occur either clockwise or counter-clockwise depending on the
electrode desired by design to be at the jelly roll's outermost
radius, e.g., the anode at the outermost radius of the jelly that
is generally referred to as an anode outer-wrap design or the
cathode at the outermost radius of the jelly that is generally
referred to as an cathode outer-wrap design. The finished jelly
roll may have either the anode or cathode located towards its
outermost radius.
[0027] The anode and cathode each have a total theoretical capacity
that results from the electrochemically active materials, i.e.,
materials that may contribute to the electrochemical capacity of
the assembled battery, within the electrode structures. The total
theoretical capacity of an electrode is determined by multiplying
the mass of active electrode material(s) in the electrode, in
grams, by the specific theoretical capacity of the active electrode
material(s), in amp-hours per gram. For example, the specific
theoretical capacity of lithium metal is 3861 mAh/g. An anode may
contain 1 gram of 100% pure lithium as the active material. The
resulting total theoretical capacity of the example anode would be
3861 mAh. Similarly, the specific theoretical capacity of iron
disulfide is 893.5 mAh/g. A cathode may contain 4.95 grams of iron
disulfide as the active material. The resulting total theoretical
capacity of the cathode would be 4423 mAh.
[0028] A useful expression relating to the overall design of a
battery is the anode to cathode (A/C) ratio. The A/C ratio enables
persons skilled in the art to readily determine the amount of
capacity of active electrode material(s) within a battery's anode
in relation to the battery's cathode for a particular battery
design. The skilled artisan may use an A/C ratio that has a value,
or sometimes termed "balance," that suits the overall performance
of a battery design. For example, the artisan designing a battery
to perform predominantly in high-rate discharge applications may
desire to have a cathode capacity that is greater than the anode
capacity to account for efficiency losses within the discharge of
the cathode active material. Such a design would have an A/C ratio,
or balance, of less than one.
[0029] The A/C ratio may be expressed in relation to the total
anode and cathode active material(s) within a battery design. Such
an expression may be referred to as the total A/C ratio or total
input ratio. To determine the total A/C ratio, the total
theoretical capacity of anode active material(s) included within
the cell is divided by the total theoretical capacity of cathode
active material(s) included within the cell. Utilizing the
theoretical electrode capacity examples provided above, the total
A/C ratio would be 0.87 (3861 mAh/4423 mAh).
[0030] The total A/C ratio may be adjusted, or balanced, in
accordance with the desired discharge characteristics of the
assembled battery. Generally, the Li/FeS.sub.2 battery is balanced
to have a total A/C ratio of less than about 1.2, regardless of
cell size, e.g., AA or AAA cylindrical size or smaller or larger
sizes. Preferably, the Li/FeS.sub.2 cell is balanced so that the
total A/C ratio is between about 0.80, 0.90 and 1.0, 1.05,
regardless of cell size.
[0031] The A/C ratio may also be defined in relation to the amount
of active material(s) within the electrodes along with the
interfacial area between the electrode assemblies. Such an
expression may be referred to as the interfacial A/C ratio or
interfacial input ratio. The interfacial A/C ratio takes into
account design variations associated with specific electrode
parameters and design considerations, e.g., jelly roll
construction, anode to cathode alignment, etc. It may also be
possible that certain amounts of anode or cathode active
material(s) do not discharge during use, which may be due to cell
design, discharge rate, or other factors. The interfacial A/C ratio
is useful in describing the battery design while taking into
account active materials that in practice may not discharge, but
yet may be important to overall cell design or construction. The
interfacial A/C ratio may be defined as the ratio of the anode
active material(s) theoretical capacity to the cathode active
material(s) theoretical capacity for the largest surface area
facing between the anode and the cathode with separator
therebetween.
[0032] To determine the interfacial A/C ratio for batteries
employing a jelly roll assembly with an anode outer-wrap design, it
is useful to first define segments within the jelly roll assembly
to account for varying contributions to the overall interfacial A/C
ratio calculation across the length of the jelly roll assembly by
the electrodes. It should be appreciated that a similar process may
be followed to determine the interfacial A/C ratio for alternative
jelly roll designs, such as the cathode outer-wrap design, designs
employing multiple tabs for each electrode, and designs locating
electrode tabs in locations other than the ends of the electrode
assembly.
[0033] An electrode segment may be defined as a section of the
electrode with a specified length and, when segmented along the
segment length, has an equal thickness and height. An electrode tab
segment containing an electrode tab and tape, does not contribute
in any manner to the overall chemical reaction of the cell, and has
no opposing electrode on either of its side.
[0034] The electrode outer wrap segment may be defined as the
electrode, e.g., an anode, segment that has an opposing electrode,
e.g., a cathode, facing the inside face of the electrode. The
electrode inner winds segment may be defined as the electrode
segment that has an opposing electrode, e.g., a cathode, facing an
anode, on both of its sides. The total electrode length is the sum
of the electrode tab segment length, the electrode outer wrap
segment length, and the electrode inner wrap segment length. The
active electrode segment may be defined as the total electrode
length minus the electrode tab length or, alternatively, the sum of
the electrode outer wrap segment length and the electrode inner
winds segment length.
[0035] The interfacial A/C ratio may be determined by: (1)
calculating the interfacial A/C ratio for each segment; (2)
adjusting the interfacial A/C ratio for each segment according to
the overall contribution of the segment; and (3) summing the
adjusted interfacial A/C ratios for each segment to determine the
overall interfacial A/C ratio for the battery. An example
calculation of the interfacial A/C ratio for a Li/FeS.sub.2 battery
utilizing a jelly roll electrode assembly with the anode as the
outermost electrode within the jelly roll assembly, with anode and
cathode electrodes including a single tab respectively,
follows.
[0036] The alignment of the anode on the cathode may be such that
the total surface area of the anode has opposing cathode with
separator therebetween. The anode may be 308.5 mm in length, 39 mm
in width, and 0.1575 mm in thickness. The density of lithium, the
active anode material, is 0.534 g/cm.sup.3. The purity of the
lithium anode active material is assumed to be 100%.
[0037] The anode outer wrap segment length may be 39 mm. The anode
inner wrap segment length may be 259.5 mm. The anode tab segment
length may be 10 mm. The active anode segment length may be 298.5
mm. Additionally, the cathode may have a cathode material loading
of 24 mg per cm.sup.2 per side of the cathode. The FeS.sub.2 may
have a purity of 95% and may comprise 89% of the total cathode
composition.
[0038] The anode capacity for the example described above would be
16.24 mAhr/cm.sup.2/side. The cathode capacity for the example
described above would be 18.14 mAhr/cm.sup.2/side. The interfacial
A/C ratio for the anode outer wrap segment, where one side of the
cathode and two sides of the anode are participating in the
reaction, would be 1.79 [(16.24 mAhr/cm.sup.2/side2 sides)/(18.14
mAhr/cm.sup.2/side1 side)]. The interfacial A/C ratio for the anode
inner wrap segment, where two sides of the cathode and two sides of
the anode are participating in the reaction, would be 0.90 [(16.24
mAhr/cm.sup.2/side2 sides)/(18.14 mAhr/cm.sup.2/side2 sides)].
[0039] The contributions of these segments to the overall
interfacial A/C ratio of the battery is determined by adjusting
anode inner and outer wrap interfacial A/C ratios relative to the
segment fraction of the overall length. The anode outer wrap
segment fraction is 0.13 (39 mm/298.5 mm) and the anode inner wrap
segment fraction is 0.87 (259.5 mm/298.5 mm) The anode outer and
inner wrap interfacial A/C ratios after adjustment by the
respective segment factors are 0.22 (1.790.13) and 0.78 (0.900.87)
respectively. The adjusted anode outer and inner wrap interfacial
A/C ratios are now summed, resulting in an interfacial A/C ratio
for the assembled example cell of 1.01.
[0040] The interfacial A/C ratio may be adjusted, or balanced, in
accordance with the desired discharge characteristics of the
assembled battery. Generally, the Li/FeS.sub.2 battery is balanced
to have an interfacial A/C ratio of less than about 1.1, regardless
of cell size, e.g., AA or AAA cylindrical size or smaller or larger
sizes. Preferably, the Li/FeS.sub.2 cell is balanced so that the
interfacial A/C ratio is between about 0.80, 0.90 and about 1.0,
1.05, regardless of cell size.
[0041] The ionizable salt for use in this invention may be a simple
salt such as LiCF.sub.3SO.sub.3 or lithium
bistrifluoromethylsulfonyl imide (Li(CF.sub.3SO.sub.2).sub.2N) or a
double salt or mixtures thereof which will produce an ionically
conductive solution when dissolved in these solvents. Suitable
salts are complexes of inorganic or organic Lewis acids and
inorganic ionizable salts. One of the requirements for utility is
that the salts, whether simple or complex, be compatible with the
solvent(s) being employed and that they yield a solution which is
sufficiently ionically conductive, e.g., at least about 10.sup.-4
ohm.sup.-1 cm.sup.-1. Generally, an amount of at least about 0.5M
(moles/liter) would be sufficient for most cell applications.
[0042] Useful ionizable salts include lithium fluoride, lithium
chloride, lithium bromide, lithium sulfide, LiTFS, LiI, LiTFSI,
LiBF.sub.4, LiPF.sub.6, LiAsF.sub.6, LiBOB,
Li(CF.sub.3SO.sub.2).sub.2N, Li(CF.sub.3SO.sub.2).sub.3C, sodium
bromide, potassium bromide, lithium bromide, and mixtures
thereof.
[0043] The ionizable salt for use in conjunction with iron
sulfide-containing cathodes can include lithium trifluoromethane
sulfonate (LiCF.sub.3SO.sub.3), lithium bistrifluoromethylsulfonyl
imide (Li(CF.sub.3SO.sub.2).sub.2N), lithium perchlorate
(LiClO.sub.4), lithium hexafluoroarsenate (LiAsF.sub.6) or mixtures
thereof with lithium trifluoromethane sulfonate being the most
preferred. Suitable double salts for various cell applications
would be lithium tetrafluoroborate (LiBF.sub.4), and lithium
hexafluorophosphate (LiPF.sub.6).
Experimental Testing
[0044] Resistance measurements are conducted in a resistivity cell.
The resistivity cell consists of two stainless steel electrodes
encased in Teflon.RTM.. The lower electrode is constructed such
that a small reservoir of electrolyte may be maintained in the
cell. The top electrode assembly is removable and is aligned to the
bottom assembly via two metal pins. The top electrode assembly is
spring loaded so that that force may be applied (approximately 4 to
5 lbs.) to the top of a material sample being analyzed. The lower
electrode assembly is screwed to a fixture base and electrical
leads are attached to each electrode. The leads are then attached
to the leads of an impedance analyzer, such as a Solartron
Impedance Analyzer, that is used to complete impedance sweeps to
determine resistances of the cell or sample materials.
[0045] The background resistance of the resistivity cell is
determined by running an impedance sweep on the fixture filled with
electrolyte when its electrodes are shorted. The sweep starts at
100,000 kHz and finishes at 100 Hz using a 10 mV amplitude, using
the software program ZPlot by Scribner Instruments to control the
instrumentation. The resistance of the fixture (R.sub.CELL) may
have typical values between about 10 and 150 m.OMEGA. depending
upon the condition of the stainless steel electrodes. Several
sweeps may be completed to ensure the value obtained is relatively
constant.
[0046] The resistance of the separator and electrolyte combination
is determined by running an impedance sweep on a separator sample.
The fixture includes a center disk upon which the separator sample
may be placed. Electrolyte is placed within the cavity of the
resistivity cell to a level that ensures the separator sample is
well-wetted on both sides. The same impedance sweep as described
above is run. Again, several sweeps may be completed to ensure the
value obtained is relatively consistent. The data obtained from the
sweeps is plotted on a Nyquist plot. The ohmic resistance
(R.sub.REAL) of the separator and electrolyte combination is
determined at the Z''=0 point on the Nyquist plot. However, this
value includes the resistance of the resistivity cell. By
subtracting the resistance value of the resistivity cell
(R.sub.CELL) from the resistance determined for the separator and
electrolyte combination sample that includes resistivity cell
impedance (R.sub.REAL), the adjusted resistance value for the
separator and electrolyte combination [R.sub.REAL(ADJ)] is
calculated.
[0047] The area specific resistance (ASR) of the separator and
electrolyte combination is determined by multiplying the
geometrical surface area of the resistivity cell's working
electrode by the adjusted separator and electrolyte combination
resistance value. The working electrode surface area of resistivity
cell used in these experiments had been 3.829 cm.sup.2. The units
of ASR are .OMEGA.cm.sup.2.
[0048] The combinations of two separators with three different
electrolytes are screened for inclusion within assembled cells for
discharge testing.
Separator 1--Celgard 2400, a microporous polypropylene monolayer
membrane with a thickness of 25 .mu.m and a porosity of 41%.
Separator 2--Celgard 2500, a microporous polypropylene monolayer
membrane with a thickness of 25 .mu.m and a porosity of 55%.
Electrolyte A--0.8M LiTFSI in a mixture of 80% by volume dioxolane
and 20% by volume sulfolane with 1000 ppm of added pyridine and 150
ppm of added water. Electrolyte B--1.5M LiTFS in a mixture of 25%
by volume dioxolane and 75% by volume DME. Electrolyte C--1.0M LiI,
0.1% by weight LiTFS, and 2000 ppm of DMI in a mixture of 70% by
weight dioxolane and 30% by weight DME with 200 ppm of added
water.
[0049] The impedance of the resistivity cell is first determined
with each specific electrolyte as described above. The impedance of
the separator/electrolyte combination is then determined with each
specific electrolyte. The adjusted separator/electrolyte
combination resistance is then determined and used in the
calculation of the ASR. The results are included within Table 1.
The separator/electrolyte combinations that have lower ASR's
provide lower overall cell impedance and potentially improved
overall cell discharge performance.
TABLE-US-00001 TABLE 1 Area Specific Resistance (ASR) for
separator/electrolyte combinations. R.sub.CELL R.sub.REAL
R.sub.REAL (ADJ) ASR Interfacial SEPARATOR ELECTROLYTE (.OMEGA.)
(.OMEGA.) (.OMEGA.) (.OMEGA. cm.sup.2) A/C Ratio 1 A 0.163 0.835
0.672 2.573 1.01 1 B 0.112 1.686 1.574 6.028 1.01 1 C 0.118 1.013
0.895 3.426 1.01 2 A 0.163 0.454 0.291 1.113 1.01 2 B 0.112 0.837
0.725 2.775 1.01 2 C 0.118 0.566 0.448 1.716 1.01
[0050] Discharge performance testing follows an ANSI protocol
commonly referred to as the digital camera test, or Digicam. The
protocol consists of applying pulsed discharge cycles to the cell.
Each cycle consists of both a 1.5 Watt pulse for 2 seconds followed
immediately by a 0.65 Watt pulse for 28 seconds. After 10
consecutive pulses, the cell is then allowed to rest for a period
of 55 minutes, after which the prescribed pulse regime is commenced
for a second cycle. Cycles continue to repeat until a cutoff
voltage of 1.05 V is reached. The total number of 1.5 Watt pulses
required to reach the cutoff voltage is recorded.
[0051] A cell is assembled that includes the combination of
Separator 2 and Electrolyte A with an ASR of 1.113 .OMEGA.cm.sup.2
and an interfacial A/C ratio of 1.01 After ambient storage followed
by a pre-discharge of 3% cell capacity, Digicam testing is
performed on the cell. The cell may exhibit an average of 592
pulses, an improvement of about 6% versus a cell that includes a
separator/electrolyte combination that has an ASR of greater than 2
.OMEGA.cm.sup.2 and an interfacial A/C ratio of 1.01.
[0052] A cell is assembled that includes the combination of
Separator 2 and Electrolyte C with an ASR of 1.716 .OMEGA.cm.sup.2
and an interfacial A/C ratio of 1.01. After ambient storage
followed by a pre-discharge of 3% cell capacity, Digicam testing is
performed on the cell. The cell may exhibit an average of 638
pulses, an improvement of about 2% versus a cell that includes a
separator/electrolyte combination that has an ASR of greater than 2
.OMEGA.cm.sup.2 and an interfacial A/C ratio of 1.01.
TABLE-US-00002 TABLE 2 Digicam Performance Testing for selected
separator/electrolyte combinations. INTERFACIAL PERFORMANCE
SEPARATOR ELECTROLYTE A/C RAITO (Pulses) 1 A 1.01 559 2 A 1.01 592
1 C 1.01 624 2 C 1.01 638
[0053] The dimensions and values disclosed herein are not to be
understood as being strictly limited to the exact numerical values
recited. Instead, unless otherwise specified, each such dimension
is intended to mean both the recited value and a functionally
equivalent range surrounding that value. For example, a dimension
disclosed as "40 mm" is intended to mean "about 40 mm."
[0054] Every document cited herein, including any cross referenced
or related patent or application, is hereby incorporated herein by
reference in its entirety unless expressly excluded or otherwise
limited. The citation of any document is not an admission that it
is prior art with respect to any invention disclosed or claimed
herein or that it alone, or in any combination with any other
reference or references, teaches, suggests or discloses any such
invention. Further, to the extent that any meaning or definition of
a term in this document conflicts with any meaning or definition of
the same term in a document incorporated by reference, the meaning
or definition assigned to that term in this document shall
govern.
[0055] While particular embodiments of the present invention have
been illustrated and described, it would be obvious to those
skilled in the art that various other changes and modifications can
be made without departing from the spirit and scope of the
invention. It is therefore intended to cover in the appended claims
all such changes and modifications that are within the scope of
this invention.
* * * * *