FIELD OF INVENTION
The present embodiments relate generally to non-woven webs, and specifically5 ,
to non-woven webs that can be used as battery separators for batteries, such as lead acid
batteries.
BACKGROUND
10 Batteries convert stored chemical energy into electrical energy and are commonly
used as energy sources. Typically, a battery comprises one or more electrochemical cells
including a negative electrode, a positive electrode, an electrolyte, and a battery
separator. Battery separators are a critical component in many batteries. The battery
separator mechanically and electrically isolates the negative and positive electrodes,
15 while also allowing ions in the electrolyte to move between the electrodes.
Battery separators should be chemically, mechanically, and electrochemically
stable under the strongly reactive environments in the battery during operation, should
not adversely interact with the electrolyte and/or electrode materials, and have no
deleterious effect on of the battery’s performance (e.g., energy production, cycle life,
20 safety). For example, the battery separator should not degrade, leach harmful
components, react in a negative way with the electrode materials, allow short circuits to
form between the electrodes, and/or crack or break during battery assembly and/or
operation. Though many battery separators exist, improvements in the stability of
battery separators and/or battery separators that lead to enhanced battery performance are
25 needed.
SUMMARY
In one set of embodiments, battery separators are provided. In one embodiment,
a battery separator comprises a non-woven web comprising a plurality of glass fibers
30 having an average diameter of greater than or equal to about 0.1 microns and less than or
equal to about 15 microns, wherein the glass fibers are present in an amount of greater
than or equal to about 2 wt.% and less than or equal to about 95 wt.% of the non-woven
web; a plurality of synthetic fibers, wherein the synthetic fibers are present in the nonwoven
web in an amount of greater than or equal to about 1 wt.% and less than or equal
2
to about 80 wt.% of the non-woven web; and a plurality of inorganic particles, wherein
the inorganic particles are present in an amount of greater than or equal to about 10 wt.%
and less than or equal to about 80 wt.% of the non-woven web and wherein the apparent
density of the battery separator is greater than or equal to about 40 g/m2/mm and less
than or equal to about 300 g/m2/5 mm.
In another embodiment, a battery separator comprises a non-woven web
comprising a plurality of glass fibers having an average diameter of greater than or equal
to about 0.1 microns; a plurality of synthetic fibers, wherein the synthetic fibers are
present in an amount of greater than or equal to about 1 wt.% and less than or equal to
10 about 80 wt.% of the non-woven web; and a plurality of inorganic particles, wherein the
inorganic particles are present in an amount of greater than or equal to about 10 wt.%
and less than or equal to about 80 wt.% of the non-woven web, wherein the non-woven
web is corrugated, embossed, pleated, creped, or micrexed.
In one embodiment, a battery separator comprises a non-woven web comprising a
15 plurality of glass fibers having an average diameter of greater than or equal to about 0.1
microns; a plurality of synthetic fibers, wherein the synthetic fibers are present in an
amount of greater than or equal to about 1 wt.% and less than or equal to about 80 wt.%
of the non-woven web; a plurality of inorganic particles, wherein the inorganic particles
are present in an amount of greater than or equal to about 10 wt.% and less than or equal
20 to about 80 wt.% of the non-woven web; and an additional layer adjacent the non-woven
web, wherein the additional layer is corrugated, embossed, pleated, creped, or micrexed.
Other advantages and novel features of the present invention will become
apparent from the following detailed description of various non-limiting embodiments of
the invention when considered in conjunction with the accompanying figures. In cases
25 where the present specification and a document incorporated by reference include
conflicting and/or inconsistent disclosure, the present specification shall control. If two
or more documents incorporated by reference include conflicting and/or inconsistent
disclosure with respect to each other, then the document having the later effective date
shall control.
30
BRIEF DESCRIPTION OF THE DRAWINGS
Non-limiting embodiments of the present invention will be described by way of
example with reference to the accompanying figure, which is schematic and is not
3
intended to be drawn to scale. In the figure, each identical or nearly identical component
illustrated is typically represented by a single numeral. For purposes of clarity, not every
component is labeled, nor is every component of each embodiment of the invention
shown where illustration is not necessary to allow those of ordinary skill in the art to
understand the invention. In the figures5 :
FIG. 1 is a schematic diagram of a battery separator including a non-woven web
according to one set of embodiments;
FIG. 2A is a schematic diagram of the thickness and overall thickness of a planar
layer that can be included in a battery separator according to one set of embodiments;
10 FIG. 2B is a schematic diagram of the thickness and overall thickness of a nonplanar
layer that can be included in a battery separator according to one set of
embodiments;
FIGs. 3A-3D are schematic diagrams showing different battery arrangements
according to one set of embodiments; and
15 FIGs. 4A-4D are schematic diagrams of a battery separator and an electrode,
according to one set of embodiments.
DETAILED DESCRIPTION
Battery separators are provided. In some embodiments, a battery separator
20 described herein may have at least one non-planar layer (e.g., a shaped layer, such as a
corrugated layer, an embossed layer, a crimped layer). The non-planar layer may have
undulations or other surface features, as described in more detail below. In some
embodiments, a layer and/or battery separator described herein has a relatively low
apparent density; i.e., the basis weight of the layer/separator over the volume within the
25 outermost boundaries of the layer/separator may be relatively low. The low apparent
density may be attributed to, at least in part, the geometry of the layer. In some
embodiments, a battery comprising a non-planar layer and/or a layer having a relatively
low apparent density may have desirable properties, including relatively low electrical
resistance and/or relatively high capacity. The battery separators described herein may
30 be well suited for a variety of battery types, including lead acid batteries.
In a typical battery, the battery separator primarily functions to electrically and
mechanically isolate the negative electrode and positive electrode, while allowing ionic
conduction. However, the presence of the battery separator between the electrodes can
4
affect battery performance (e.g., electrical resistance, lifetime). For instance, the battery
separator generally increases the resistance to ion movement between the electrodes
compared to the electrolyte alone and thus increases the electrical resistance of the
battery. Moreover, the battery separator can reduce the amount of electrolyte between
the electrodes compared to the electrolyte alone for a given volume between 5 n the
electrodes), due to the volume occupied by the battery separator. This reduction of
electrolyte can limit the battery capacity.
In general, the chemical (e.g., composition, stability, wettability), structural (e.g.,
porosity, pore size, thickness, permeability), and/or mechanical (e.g., strength, stiffness)
10 properties of the battery separator can affect battery performance (e.g. electrical
resistance, lifetime). In some battery applications, a trade-off exists between the
properties of the battery separator that provide sufficient isolation and/or ion movement,
and battery performance. For instance, a battery separator having a sufficient porosity to
allow for ion mobility may be brittle and result in early battery failure due to damage to
15 the separator. The balance of separator and battery performance is further aggravated in
battery applications that utilize highly reactive operating conditions, such as lead acid
batteries. In such applications, the chemical, mechanical, and electrochemical stability
of the battery separator may be important design parameters to be balanced with
separator and battery performance. Often, conventional battery separators are designed
20 to have desirable stability, separation performance, or battery performance at the expense
of one or more other properties such as stability, separation performance, and/or battery
performance.
For example, some conventional battery separators have attempted to minimize
the influence of the battery separator on capacity and electrical resistance by reducing the
25 mass of the battery separator to increase the volume porosity. However, the tradeoff
between mass and mechanical stability can limit this approach. Accordingly, there is a
need for improved battery separators.
In the present disclosure, battery separators are provided. In some embodiments,
a battery separator may include a layer (e.g., non-woven web) that has at least one non30
planar surface (e.g., a shaped layer, or a layer that includes undulations or other surface
topography, as described herein). Such a layer may be used alone, or in combination
with an additional layer, in a battery separator as described herein. The layer
shape/topography can be used to impart desirable properties to the battery separator
5
and/or overall battery (e.g. stability, separation performance, battery performance). For
instance, in some embodiments involving a battery comprising a layer that includes
undulations and/or has at least one non-planar surface (i.e., a non-planar layer)
positioned between two electrodes, the shape of the layer may increase the void volume
between the electrodes resulting in a decrease in electrical resistance and dendrit5 e
formation. In certain embodiments, these desirable properties can be imparted while
having little or no adverse effects on another property of the battery separator and/or
overall battery. In some such embodiments, a battery separator comprising a layer (e.g.,
non-woven web) described herein does not suffer from one or more limitations of certain
10 existing battery separators. As described further below, such a battery separator may
include, in some embodiments, a non-woven web comprising glass fibers, synthetic
fibers, inorganic particles, and/or other components (e.g., binder resin) as described
herein.
In certain embodiments, the battery separator may include a non-woven web (e.g.
15 a planar non-woven web or a non-woven web including at least one non-planar surface)
and an additional layer that has at least one non-planar surface (e.g., includes
undulations). As used herein a “non-planar layer” refers to a layer that includes repeated
undulations and/or has at least one non-planar surface. An undulating layer (i.e., a layer
that includes undulations) refers to a layer that includes repeated bends that distorts both
20 the top and bottom face of the layer in a similar manner. For instance, a cross-section of
a bend or curve of the layer will have a top line 56 that is parallel to the bottom line 57,
e.g., as shown in FIG. 2B. In some embodiments, the size or amplitude of the bends or
curves may be on the order of the thickness of the layer (e.g., 0.1-2 times the thickness of
the layer) or greater, as described in more detail below. The bends or curves in the
25 undulating layer may be irregular or regular. In some embodiments, the undulating layer
may have a wavelike form. Examples of such layers include corrugated layers, pleated
layers, and crimped layers, amongst others.
A non-limiting example of a battery separator including a non-woven web is
shown schematically in FIG. 1. In some embodiments, a battery separator 5 may include
30 a non-woven web 6. In some embodiments, non-woven web 6 may be a non-planar
layer. In some embodiments, the battery separator may be a single layer (e.g., the
separator does not include layers 7 or 8 in FIG. 1). For instance, the battery separator
may be formed of a single non-woven web.
6
In other embodiments, the battery separator may comprise multiple layers. The
multi-layer battery separator may include at least one non-woven web (e.g., at least two
non-woven webs, at least three non-woven webs). In some embodiments, the at least one
non-woven web may have one or more non-planar surfaces, as described herein. In some
embodiments, in addition to non-woven web 6, the battery separator may include 5 an
optional layer 7 and/or 8 (e.g., additional layers), which may be adjacent the non-woven
web. The additional layer may be planar or non-planar as described herein.
For instance, in one particular embodiment, the battery separator may comprise a
non-planar, non-woven layer 6, a layer 7 (e.g., non-woven web) (that may, for example,
10 allow even pressure distribution of non-woven layer 6 in a battery configuration), and a
non-woven web 8. In some such cases, layer 7 may be a non-planar, non-woven layer
having a relatively high Gurley stiffness (e.g., greater than or equal to about 500 mg and
less than or equal to about 5000 mg, greater than or equal to about 800 to less than or
equal to about 1200 mg). Such a layer may have, in some embodiments, substantially
15 the same or similar attributes as non-woven layer 6 (e.g., chemical stability, volume
porosity). However, other configurations are also possible. In some embodiments in
which non-woven layer 6 is non-planar, layer 7 may be a planar layer. For instance, in
one embodiment, layer 7 may be the planar version of non-woven layer 6. In other
embodiments, optional layer 7 and/or 8 may be a non-planar layer. In general, any layer
20 of the battery separator may be non-planar, as described herein.
In general, a layer within a battery separator, including any optional layer(s) (e.g.,
additional layer(s)) should be stable in a battery environment, have sufficient porosity to
allow for sufficient ionic conduction, and have a suitable thickness. For instance, in a
lead acid battery, the layer(s) may have an acid weight loss of less than 5% according to
25 the standard BCI 03-A. As used herein, acid weight loss refers to the percent of weight
loss due to acid erosion, as described in more detail below. In certain embodiments, the
layer(s), including the optional layer(s), may have a porosity of greater than or equal to
about 10% and less than or equal to about 99% (e.g., greater than or equal to about 65%
and less than or equal to about 95%) and a thickness of greater than or equal to about
30 0.05 mm and less than or equal to about 30 mm (e.g., greater than or equal to about 0.1
mm and less than or equal to about 3 mm). It should be appreciated, however, that other
ranges of acid weight loss, porosity, and/or thickness are possible.
7
In some embodiments, one or more optional layers (e.g., additional layers) may
be a non-woven web. For instance, in some embodiments a second non-woven web may
be present in the battery separator. In certain embodiments, the optional layer may be a
planar layer having a relatively low apparent density (e.g., an open layer), as described
herein. Non-limiting examples of optional/additional layers include non-woven we5 bs
formed of long, coarsely drawn individual glass fibers (e.g., having a fiber diameter of
greater than about 13 microns) bonded with an adhesive in the parallel direction (e.g., a
sliver), rovings (e.g., a long fiber adhesive-bonded non-woven web used for insulation),
braids, spacer fabrics (e.g., layers separated by a system of rigid support members
10 running perpendicular to the outer surfaces), corduroy fabrics, ribbed knits, porous
membranes, functionalized needle punched and hydroentangled non-woven webs, and
nets (e.g., synthetic expanded mesh). Woven webs can also be used. In other
embodiments, one or more optional layers (e.g., additional layers) may be an extruded
layer (e.g., a non-fibrous layer). Other types of layers are also possible.
15 As used herein, when a layer is referred to as being “adjacent” another layer, it
can be directly adjacent to the layer, or an intervening layer also may be present. A layer
that is “directly adjacent” another layer means that no intervening layer is present.
In some embodiments, one or more layer in the battery separator may be
designed to be discrete from another layer. That is, the components (e.g., fibers) from
20 one layer do not substantially intermingle (e.g., do not intermingle at all) with
components (e.g., fibers) from another layer. For example, with respect to FIG. 1, in one
set of embodiments, fibers from non-woven web 6 do not substantially intermingle with
fibers of optional layer 8. Discrete layers may be joined by any suitable process
including, for example, lamination, thermo-dot bonding, calendering, ultrasonic
25 processes, or by adhesives, as described in more detail below. It should be appreciated,
however, that certain embodiments may include one or more layers that are not discrete
with respect to one another.
It should be understood that the configurations of the layers shown in the figures
are by way of example only, and that in other embodiments, battery separators including
30 other configurations of layers may be possible. For example, while the optional layers
are shown in a specific order in FIG. 1, other configurations are also possible. For
example, optional layer 7 may be positioned between the non-woven web and optional
layer 8. Furthermore, in some embodiments, additional layers may be present in addition
8
to the ones shown in the figures. It should also be appreciated that not all components
shown in the figures need be present in some embodiments.
A design of a battery separator that produces desirable separator performance,
battery performance, and/or chemical stability is difficult to achieve for batteries having
highly reactive operating conditions. For instance, in some embodiments, batter5 y
separators having the requisite chemical stability may only be formed from a limited
number of materials and/or may be required to have a certain structure. Conversely,
separators that produce excellent battery performance may be susceptible to degradation
and/or adverse chemical reaction in a highly reactive battery environment. Certain
10 features of a battery separator described herein will now be described in the context of an
exemplary application: lead acid batteries. Lead acid batteries are used herein as one
example of a battery that has highly reactive operating conditions. It should be
understood, however, that the battery separators described herein may be suitable for a
wide variety of applications and are not limited to use in lead acid batteries.
15 Lead acid batteries comprise a positive electrode comprising lead dioxide (PbO2),
and negative electrode comprising metallic lead, and an electrolyte comprising a high
molarity aqueous sulfuric acid solution. During discharge of the lead acid batteries, the
following half reactions occur at the negative electrode and positive electrode,
respectively.
20
Pb0 + HSO4
- PbSO4 + H+ +2e- (negative electrode)
PbO2 + 3H+ + HSO4
- + 2e- PbSO4 + 2H2O (positive electrode)
Without being bound by theory, it is believed that the PbO2 and metallic lead, which is
25 formed from PbSO4 during charging, are more loosely bound to the positive and negative
electrode, respectively, than the PbO2 and metallic lead that has not undergone an
electrochemical reaction. It is believed that cycling of the battery results in shedding of
the active material in the electrode due to this loss of cohesiveness of the active material.
The end of battery cycle life may come from the shedding of the active mass.
30 As described herein, a battery separator may comprise a layer having a relatively
low apparent density. As used herein, apparent density has its ordinary meaning in the
art and may be represented by the following equation.
9
Apparent density (g/m2×mm) = Basis weight (g/m2) ÷ Overall thickness (mm)
As illustrated by the equation, apparent density is a measure of the mass of the layer
divided by the volume (i.e., area times overall thickness) of the layer that includes any
unoccupied space within the outermost boundaries of the layer, also referred to as 5 voids.
The overall thickness is measured according to BCIS-03A under 10kPa as
described in more detail below. The voids of the layer are accounted for in the overall
thickness. FIG.2 shows the difference between overall thickness and thickness for a
layer having planar surfaces (e.g., planar layer 50) and a layer having at least one non10
planar surface and/or that includes undulations (e.g.., non-planar layer 55). The overall
thickness 60, as well as thickness 61, of the planar layer is measured along surfaces 51
and 52 as shown in FIG. 2A. The overall thickness and thickness for the planar layer are
the same. FIG.2B shows planar layer 50 after undergoing a shaping process (e.g.,
corrugation, embossing, pleating) to form a non-planar layer 55, which has the same
15 thickness 61 as planar layer 50. The thickness 61 of non-planar layer 55 is also
measured from surfaces 51 and 52. The overall thickness 60, however, is measured from
outermost surfaces 56 and 57, which are the most external surfaces of the layer. As
shown in FIG. 2B, the overall thickness takes into account voids 58 in the layer. Thus,
the thickness of the layer refers to the thickness of the material used to form the layer
20 while the overall thickness refers to the spatial thickness of the layer.
In some embodiments, the apparent density of a layer may be lowered by
increasing the overall thickness of the layer as shown illustratively in FIG. 2 (or by
increasing the overall thickness of the layer by a factor larger than a factor of the layer’s
increase in basis weight). For example, planar layer 50 may have an overall thickness of
25 2 mm prior to any shaping process. After subjecting the layer to a shaping process, the
layer may have a non-planar surface and/or undulations in the layer. The non-planar
layer may have an overall thickness 60 (e.g., 10 mm) greater than the overall thickness
60 of the layer prior to shaping. In this example, the basis weight of layer 55 in FIG. 2B
would be greater than the basis weight of layer 50 in FIG. 2A for the same size/area layer
30 (e.g., 10 cm x 10 cm); however, as long as the proportional increase in thickness of layer
55 is larger than its proportional increase in basis weight, the apparent density of layer 55
would be lower than its apparent density prior to shaping (e.g., layer 50 of FIG. 2A). For
example, layer 55 of FIG. 2B having an increase in overall thickness by a factor of 5
10
(e.g., 2 mm to 10 mm) and an increase in basis weight by a factor of about 1.33 (e.g., 300
g/m2 to 400 g/m2), would have an apparent density that is lower by a factor of 3.75 (e.g.,
150 g/m2mm to 40 g/m2mm) compared to that for layer 50 of FIG. 2A.
In some embodiments, a battery separator including a layer having a relatively
low apparent density may result in a battery arrangement having a relatively high tota5 l
void volume between the electrodes. As used herein, total void volume of a layer has its
ordinary meaning in the art and refers to the empty (i.e., void) volume, e.g., that is
capable of being filled with matter (e.g., an electrolyte). The total void volume includes
the internal void volume and the external void volume. The internal void volume refers
10 to the volume within the internal voids (e.g., pores) in the layer itself; that is the empty
(i.e., void) volume within the outermost boundaries of the layer, e.g., that is capable of
being filled with matter (e.g., an electrolyte). The external void volume refers to the
volume within the external voids (e.g., the volume under a bend in the layer) formed as a
result of the shape of the layer. The total void volume percentage, also referred to as the
15 total volume porosity, may be determined using the following formula:
% Total Volume Porosity = 100 – (Basis weight / (Matter density x overall thickness))
where matter density refers to the density of the components forming the separator/layer
20 (e.g., fibers), e.g., as measured by BCIS-03A, Sept-09 Method 11. For example, the
matter density for a battery separator containing only glass fibers would be the density of
the glass fibers. The matter density of a battery separator comprising a mixture of fibers,
inorganic particles, and binder resin would be would be a weighted average of the
density of each material in the battery separator.
25 The internal volume porosity percent may be determined according to the
standard BCIS-03B – Method 6, which is a volume displacement method.
Non-limiting examples of void volumes within battery separators comprising a
conventional planar layer, a conventional ribbed layer, or non-planar layers of the present
disclosure are shown in FIG. 3. FIG. 3A shows a cross-section of a battery arrangement
30 comprising a conventional planar battery separator 70 positioned between and in direct
contact with a negative electrode 75 and a positive electrode 80. When a battery
separator is configured between (e.g., in direct contact with) a negative electrode and a
positive electrode, the external void volume refers to the volume between the negative
11
electrode and the surface of the battery separator closest to the negative electrode, and
the volume between the positive electrode and the surface of the battery separator closest
to the positive electrode that is void prior to addition of the electrolyte. In FIG. 3A, the
entire surface area of the negative electrode and the positive electrode are in contact with
the planar battery separator. Thus, in this illustration, the total volume porosity is equa5 l
to the internal void volume (i.e., internal volume porosity) of the battery separator. In
embodiments in which the total volume porosity of the battery separator is equal to the
internal volume porosity of the battery separator, the majority of ion movement occurs
within the battery separator.
10 FIG. 3B shows a cross-section of a battery arrangement comprising a
conventional battery separator 85 comprising ribs 90 on the top and bottom surfaces of
planar layer 88. Ribs, as shown in FIG. 3B, are material added to at least one surface of
the battery separator in a discontinuous arrangement (e.g., the rib material does not form
a continuous sheet of material along the whole surface of the layer on which the ribs are
15 positioned). The ribs act as a spacer between the battery separator and the positive
electrode and/or negative electrode, and creates unoccupied space (e.g., voids) between
the surface of the layer and the surface of the negative electrode and/or positive
electrode. This unoccupied space can be used to increase the volume of electrolyte
between the electrodes. Movement of ions in the unoccupied space (e.g., “freely”
20 moving ions) is not hindered by the battery separator and thus serves to lower electrical
resistance. The unoccupied space may also serve to minimize dendrite formation
because it is easier for dendrites to grow on solid material, such as the fibers of the
separator where there are more potential points of attachment, than to grow in a liquid
(e.g., electrolyte) where there is active ionic conduction. However, since ribs are
25 additional material added to at least one surface of the battery separator, some
conventional ribs may block at least a portion of the separator’s pores and increase the
electrical resistance of the battery separator. Conventional ribs may also reduce the
surface area of the electrode(s) that is/are in direct contact with the battery separator.
The reduction in contact area between the electrode and the separator may result in non30
uniform pressure distribution across the electrodes and may increase shedding of active
material from areas of the electrode that are not in contact with the ribs.
Referring back to FIG. 3B, battery separator 85 may be positioned between
negative electrode 75 and positive electrode 80, such that the ribs are in contact with
12
electrodes but the top and bottom surfaces of planar layer 88 are not in direct contact
with the electrodes. The presence of the ribs creates voids 92 that can allow ions within
the void volume to move “freely” without interference of portions of the battery
separator. In this configuration, the void volume will depend on the size (e.g., height,
width) of the ribs. In some instances, ribs 90 may block portions 94 of layer 5 88 and
hinder the movement of ions through those portions of the layer. Moreover, since the
ribs have a different surface area than layer 88, and may have a different composition
than layer 88, the chemical stability and/or mechanical properties of the ribs may differ
from those of the layer. That is, ribs may change the overall chemical stability and
10 mechanical properties of the battery separator. The use of ribs can also be costly since
additional material used to form the ribs and an additional process step of adding the ribs
to the separator are typically needed.
In some embodiments, a battery separator described herein having at least one
non-planar surface and/or including undulations may have advantages of a separator
15 including ribs (e.g., increase in void volume and freely moving ions), but without (or
reduced degree of) certain limitations of the ribs (e.g., electrical resistance and/or
shedding of active material from areas of the electrode that are not in contact with the
ribs). It is noted that a non-planar layer and/or a surface that includes undulations, as
described herein, does not encompass a planar layer including ribs alone like that shown
20 in FIG. 3B, though a non-planar layer and/or a surface that includes undulations is not
precluded from including ribs.
Examples of a battery separator including a layer having at least one non-planar
surface and/or including undulations are shown in FIGs.3C-3D. As shown illustratively
in these figures, each of the battery separators may be a layer having two non-planar
25 (opposing) faces. In some instances, the layer may have a patterned shape. For instance,
layer 100 may comprise a regular pattern as in FIG. 3C. In certain embodiments, layer
105 may have an irregular pattern as shown in FIG.3D. In both FIGs. 3C and 3D, the
undulating layers include repeated bends and/or curves that distort both the top and
bottom face of the layer in a similar manner. Regardless of whether the pattern or shape
30 of the non-planar layer is regular or irregular, the shape of the layer may create voids 110
that can allow “free” ion movement.
13
In some embodiments, the shape of the layer may be produced by a process that
does not negatively influence the chemical stability and/or mechanical properties of the
battery separator (e.g., ion conductivity, chemical stability, mechanical strength).
The shaping of the layer/separator may result in different amounts of surface
contact area, i.e., the area of the layer/battery separator in contact with a positive and/5 or
negative electrode (or in direct contact with a planar surface positioned adjacent the
battery separator). In some embodiments, the surface contact area percentage of a
layer/battery separator may be greater than or equal to about 5%, greater than or equal to
about 10%, greater than or equal to about 20%, greater than or equal to about 30%,
10 greater than or equal to about 40%, greater than or equal to about 50%, greater than or
equal to about 60%, greater than or equal to about 70%, greater than or equal to about
75%, greater than or equal to about 80%, or greater than or equal to about 90%. In some
instances, the surface contact area percentage may be less than 100%, less than or equal
to about 90%, less than or equal to about 80%, less than or equal to about 75%, less than
15 or equal to about 70%, less than or equal to about 60%, less than or equal to about 50%,
less than or equal to about 40%, less than or equal to about 30%, less than or equal to
about 20%, or less than or equal to about 15%. Combination of the above-referenced
ranges are also possible (e.g., greater than or equal to about 10% and less than or equal to
about 30%). Other values are also possible. In some embodiments, both sides/surfaces
20 of the battery separator may have percentages of surface contact area within one or more
of the above-referenced ranges. In certain embodiments, the percentage surface contact
area may be measured while applying a pressure of 10 kPa to the layer/battery separator.
In other embodiments, the percentage surface contact area may be measured without
applying any pressure to the layer/battery separator.
25 Various shaping techniques can be used to form a non-planar or shaped layer
described herein. In some embodiments, a shaping technique that allows the geometry of
the layer to be controlled without negatively affecting another beneficial property of the
layer (e.g., volume porosity) may be used. The shape or geometry of the layer may be
altered during and/or after fabrication of the layer. Non-limiting examples of suitable
30 processes include, but are not limited to, corrugation, pleating, embossing creping,
micrexing, and combinations thereof.
As described herein, shaping of a layer may result in the formation of a nonplanar
layer (a layer that includes repeated undulations and/or has at least one non-planar
14
surface). The undulating layer may include repeated bends and/or curves (e.g., waves,
pleats) that distort both the top and bottom face of the layer in a similar manner. In some
embodiments, the average size or amplitude of the bends or curves (e.g., waves, pleats)
may be on the order of the average thickness of the layer (e.g., at least 0.1, at least 0.2
times, at least 0.5 times, at least 1 time, at least 2 times) the thickness of the layer, 5 , or
greater (e.g., at least 4, at least 6, at least 8, at least 10 times the average thickness of the
layer). The average size or amplitude of the bends or curves (e.g., waves, pleats) may be,
in some instances, less than or equal to 20 times, less than or equal to 15 times, less than
or equal to 10 times, less than or equal to 8 times, less than or equal to 5 times, less than
10 or equal to 3 times, less than or equal to 2 times, or less than or equal to 1 time the
average thickness of the layer. Combinations of the above-referenced ranges are also
possible (e.g., average size or amplitude of at least 1 time and less than or equal to 10
times the average thickness of the layer). Other ranges are also possible.
The frequency of bends and/or curves (e.g., waves, pleats) in a layer may also
15 vary. In some embodiments, a layer described herein (e.g., a non-planar layer, an
undulating layer) may have at least 1 bend/100 mm, at least 10 bends/100 mm, at least
50 bends/100 mm, at least 100 bends/100 mm, at least 200 bends/100 mm, at least 300
bends/100 mm, at least 400 bends/100 mm, at least 500 bends/100 mm, at least 600
bends/100 mm, at least 700 bends/100 mm, at least 800 bends/100 mm, or at least 900
20 bends/100 mm. In certain embodiments, a layer described herein (e.g., a non-planar
layer, an undulating layer) may have less than or equal to 1000 bends/100 mm, less than
or equal to 900 bends/100 mm, less than or equal to 800 bends/100 mm, less than or
equal to 700 bends/100 mm, less than or equal to 600 bends/100 mm, less than or equal
to 500 bends/100 mm, less than or equal to 400 bends/100 mm, less than or equal to 300
25 bends/100 mm, less than or equal to 200 bends/100 mm, less than or equal to 100
bends/100 mm, less than or equal to 50 bends/100 mm, or less than or equal to 10
bends/100 mm. Combinations of the above-referenced ranges are also possible (e.g., at
least 100 bends/100 mm and less than or equal to 1000 bends/100 mm). Other ranges are
also possible. It should appreciated that the ranges above for bends can also be applied
30 to curves, waves, pleats or other repeated units of shape (e.g., embossed patterns) as
described herein.
The percent surface area of the layer that is shaped (i.e., the percent surface area
that is non-planar, or at a non-zero angle (e.g., at an angle of greater than or equal to
15
about 5 degrees, at an angle of greater than or equal to about 10 degrees, at an angle of
greater than or equal to about 15 degrees), with respect to the plane of the layer) may
also vary. In some embodiments, the percent surface area of the layer that is shaped may
be greater than or equal to about 5%, greater than or equal to about 10%, greater than or
equal to about 20%, greater than or equal to about 30%, greater than or equal to 5 o about
40%, greater than or equal to about 50%, greater than or equal to about 60%, greater than
or equal to about 70%, greater than or equal to about 75%, greater than or equal to about
80%, or greater than or equal to about 90%. In some instances, the percent surface area
of the layer that is shaped may be less than 100%, less than or equal to about 90%, less
10 than or equal to about 80%, less than or equal to about 75%, less than or equal to about
70%, less than or equal to about 60%, less than or equal to about 50%, less than or equal
to about 40%, less than or equal to about 30%, less than or equal to about 20%, or less
than or equal to about 15%. Combination of the above-referenced ranges are also
possible (e.g., greater than or equal to about 10% and less than or equal to about 30%).
15 Other values are also possible. In some embodiments, both sides/surfaces of the layer
may have percentages within one or more of the above-referenced ranges. The percent
surface area of the layer that is shaped may be occupied by bends, curves, waves, pleats
or other repeated units of shape as described herein.
In some embodiments, corrugation or pleating may be used to shape a layer (e.g.,
20 non-woven web). The corrugation or pleating may be performed in the machine
direction or cross direction. In some embodiments, corrugation or pleating may result in
bends, curves, waves, or pleats within the layer having an amplitude, frequency and/or
percent surface area of coverage as described herein.
In some embodiments, embossing may be used to shape a layer. Several different
25 techniques may be used to emboss the layer. For example, pressure may be applied to a
layer using a roll system to form surface features (e.g., indentations) having a specific
pattern. In some instances, the layer may be formed on a wire (e.g., inclined table, flat
table, rotoformer, round former) that has a mesh pattern. The mesh pattern may generate
zones with more or less pulp and, accordingly, may produce an uneven thickness profile
30 (e.g., indentations) across the layer. In some such embodiments, the indendations may
be in the form of a mesh pattern, and may have a depth and/or a percent area coverage in
the layer in one or more ranges described herein. In embodiments in which the layer is a
wet laid layer, the layer may be embossed during the wet stage using a dandy roll with a
16
defined pattern. An embossed layer may comprise repeated units of one or more shape
(e.g., square indentations). The repeated units may have a defined shape, which may be,
for example, substantially circular, square, rectangular, trapezoidal, polygonal, or oval in
cross-section and/or in plan view (i.e., viewed from above). The shapes may be regular
or irregular. Any suitable shape may be embossed onto the layer5 .
In certain embodiments, the plurality of indentations in an embossed layer may
be arranged to form a pattern. In some embodiments, the pattern of indentations may be
simple, such as a checkerboard pattern, or more complex like a honeycomb pattern. In
other cases, for example, the pattern may be cubic, hexagonal, and/or polygonal. The
10 pattern of indentations may be regular or irregular.
In embodiments in which a layer described herein includes a non-planar surface
(e.g., an embossed surface), the average size or depth of the surface features (e.g.,
indentations) in the layer may be at least at least 0.05 times, at least 0.1 times, at least 0.2
times, at least 0.5 times, at least 1 time, at least 2 times, at least 4 times, at least 6 times,
15 or at least 8 times the average thickness of the layer. The average size or depth of the
surface features (e.g., indentations) in the layer may be less than or equal to 10 times,
less than or equal to 8 times, less than or equal to 5 times, less than or equal to 3 times,
less than or equal to 2 times, or less than or equal to 1 time the average thickness of the
layer. Combinations of the above-referenced ranges are also possible (e.g., average size
20 or depth of at least 0.1 times and less than or equal to 4 times the average thickness of
the layer). Other ranges are also possible.
In embodiments in which a layer described herein includes a non-planar surface
(e.g., an embossed surface), the average size or depth of the surface features (e.g.,
indentations) in the layer may be at least 0.05 times, at least 0.1 times, at least 0.2 times,
25 at least 0.5 times, at least 1 time the overall thickness of the layer. The average size or
depth of the surface features (e.g., indentations) in the layer may be less than or equal to
1 time, less than or equal to 0.5 times, less than or equal to 0.2 times, or less than or
equal to 0.1 times the overall thickness of the layer. Combinations of the abovereferenced
ranges are also possible (e.g., average size or depth of at least 0.1 times and
30 less than or equal to 1 times the overall thickness of the layer). Other ranges are also
possible.
The frequency of indentations in a layer may also vary. In some embodiments, a
layer described herein (e.g., an embossed layer) may have at least 1 indentation/100
17
mm2, at least 2 indentations/100 mm2, at least 5 indentations/100 mm2, at least 10
indentations/100 mm2, at least 20 indentations/10 mm2, at least 30 indentations/100 mm2,
at least 40 indentations/100 mm2, at least 50 indentations/100 mm2, at least 60
indentations/100 mm2, at least 70 indentations/100 mm2, at least 80 indentations/100
mm2, or at least 90 indentations/100 mm2. In certain embodiments, a layer describe5 d
herein (e.g., an embossed layer) may have less than or equal to 100 indentations/100
mm2, less than or equal to 90 indentations/100 mm2, less than or equal to 80
indentations/100 mm2, less than or equal to 70 indentations/100 mm2, less than or equal
to 60 indentations/100 mm2, less than or equal to 50 indentations/100 mm2, less than or
equal to 40 indentations/100 mm2, less than or equal to 30 indentations/100 mm210 , less
than or equal to 20 indentations/100 mm2, less than or equal to 10 indentations/100 mm2,
less than or equal to 5 indentations/100 mm2, or less than or equal to 2 indentations/100
mm2. Combinations of the above-referenced ranges are also possible (e.g., at least 10
indentations/100 mm2 and less than or equal to 100 indentations/100 mm2). Other ranges
15 are also possible.
The percent surface area of the layer that is embossed (i.e., the percent surface
area that is indented) may also vary. In some embodiments, the percent surface area of
the layer that is embossed may be greater than or equal to about 5%, greater than or equal
to about 10%, greater than or equal to about 20%, greater than or equal to about 30%,
20 greater than or equal to about 40%, greater than or equal to about 50%, greater than or
equal to about 60%, greater than or equal to about 70%, greater than or equal to about
75%, greater than or equal to about 80%, or greater than or equal to about 90%. In some
instances, the percent surface area of the layer that is embossed may be less than 100%,
less than or equal to about 90%, less than or equal to about 80%, less than or equal to
25 about 75%, less than or equal to about 70%, less than or equal to about 60%, less than or
equal to about 50%, less than or equal to about 40%, less than or equal to about 30%,
less than or equal to about 20%, or less than or equal to about 15%. Combination of the
above-referenced ranges are also possible (e.g., greater than or equal to about 10% and
less than or equal to about 30%). Other values are also possible. In some embodiments,
30 both sides/surfaces of the layer may have percentages within one or more of the abovereferenced
ranges.
In some embodiments, creping may be used to shape the layer. In some
embodiments, creping refers to the generation of a 3D structure of a flat wet sheet using
18
a quick change of speed and angle of the sheet path from a smooth roll. In some
embodiments, creping may be used to form an irregular shape in the layer, such as an
irregular wave pattern. In some embodiments, creping may be used to form a regular
shape. In some embodiments, creping may result in bends, curves, waves or patterns
within the layer having an amplitude, frequency and/or percent surface area of covera5 ge
as described herein.
In some embodiments, micrexing may be used to shape the layer. Micrex is
similar to creping but is performed on a fully dried sheet. In some embodiments,
micrexing may be used to form an irregular shape in the layer, such as an irregular wave
10 pattern. In some embodiments, microexing may be used to form a regular shape. In
some embodiments, micrexing may result in bends, curves, waves or patterns within the
layer having an amplitude, frequency and/or percent surface area of coverage as
described herein.
It should be appreciated that while in some embodiments a layer may be shaped,
15 e.g., corrugated, pleated, embossed, creped, and/or micrexed, in some embodiments, a
layer described herein (e.g., a shaped layer, a non-woven layer) is not corrugated, not
pleated, not embossed, not creped, and/or not micrexed. Additionally, it should be
understood that in certain embodiments, more than one shaping technique can be used to
form a layer and/or separator described herein (e.g., corrugation and embossing). Other
20 configurations are also possible.
In some embodiments, a non-woven web may include glass fibers (e.g.,
microglass fibers, chopped strand glass fibers, or a combination thereof). Microglass
fibers and chopped strand glass fibers are known to those of ordinary skill in the art.
One of ordinary skill in the art is able to determine whether a glass fiber is microglass or
25 chopped strand by observation (e.g., optical microscopy, electron microscopy).
Microglass fibers may also have chemical differences from chopped strand glass fibers.
In some cases, though not required, chopped strand glass fibers may contain a greater
content of calcium or sodium than microglass fibers. For example, chopped strand glass
fibers may be close to alkali free with high calcium oxide and alumina content.
30 Microglass fibers may contain 10-15% alkali (e.g., sodium, magnesium oxides) and have
relatively lower melting and processing temperatures. The terms refer to the
technique(s) used to manufacture the glass fibers. Such techniques impart the glass
fibers with certain characteristics. In general, chopped strand glass fibers are drawn from
19
bushing tips and cut into fibers in a process similar to textile production. Chopped strand
glass fibers are produced in a more controlled manner than microglass fibers, and as a
result, chopped strand glass fibers will generally have less variation in fiber diameter and
length than microglass fibers. Microglass fibers are drawn from bushing tips and further
subjected to flame blowing or rotary spinning processes. In some cases, fine microglas5 s
fibers may be made using a remelting process. In this respect, microglass fibers may be
fine or coarse. As used herein, fine microglass fibers are less than or equal to 1 micron
in diameter and coarse microglass fibers are greater than or equal to 1 micron in
diameter.
10 The microglass fibers may have small diameters. For instance, in some
embodiments, the average diameter of the microglass fibers may be less than or equal to
about 10 microns, less than or equal to about 9 microns, less than or equal to about 7
microns, less than or equal to about 5 microns, less than or equal to about 3 microns, or
less than or equal to about 1 micron. In some instances, the microglass fibers may have
15 an average fiber diameter of greater than or equal to about 0.1 microns, greater than or
equal to about 0.3 microns, greater than or equal to about 1 micron, greater than or equal
to about 3 microns, or greater than or equal to about 7 microns. Combinations of the
above-referenced ranges are also possible (e.g., greater than or equal to about 0.1
microns and less than or equal to about 10 microns, greater than or equal to about 0.1
20 microns and less than or equal to about 5 microns, greater than or equal to about 0.3
microns and less than or equal to about 3 microns). Other values of average fiber
diameter are also possible. Average diameter distributions for microglass fibers are
generally log-normal. However, it can be appreciated that microglass fibers may be
provided in any other appropriate average diameter distribution (e.g., Gaussian
25 distribution).
In some embodiments, the average length of microglass fibers may be less than
or equal to about 10 mm, less than or equal to about 10 mm, less than or equal to about 8
mm, less than or equal to about 6 mm, less than or equal to about 5 mm, less than or
equal to about 4 mm, less than or equal to about 3 mm, or less than or equal to about 2
30 mm. In certain embodiments, the average length of microglass fibers may be greater
than or equal to about 1 mm, greater than or equal to about 2 mm, greater than or equal
to about 4 mm, greater than or equal to about 5 mm, greater than equal to about 6 mm, or
greater than or equal to about 8 mm. Combinations of the above referenced ranges are
20
also possible (e.g., microglass fibers having an average length of greater than or equal to
about 4 mm and less than about 6 mm). Other ranges are also possible.
In other embodiments, the microglass fibers may vary significantly in length as a
result of process variations. For instance, in some embodiments, the average aspect
ratios (length to diameter ratio) of the microglass fibers in a non-woven web may 5 be
greater than or equal to about 100, greater than or equal to about 200, greater than or
equal to about 300, greater than or equal to about 1000, greater than or equal to about
3,000, greater than or equal to about 6,000, greater than or equal to about 9,000. In some
instances, the microglass fibers may have an average aspect ratio of less than or equal to
10 about 10,000, less than or equal to about 5,000, less than or equal to about 2,500, less
than or equal to about 600, or less than or equal to about 300. Combinations of the
above-referenced ranges are also possible (e.g., greater than or equal to about 200 and
less than or equal to about 2,500). Other values of average aspect ratio are also possible.
It should be appreciated that the above-noted dimensions are not limiting and that the
15 microglass fibers may also have other dimensions.
In general, chopped strand glass fibers may have an average fiber diameter that is
greater than the diameter of the microglass fibers. For instance, in some embodiments,
the average diameter of the chopped strand glass fibers may be greater than or equal to
about 5 microns, greater than or equal to about 7 microns, greater than or equal to about
20 9 microns, greater than or equal to about 11 microns, or greater than or equal to about 20
microns. In some instances, the chopped strand glass fibers may have an average fiber
diameter of less than or equal to about 30 microns, less than or equal to about 25
microns, less than or equal to about 15 microns, less than or equal to about 12 microns,
or less than or equal to about 10 microns. Combinations of the above-referenced ranges
25 are also possible (e.g., greater than or equal to about 5 microns and less than or equal to
about 12 microns). Other values of average fiber diameter are also possible. Chopped
strand diameters tend to follow a normal distribution. Though, it can be appreciated that
chopped strand glass fibers may be provided in any appropriate average diameter
distribution (e.g., Gaussian distribution).
30 In some embodiments, chopped strand glass fibers may have a length in the range
of between about 0.125 inches and about 1 inch (e.g., about 0.25 inches, or about 0.5
inches). In some embodiments, the average length of chopped strand glass fibers may be
less than or equal to about 1 inch, less than or equal to about 0.8 inches, less than or
21
equal to about 0.6 inches, less than or equal to about 0.5 inches, less than or equal to
about 0.4 inches, less than or equal to about 0.3 inches, or less than or equal to about 0.2
inches. In certain embodiments, the average length of chopped strand glass fibers may
be greater than or equal to about 0.125 inches, greater than or equal to about 0.2 inches,
greater than or equal to about 0.4 inches, greater than or equal to about 0.5 inches5 ,
greater than equal to about 0.6 inches, or greater than or equal to about 0.8 inches.
Combinations of the above referenced ranges are also possible (e.g., chopped strand
glass fibers having an average length of greater than or equal to about 0.125 inches and
less than about 1 inch). Other ranges are also possible.
10 It should be appreciated that the above-noted dimensions are not limiting and that
the microglass and/or chopped strand fibers, as well as the other fibers described herein,
may also have other dimensions.
In some embodiments, the average diameter of the glass fibers in the non-woven
web may be greater than or equal to about 0.1 microns, greater than or equal to about 0.3
15 microns, greater than or equal to about 0.5 microns, greater than or equal to about 1
micron, greater than or equal to about 2 microns, greater than or equal to about 3
microns, greater than or equal to about 5 microns, greater than or equal to about 7
microns, greater than or equal to about 9 microns, greater than or equal to about 10
microns, or greater than or equal to about 12 microns. In some instances, the average
20 diameter of the glass fibers in the non-woven web may have an average fiber diameter of
less than or equal to about 15 microns, less than or equal to about 12 microns, less than
or equal to about 10 microns, less than or equal to about 8 microns, less than or equal to
about 5 microns, less than or equal to about 3 microns, or less than or equal to about 1
micron. Combinations of the above-referenced ranges are also possible (e.g., greater
25 than or equal to about 0.1 microns and less than or equal to about 15 microns, greater
than or equal to about 0.1 microns and less than or equal to about 10 microns, greater
than or equal to about 0.1 microns and less than or equal to about 5 microns, greater than
or equal to about 0.3 microns and less than or equal to about 3 microns).
In some embodiments, the average length of the glass fibers in the non-woven
30 web may be less than or equal to about 50 mm, less than or equal to about 40 mm, less
than or equal to about 30 mm, less than or equal to about 25 mm, less than or equal to
about 20 mm, less than or equal to about 15 mm, less than or equal to about 12 mm, less
than or equal to about 10 mm, less than or equal to about 8 mm, less than or equal to
22
about 5 mm, less than or equal to about 3 mm, or less than or equal to about 1 mm. In
certain embodiments, the average length diameter of the glass fibers in the non-woven
web may be greater than or equal to about 0.05 mm, greater than or equal to about 0.1
mm, greater than or equal to about 0.2 mm, greater than or equal to about 0.5 mm,
greater than equal to about 1 mm, greater than or equal to about 5 mm, greater than equa5 l
to about 10 mm, greater than or equal to about 15 mm, greater than equal to about 20
mm, greater than or equal to about 30 mm, or greater than or equal to about 40 mm.
Combinations of the above referenced ranges are also possible (e.g., greater than or equal
to about 0.05 mm and less than about 50 mm, greater than or equal to about 1 mm and
10 less than about 25 mm, greater than or equal to about 0.1 mm and less than about 12 mm,
greater than or equal to about 0.2 mm and less than about 6 mm, greater than or equal to
about 0.5 mm and less than about 3 mm). Other ranges are also possible.
A non-woven web may include a suitable percentage of glass fibers. In some
embodiments, the weight percentage of glass fibers in the non-woven web may be
15 greater than or equal to about 2 wt.%, greater than or equal to about 5 wt.%, greater than
or equal to about 10 wt.%, greater than or equal to about 20 wt.%, greater than or equal
to about 30 wt.%, greater than or equal to about 40 wt.%, greater than or equal to about
50 wt.%, greater than or equal to about 60 wt.%, greater than or equal to about 70 wt.%,
greater than or equal to about 80 wt.%, or greater than or equal to about 90 wt.%. In
20 some embodiments, the weight percentage of the glass fibers in the non-woven web may
be less than or equal to about 95 wt.%, less than or equal to about 90 wt.%, less than or
equal to about 80 wt.%, less than or equal to about 70 wt.%, less than or equal to about
60 wt.%, less than or equal to about 50 wt.%, less than or equal to about 40 wt.%, less
than or equal to about 30 wt.%, less than or equal to about 20 wt.%, less than or equal to
25 about10 wt.%, or less than or equal to about 5 wt.%. Combinations of the abovereferenced
ranges are also possible (e.g., greater than about 2 wt.% and less than or equal
to about 95 wt.%, greater than about 5 wt.% and less than or equal to about 50 wt.%,
greater than about 10 wt.% and less than or equal to about 50 wt.%, greater than about 10
wt.% and less than or equal to about 30 wt.%). Other ranges are also possible. In some
30 embodiments, a non-woven web includes the above-noted ranges of glass fibers with
respect to the total weight of fibers in the non-woven web and/or the battery separator.
In some embodiments, a non-woven web described herein includes one or more
synthetic fibers. Synthetic fibers may include any suitable type of synthetic polymer.
23
Examples of suitable synthetic fibers include polyester, polyaramid, polyimide,
polyolefin (e.g., polyethylene), polypropylene, Kevlar, nomex, halogenated polymers
(e.g., polyethylene terephthalate), acrylics, polyphenylene oxide, polyphenylene sulfide,
and combinations thereof. In some embodiments, the synthetic fibers are organic
polymer fibers. Synthetic fibers may also include multi-component fibers (i.e., fiber5 s
having multiple compositions such as bi-component fibers). The non-woven web may
also include combinations of more than one type of composition of synthetic fiber. It
should be understood that other compositions of synthetic fiber types may also be used.
In some embodiments, synthetic fibers may be staple fibers, which may be
10 synthetic fibers that are cut to a suitable average length and are appropriate for
incorporation into a wet-laid or dry-laid process for forming a non-woven web. In some
cases, groups of staple fibers may be cut to have a particular length with only slight
variations in length between individual fibers.
In some embodiments, synthetic fibers may be binder fibers, as described in more
15 detail below.
Non-woven webs including combinations of different types of synthetic fibers are
also possible.
A non-woven web may include a suitable percentage of synthetic fibers. In some
embodiments, the weight percentage of synthetic fibers in the non-woven web may be
20 0%, greater than or equal to about 1 wt.%, greater than or equal to about 5 wt.%, greater
than or equal to about 10 wt.%, greater than or equal to about 15 wt.%, greater than or
equal to about 20 wt.%, greater than or equal to about 30 wt.%, greater than or equal to
about 40 wt.%, greater than or equal to about 50 wt.%, greater than or equal to about 60
wt.%, or greater than or equal to about 70 wt.%. In some embodiments, the weight
25 percentage of the synthetic fibers in the non-woven web may be less than or equal to
about 80 wt.%, less than or equal to about 70 wt.%, less than or equal to about 60 wt.%,
less than or equal to about 50 wt.%, less than or equal to about 40 wt.%, less than or
equal to about 30 wt.%, less than or equal to about 20 wt.%, less than or equal to about
10 wt.%, or less than or equal to about 5 wt.%. Combinations of the above-referenced
30 ranges are also possible (e.g., greater than about 1 wt.% and less than or equal to about
80 wt.%, greater than about 1 wt.% and less than or equal to about 50 wt.%, greater than
about 5 wt.% and less than or equal to about 50 wt.%, greater than about 5 wt.% and less
than or equal to about 30 wt.%, greater than about 10 wt.% and less than or equal to
24
about 40 wt.%, greater than about 15 wt.% and less than or equal to about 25 wt.%).
Other ranges are also possible. In some embodiments, a non-woven web includes the
above-noted ranges of synthetic fibers with respect to the total weight of fibers in the
non-woven web and/or the battery separator.
In general, synthetic fibers may have any suitable dimensions. For instance, 5 , in
some embodiments, the synthetic fibers may have an average diameter of greater than or
equal to about 0.5 micron, greater than or equal to about 1 micron, greater than or equal
to about 2 microns, greater than or equal to about 4 microns, greater than or equal to
about 6 microns, greater than or equal to about 8 microns, greater than or equal to about
10 10 microns, greater than or equal to about 12 microns, greater than or equal to about 15
microns, greater than or equal to about 20 microns, greater than or equal to about 30
microns, or greater than or equal to about 40 microns. In some cases, the synthetic fibers
may have an average diameter of less than or equal to about 50 microns, less than or
equal to about 40 microns, less than or equal to about 30 microns, less than or equal to
15 about 20 microns, less than or equal to about 15 microns, less than or equal to about 12
microns, less than or equal to about 10 microns, than or equal to about 8 microns, less
than or equal to about 6 microns, less than equal to about 4 microns, or less than or equal
to about 2 microns. Combinations of the above referenced ranges are also possible (e.g.,
greater than or equal to about 0.5 microns and less than about 50 microns, greater than or
20 equal to about 5 microns and less than about 20 microns). Other ranges are also
possible.
In some embodiments, synthetic fibers may have an average length of greater
than or equal to about 0.25 mm, greater than or equal to about 0.5 mm, greater than or
equal to about 1 mm, greater than or equal to about 3 mm, greater than or equal to about
25 5 mm, greater than or equal to about 10 mm, greater than or equal to about 25 mm,
greater than or equal to about 50 mm, greater than or equal to about 75 mm, greater than
or equal to about 100 mm, greater than or equal to about 150 mm, greater than or equal
to about 200 mm, or greater than or equal to about 250 mm. In some instances, synthetic
fibers may have an average length of less than or equal to about 300 mm, less than or
30 equal to about 250 mm, less than or equal to about 200 mm, less than or equal to about
150 mm, less than or equal to about 100 mm, less than or equal to about 76 mm, less
than or equal to about 50 mm, less than or equal to about 25 mm, less than or equal to
about 20 mm, less than or equal to about 15 mm, less than or equal to about 12 mm, less
25
than or equal to about 10 mm, less than or equal to about 9 mm, less than or equal to
about 6 mm, less than or equal to about 4 mm, less than or equal to about 2 mm, or less
than or equal to about 1 mm. Combinations of the above-referenced ranges are also
possible (e.g., greater than or equal to about 0.5 mm and less than or equal to about 300
mm, greater than or equal to about 0.25 mm and less than or equal to about 5 76 mm,
greater than or equal to about 1 mm and less than or equal to about 12 mm, greater than
or equal to about 3 mm and less than or equal to about 9 mm). Other values of average
fiber length are also possible.
As described herein, in some embodiments, at least a portion of the synthetic
10 fibers may be binder fibers. The binder fibers may be mono-component (i.e., having a
single composition) or multi-component (i.e., having multiple compositions such as a bicomponent
fiber). The non-woven web may include a suitable percentage of monocomponent
fibers and/or multi-component fibers. In some embodiments, all of the
synthetic fibers are mono-component fibers. In some embodiments, at least a portion of
15 the synthetic fibers are multi-component fibers. In some embodiments, the non-woven
web may comprise a residue from a binder fiber.
An example of a multi-component fiber is a bi-component fiber which includes a
first material and a second material that is different from the first material. The different
components of a multi-component fiber may exhibit a variety of spatial arrangements.
20 For example, multi-component fibers may be arranged in a core-sheath configuration
(e.g., a first material may be a sheath material that surrounds a second material which is a
core material), a side by side configuration (e.g., a first material may be arranged
adjacent to a second material), a segmented pie arrangement (e.g., different materials
may be arranged adjacent to one another in a wedged configuration), a tri-lobal
25 arrangement (e.g., a tip of a lobe may have a material different from the lobe) and an
arrangement of localized regions of one component in a different component (e.g.,
“islands in sea”).
In some embodiments, for a core-sheath configuration, a multi-component fiber,
such as a bi-component fiber, may include a sheath of a first material that surrounds a
30 core comprising a second material. In such an arrangement, for some embodiments, the
melting point of the first material may be lower than the melting point of the second
material. Accordingly, at a suitable step during manufacture of a non-woven web (e.g.,
drying), the first material comprising the sheath may be melted (e.g., may exhibit a phase
26
change) while the second material comprising the core remains unaltered (e.g., may
exhibit no phase change). For instance, an outer sheath portion of a multi-component
fiber may have a melting temperature between about 50 ºC and about 200 ºC (e.g., 180
ºC) and an inner core of the multi-component fiber may have a melting temperature
above 200 ºC. As a result, when the fiber is subjected to a temperature during drying5 ,
e.g., at 180 ºC, then the outer sheath of the fiber may melt while the core of the fiber
does not melt.
Examples of suitable multi-component fibers include polyolefin (e.g.,
polyethylene / PET, coPET (e.g., melt amorphous, melt crystalline) / PET, and
10 polyethylene / polypropylene. In this listing of multi-component fibers, the convention
is to list the material having the lower melting temperature (e.g., first material) separated
from the material having the higher melting temperature (e.g., second material) with a
“/". Other suitable compositions are known to those of skill in the art. In some
embodiments, the binder fiber may include a vinyl compounds (e.g., polyvinyl alcohol).
15 In some embodiments, the weight percentage of multi-component fibers (e.g., bicomponent
fibers) in the non-woven web may be 0%, greater than or equal to about 1
wt.%, greater than or equal to about 5 wt.%, greater than or equal to about 10 wt.%,
greater than or equal to about 15 wt.%, greater than or equal to about 20 wt.%, greater
than or equal to about 30 wt.%, greater than or equal to about 40 wt.%, greater than or
20 equal to about 50 wt.%, greater than or equal to about 60 wt.%, or greater than or equal
to about 70 wt.%. In some embodiments, the weight percentage of the multi-component
fibers (e.g., bi-component fibers) in the non-woven web may be less than or equal to
about 80 wt.%, less than or equal to about 70 wt.%, less than or equal to about 60 wt.%,
less than or equal to about 50 wt.%, less than or equal to about 40 wt.%, less than or
25 equal to about 30 wt.%, less than or equal to about 20 wt.%, less than or equal to about
10 wt.%, or less than or equal to about 5 wt.%. Combinations of the above-referenced
ranges are also possible (e.g., greater than about 5 wt.% and less than or equal to about
30 wt.%). Other ranges are also possible. In some embodiments, a non-woven web
includes the above-noted ranges of multi-component fibers (e.g., bi-component fibers)
30 with respect to the total weight of fibers in the non-woven web and/or the battery
separator.
In general, a non-woven web and/or separator may include any suitable binder
resin. Features of the binder resin may include resistance to the battery environment
27
(e.g., acid electrolyte, oxidation), the ability to be applied in the form of a water soluble
emulsion or dispersion, even flow characteristics on the non-woven web upon drying,
thermal stability, and/or the ability to thermally cure above 100 °C within 1 minute. The
binder resin may comprise a thermoplastic, a thermoset, or a combination thereof. In
some embodiments, the resin may be provided as an aqueous solvent-based system. 5 . In
some such embodiments, the binder resin may be an emulsion or dispersion. In certain
embodiments, the binder resin may be provided as a non-aqueous solvent-based system.
In some embodiments, one or more of the polymers in the resin may comprise aryl
pendant groups. These aryl groups may impart stiffness and steric hindrance on to the
10 main chain, providing excellent chemical and electrochemical resistance.
The amount of resin in a non-woven web may vary. For example, the weight
percentage of binder resin in the non-woven web and/or battery separator may be
between 0 wt.% and 40 wt.%. In some embodiments, the weight percentage of resin in
the non-woven web may be greater than or equal to about 2 wt.%, greater than or equal
15 to about 5 wt.%, greater than or equal to about 10 wt.%, greater than or equal to about 15
wt.%, greater than or equal to about 20 wt.%, greater than or equal to about 25 wt.%,
greater than or equal to about 30 wt.%, greater than or equal to about 35 wt.%, greater
than or equal to about 40 wt.%, or greater than or equal to about 45 wt.%. In some cases,
the weight percentage of resin in the non-woven web may be less than or equal to about
20 50 wt.%, less than or equal to about 45 wt.%, less than or equal to about 40 wt.%, less
than or equal to about 35 wt.%, less than or equal to about 30 wt.%, less than or equal to
about 25 wt.%, less than or equal to about 20 wt.%, less than or equal to about 15 wt.%,
less than or equal to about 10 wt.%, or less than or equal to about 5 wt.%. Combinations
of the above-referenced ranges are also possible (e.g., greater than or equal to about 2
25 wt.% and less than about 40 wt.%, greater than or equal to about 5 wt.% and less than
about 40 wt.%, greater than or equal to about 5 wt.% and less than about 20 wt.%,
greater than or equal to about 10 wt.% and less than about 20 wt.%). Other ranges are
also possible. The weight percentage of binder resin in the entire non-woven web and/or
battery separator is based on the dry solids and can be determined prior to coating the
30 non-woven web.
To form a binder resin containing one or more components of the non-woven
web (e.g., inorganic particles), the components to be included in the binder resin may
first be added in a specific amount to a solution or suspension (e.g., water or other
28
solvent). In some embodiments, an emulsion is formed. A binder resin (and any
optional additives) may then be combined and mixed with the
solution/suspension/emulsion containing the components. It should be understood that
this method of binder resin formulation is not limiting and other methods of resin
formulation are possible. A binder resin containing components therein may be added 5 d to
the non-woven web in any suitable manner (e.g., in the wet state or in the dry state) after
the non-woven web is formed and/or during formation of the non-woven web.
In some embodiments, the non-woven web may comprise inorganic particles. In
some embodiments, inorganic particles in the non-woven web may result in one or more
10 of the following advantages: reduce the pore size of the non-woven without significantly
altering the volume porosity of the non-woven web, increase the wicking and wettability
of the non-woven web, absorb more electrolyte compared to a similar non-woven web
that lacks inorganic particles (all other factors being equal), e.g., due to the wetting
properties of the inorganic particles, and/or scavenge harmful contaminants such as
15 heavy metal ions. For instance, in some embodiments inorganic particles having very
fine pores may create enhanced capillary forces to absorb electrolyte and the trapping of
contaminants may be due, at least in part, to this capillary action. In some embodiments,
the inorganic particles may coat the fibers of the non-woven and serve to reduce the pore
size and/or the variation in pore size of the non-woven web.
20 Non-limiting examples of inorganic particles include silica (e.g., fumed,
ground/mineral, fused, precipitated, agglomerated), clay, talc, diatoms (e.g.,
diatomaceous earth), zeolites, TiO2, rice husk ash, other ashes, and combinations thereof.
In some embodiments, the inorganic particles are substantially non-porous. For certain
battery types, a suitable inorganic particle may be resistant to sulfuric acid and/or may
25 have a suitable surface area.
In some embodiments, the weight percentage of inorganic particles in the nonwoven
web and/or battery separator may be greater than or equal to about 10 wt.%,
greater than or equal to about 20 wt.%, greater than or equal to about 30 wt.%, greater
than or equal to about 40 wt.%, greater than or equal to about 50 wt.%, greater than or
30 equal to about 60 wt.%, or greater than or equal to about 70 wt.%. In some cases, the
weight percentage of inorganic particle in the non-woven web and/or battery separator
may be less than or equal to about 80 wt.%, less than or equal to about 70 wt.%, less than
or equal to about 60 wt.%, less than or equal to about 50 wt.%, less than or equal to
29
about 40 wt.%, less than or equal to about 30 wt.%, less than or equal to about 20 wt.%,
or less than or equal to about 15 wt.%. Combinations of the above-referenced ranges are
also possible (e.g., greater than or equal to about 10 wt.% and less than about 80 wt.%,
greater than or equal to about 30 wt.% and less than about 60 wt.%). Other ranges are
also possible. The weight percentage of inorganic particles in the entire non-woven 5 n web
and/or battery separator is based on the dry solids and can be determined prior to forming
the non-woven web.
In some embodiments, the inorganic particles (e.g., silica) may have a relatively
high surface area and/or may be porous. In certain embodiments, inorganic particles
10 with a high surface area may resist stratification, or layering of acid, during recharge as a
function of gravity. In some embodiments, the inorganic particles may be chemically
inert and stable in acid. The inorganic particles may also be thermally stable.
In some embodiments, the inorganic particles included in a nonwoven web and/or
separator described herein may be chosen to have a particular range of average surface
15 area. The average surface area of the inorganic particles may be, for example, greater
than or equal to about 10 m2/g, greater than or equal to about 50 m2/g, greater than or
equal to about 100 m2/g, greater than or equal to about 200 m2/g, greater than or equal to
about 400 m2/g, greater than or equal to about 600 m2/g, greater than or equal to about
800 m2/g, greater than or equal to about 1,000 m2/g, greater than or equal to about 1,250
m2/g, greater than or equal to about 1,500 m220 /g, or greater than or equal to about 1,750
m2/g. In some embodiments, the average surface area of the inorganic particles may be
less than or equal to about 2,000 m2/g, less than or equal to about 1,750 m2/g, less than or
equal to about 1,500 m2/g, less than or equal to about 1,250 m2/g, less than or equal to
about 1,000 m2/g, less than or equal to about 900 m2/g, less than or equal to about 800
m2/g, less than or equal to about 600 m2/g, less than or equal to about 400 m225 /g, less than
or equal to about 200 m2/g, less than or equal to about 100 m2/g, or less than or equal to
about 50 m2/g. Combinations of the above-referenced ranges are also possible (e.g.,
greater than or equal to about 10 m2/g and less than or equal to about 2,000 m2/g, greater
than or equal to about 50 m2/g and less than or equal to about 1,000 m2/g, greater than or
equal to about 100 m2/g and less than or equal to about 600 m230 /g, greater than or equal to
about 400 m2/g and less than or equal to about 600 m2/g). Other ranges are also possible.
As determined herein, surface area is measured according to BCIS-03A, Sept -09
revision, Method 8 (e.g., using a 0.5 gram sample).
30
In some embodiments, the average particle size (e.g., average diameter, or
average cross-sectional dimension) of the inorganic particles included in a non-woven
web and/or separator described herein may be, for example, greater than about 1 micron,
greater than or equal to about 3 microns, greater than or equal to about 5 microns, greater
than or equal to about 10 microns, greater than or equal to about 20 microns, greater tha5 n
or equal to about 30 microns, greater than or equal to about 40 microns, greater than or
equal to about 50 microns, greater than or equal to about 60 microns, greater than or
equal to about 70 microns, greater than or equal to about 80 microns, or greater than or
equal to about 90 microns. The particles may have an average particle size of, for
10 example, less than or equal to about 100 microns, less than or equal to about 90 microns,
less than or equal to about 80 microns, less than or equal to about 70 microns, less than
or equal to about 60 microns, less than or equal to about 50 microns, less than or equal to
about 40 microns, less than or equal to about 30 microns, less than or equal to about 20
microns, less than or equal to about 10 microns, or less than or equal to about 5 microns.
15 Combinations of the above-referenced ranges are also possible (e.g., greater than or
equal to about 1 micron and less than or equal to about 100 microns, greater than or
equal to about 3 micron and less than or equal to about 10 microns). Other ranges are
also possible. Particle sizes described herein (e.g., average particle sizes) refer to ones
measured by dynamic light scattering.
20 In some embodiments, the inorganic particles included in a nonwoven web and/or
battery separator may be resistant to sulfuric acid. As used herein, particles that are
resistant to sulfuric acid refer to inorganic particles that have an acid weight loss of less
than 20% (e.g., less than 15%, less than 10%, less than 5%) of the total weight of the
particles after a three-hour reflux in 1.260 SG sulfuric acid using the BCIS-03A Mar
25 2010 method 13. The weight of the inorganic particles is measured prior to and after
such sulfuric acid exposure to determine percent of weight lost (e.g., % acid weight loss
= [weight of particles before exposure – weight of particles after exposure]/weight of
particles before exposure*100). In some embodiments, inorganic particles having a total
weight loss of less than 20%, less than 15%, less than 10%, or less than 5% are used in a
30 non-woven web and/or battery separator described herein.
In general, any suitable process may be used to add the inorganic particles to the
non-woven web and/or battery separator. In some embodiments, the inorganic particles
are added with the fibers in the fiber slurry during formation of the non-woven web.
31
Alternatively, the inorganic particles may be added into the binder resin. In certain
embodiments, inorganic particles may be added to both the fiber slurry and the binder
resin.
In some embodiments, the non-woven web and/or battery separator may
comprise ribs as shown in FIG. 3B. One of ordinary skill in the art would understa5 nd
that ribs are additional material that is added to one or more surfaces of one or more
layers of the battery separator (e.g., a surface of a non-woven web described herein), and
that ribs are discrete from the layer(s) on which the ribs are added (e.g., a distinguishable
interface exists between the rib material and the layer on which the rib material is added)
10 as illustrated in FIG. 3B. For instance, the ribs are typically added in a secondary step
after the layer (e.g., non-woven web) has been formed.
In general, any suitable material that is resistant to the battery environment may
be used to form the ribs. Non-limiting examples of rib material includes thermoplastics,
such as plastisol (e.g., polyvinylchloride blended with a plasticizer, polyacrylates),
15 polyolefins (e.g., polyethylene, polypropylene, polybutylene, copolyethylene-octene,
polyethylenevinylacetate), polyester, polystyrene, acrylonitrile-butadiene-styrene (ABS),
polyvinylchloride, polyimides, polyurethanes, and thermosets, such as polyurethanes,
polyacrylates, polyepoxides, reactive plastisols, phenolic resin, polyimides, and
combinations thereof.
20 In general, the ribs may have any suitable shape and be arranged in any suitable
pattern as described in PCT/IB/064420 filed Sept. 11, 2014, entitled Battery Separator
with Ribs and a Method of Casting the Ribs on the Separator, which is incorporated
herein by reference in its entirety. For example, the ribs may be in the form of lines
(e.g., continuous, discontinuous) or dots arranged in rows on top of one or more layers of
25 the battery separator. In some embodiments, ribs may not be present on the battery
separator.
In some embodiments, the battery separator including a non-woven web and/or
non-planar layer may have desirable structural properties.
In some embodiments, the basis weight of one or more layers of the battery
30 separator (e.g., the non-woven web and/or the overall battery separator) may range from
between about 25 g/m2 and about 1,200 g/m2. For instance, in some embodiments, the
basis weight of one or more layers of the battery separator (e.g., the non-woven web
and/or the overall battery separator) may be greater than or equal to about 25 g/m2,
32
greater than or equal to about 40 g/m2, greater than or equal to about 60 g/m2, greater
than or equal to about 80 g/m2, greater than or equal to about 100 g/m2, greater than or
equal to about 150 g/m2, greater than or equal to about 200 g/m2, greater than or equal to
about 250 g/m2, greater than or equal to about 300 g/m2, or greater than or equal to about
350 g/m2. In some cases, the basis weight of one or more layers of the battery separat5 or
(e.g., the non-woven web and/or the overall battery separator) may be less than or equal
to about 400 g/m2, less than or equal to about 350 g/m2, less than or equal to about 300
g/m2, less than or equal to about 250 g/m2, less than or equal to about 200 g/m2, less than
or equal to about 150 g/m2, less than or equal to about 100 g/m2, less than or equal to
about 75 g/m2, or less than or equal to about 50 g/m210 . Combinations of the abovereferenced
ranges are also possible (e.g., greater than or equal to about 25 g/m2 and less
than or equal to about 400 g/m2, greater than or equal to about 80 g/m2 and less than or
equal to about 300 g/m2). Other ranges are also possible. As determined herein, the
basis weight of the non-woven web and/or battery separator is measured according to the
15 BCIS-03A, Sept -09, Method 3.
In certain embodiments, the basis weight of one or more layers of the battery
separator (e.g., the non-woven web and/or the overall battery separator) may be higher
than the above-recited range. In some embodiments, a non-planar (e.g., shaped) nonwoven
web or battery separator may have a greater basis weight compared to a similar
20 non-woven web in planar form (e.g., prior to shaping), as described herein. For instance,
in some embodiments, the basis weight of the non-woven web and/or battery separator
may be greater than or equal to about 500 g/m2, greater than or equal to about 600 g/m2,
greater than or equal to about 800 g/m2, or greater than or equal to about 1,000 g/m2. In
some cases, the basis weight of one or more layers of the battery separator (e.g., the non25
woven web and/or the overall battery separator) may be less than or equal to about 1,200
g/m2, less than or equal to about 1,000 g/m2, less than or equal to about 800 g/m2, less
than or equal to about 600 g/m2, or less than or equal to about 500 g/m2. Combinations
of the above-referenced ranges are also possible (e.g., greater than or equal to about 25
g/m2 and less than or equal to about 1,200 g/m2, greater than or equal to about 100 g/m2
and less than or equal to about 375 g/m230 ). Other ranges are also possible. As determined
herein, the basis weight of the non-woven web and/or battery separator is measured
according to the BCIS-03A Sept -09 Method 3.
33
Thickness, as referred to herein, is determined according to BCIS 03-A Sept-09,
Method 10 using 10 kPa pressure. The thickness of one or more layers of the battery
separator (e.g., the non-woven web and/or the overall battery separator) may be between
about 0.05 mm and about 3 mm. In some embodiments, the thickness of the non-woven
web and/or battery separator may be greater than or equal to about 0.05 mm, greater tha5 n
or equal to about 0.1 mm, greater than or equal to about 0.2 mm, greater than or equal to
about 0.3 mm, greater than or equal to about 0.5 mm, greater than or equal to about 0.8
mm, greater than or equal to about 1 mm, greater than or equal to about 1.2 mm, greater
than or equal to about 1.5 mm, greater than or equal to about 1.8 mm, greater than or
10 equal to about 2 mm, or greater than or equal to about 2.5 mm. In certain embodiments,
the thickness of one or more layers of the battery separator (e.g., the non-woven web
and/or the overall battery separator) may be less than or equal to about 3 mm, less than
or equal to about 2.8 mm, less than or equal to about 2.5 mm, less than or equal to about
2.0 mm, less than or equal to about 1.8 mm, less than or equal to about 1.5 mm, less than
15 or equal to about 1.2 mm, less than or equal to about 1 mm, less than or equal to about
0.8 mm, less than or equal to about 0.6 mm, less than or equal to about 0.4 mm, or less
than or equal to about 0.2 mm. Combinations of the above-referenced ranges are also
possible (e.g., greater than about 0.05 mm and less than or equal to about 3 mm, greater
than about 0.1 mm and less than or equal to about 1 mm). Other ranges are also possible.
20 The overall thickness of one or more layers of the battery separator (e.g., the nonwoven
web and/or the overall battery separator) described herein may vary, for example,
between about 0.05 mm and about 30 mm. In some embodiments, the overall thickness
of the non-woven web and/or battery separator may be greater than or equal to about
0.05 mm, greater than or equal to about 0.1 mm, greater than or equal to about 0.5 mm,
25 greater than or equal to about 1 mm, greater than or equal to about 2 mm, greater than or
equal to about 3 mm, greater than or equal to about 5 mm, greater than or equal to about
8 mm, greater than or equal to about 10 mm, greater than or equal to about 12 mm,
greater than or equal to about 15 mm, greater than or equal to about 20 mm, or greater
than or equal to about 25 mm. In certain embodiments, the overall thickness of one or
30 more layers of the battery separator (e.g., the non-woven web and/or the overall battery
separator) may be less than or equal to about 30 mm, less than or equal to about 28 mm,
less than or equal to about 25 mm, less than or equal to about 20 mm, less than or equal
to about 18 mm, less than or equal to about 15 mm, less than or equal to about 12 mm,
34
less than or equal to about 10 mm, less than or equal to about 8 mm, less than or equal to
about 6 mm, less than or equal to about 3 mm, less than or equal to about 2 mm, less than
or equal to about 1 mm, or less than or equal to about 0.5 mm. Combinations of the
above-referenced ranges are also possible (e.g., greater than about 0.05 mm and less than
or equal to about 30 mm, greater than about 0.5 mm and less than or equal to 5 o about 3
mm). Overall thickness, as referred to herein, is determined according to BCIS 03-A
Sept-09, Method 10 using 10 kPa pressure.
In some embodiments, a non-woven web and/or battery separator described
herein may have an apparent density of, for example, between about 40 g/m2/mm and
about 300 g/m210 /mm. For instance, in some embodiments, the apparent density of one or
more layers of the battery separator (e.g., the non-woven web and/or the overall battery
separator) may be less than or equal to about less than or equal to about 300 g/m2/mm,
less than or equal to about less than or equal to about 275 g/m2/mm, less than or equal to
about 250 g/m2/mm, less than or equal to about less than or equal to about 225 g/m2/mm,
less than or equal to about 200 g/m2/mm, less than or equal to about 175 g/m215 /mm, less
than or equal to about 150 g/m2/mm, less than or equal to about 125 g/m2/mm, less than
or equal to about 100 g/m2/mm, less than or equal to about 75 g/m2/mm, or less than or
equal to about 50 g/m2/mm. In some cases, the apparent density of one or more layers of
the battery separator (e.g., the non-woven web and/or the overall battery separator) may
be greater than or equal to about 40 g/m220 /mm, greater than or equal to about 60
g/m2/mm, greater than or equal to about 80 g/m2/mm, greater than or equal to about 100
g/m2/mm, greater than or equal to about 150 g/m2/mm, greater than or equal to about 200
g/m2/mm, greater than or equal to about 250 g/m2/mm, greater than or equal to about 300
g/m2/mm, or greater than or equal to about 350 g/m2/mm. Combinations of the abovereferenced
ranges are also possible (e.g., greater than or equal to about 40 g/m225 /mm and
less than or equal to about 300 g/m2/mm greater than or equal to about 80 g/m2/mm and
less than or equal to about 150 g/m2/mm). Other ranges are also possible. As
determined herein, the apparent density of one or more layers of the battery separator
(e.g., the non-woven web and/or the overall battery separator) is measured by dividing
30 the basis weight determined according to BCIS-03A Sept-09, Method 3 of the nonwoven
web (and/or battery separator) by the overall thickness of the non-woven web
(and/or battery separator) determined according to BCIS 03-A Sept-09, Method 10 under
10kPa.
35
In some embodiments, one or more layers of the battery separator (e.g., the nonwoven
web and/or the overall battery separator) described herein may have an internal
volume porosity of greater than or equal to about 80%, greater than or equal to about
82%, greater than or equal to about 84%, greater than or equal to about 86%, greater than
or equal to about 88%, greater than or equal to about 90%, greater than or equal to 5 o about
92%, greater than or equal to about 94%, or greater than or equal to about 96%. In some
cases, one or more layers of the battery separator (e.g., the non-woven web and/or the
overall battery separator) may have an internal volume porosity of less than or equal to
about 99%, less than or equal to about 98 %, less than or equal to about 96%, less than
10 or equal to about 94%, less than or equal to about 92%, less than or equal to about 90%,
less than or equal to about 88%, less than or equal to about 86%, less than or equal to
about 84%, or less than or equal to about 82%. Combinations of the above-referenced
ranges are also possible (e.g., greater than or equal to about 80% and less than about
98%, greater than or equal to about 90% and less than about 96%). Other ranges are also
15 possible.
In some embodiments, one or more layers of the battery separator (e.g., the nonwoven
web and/or the overall battery separator) described herein may have a total
volume porosity of greater than or equal to about 80%, greater than or equal to about
82%, greater than or equal to about 84%, greater than or equal to about 86%, greater than
20 or equal to about 88%, greater than or equal to about 90%, greater than or equal to about
92%, greater than or equal to about 94%, or greater than or equal to about 96%. In some
cases, the total volume porosity may have a volume porosity of less than or equal to
about 99%, less than or equal to about 98%, less than or equal to about 96%, less than or
equal to about 94%, less than or equal to about 92%, less than or equal to about 90%,
25 less than or equal to about 88%, less than or equal to about 86%, less than or equal to
about 84%, or less than or equal to about 82%. Combinations of the above-referenced
ranges are also possible (e.g., greater than or equal to about 80% and less than about
98%, greater than or equal to about 80% and less than about 98%). Other ranges are also
possible.
30 One or more layers of the battery separator (e.g., the non-woven web and/or the
overall battery separator) may exhibit a suitable mean flow pore size for ionic
conduction. In some embodiments, the mean flow pore size of the non-woven web
and/or battery separator may be less than or equal to about 60 microns, less than or equal
36
to about 50 microns, less than or equal to about 45 microns, less than or equal to about
40 microns, less than or equal to about 30 microns, less than or equal to about 25
microns, less than or equal to about 20 microns, less than or equal to about 15 microns,
less than or equal to about 10 microns, or less than or equal to about 5 microns, less than
or equal to about 3 microns, less than or equal to about 2 microns, less than or equal 5 to
about 1 micron, less than or equal to about 0.8 microns, less than or equal to about 0.5
microns, or less than or equal to about 0.2 microns. In other embodiments, the mean
flow pore size may be greater than or equal to about 0.1 microns, greater than or equal to
about 0.2 microns, greater than or equal to about 0.5 microns, greater than or equal to
10 about 0.8 microns, greater than or equal to about 1 micron, greater than or equal to about
2 microns, greater than or equal to about 5 microns, greater than or equal to about 10
microns, greater than or equal to about 15 microns, greater than or equal to about 20
microns, greater than or equal to about 25 microns, greater than or equal to about 30
microns, greater than or equal to about 35 microns, greater than or equal to about 50
15 microns or greater than or equal to about 60 microns. Combinations of the abovereferenced
ranges are also possible (e.g., greater than or equal to about 0.1 microns and
less than or equal to about 60 microns, greater than or equal to about 0.2 microns and
less than or equal to about 30 microns). Other values and ranges of mean flow pore size
are also possible. Mean flow pore size, as determined herein, is measured according to
20 the standard BCIS-03A, Sept -09, Method 6.
In some embodiments, a non-woven web and/or battery separator described
herein may have desirable mechanical strength characteristics. For example, the nonwoven
web and/or battery separator may be sufficiently strong to be used as a leaf and/or
an envelope separator. In some embodiments, one or more layers of the battery separator
25 (e.g., the non-woven web and/or the overall battery separator) may have a tensile
strength in the machine direction of greater than or equal to about 10 kg/cm2, greater than
or equal to about 15 kg/cm2, greater than or equal to about 20 kg/cm2, greater than or
equal to about 30 kg/cm2, greater than or equal to about 40 kg/cm2, greater than or equal
to about 50 kg/cm2, greater than or equal to about 60 kg/cm2, greater than or equal to
about 70 kg/cm2, or greater than or equal to about 75 kg/cm230 . In some instances, the
tensile strength in the machine direction may be less than or equal to about 80 kg/cm2,
less than or equal to about 70 kg/cm2, less than or equal to about 60 kg/cm2, less than or
equal to about 50 kg/cm2, less than or equal to about 40 kg/cm2, less than or equal to
37
about 30 kg/cm2, less than or equal to about 20 kg/cm2, or less than or equal to about 15
kg/cm2. Combinations of the above-referenced ranges are also possible (e.g., greater
than or equal to about 10 kg/cm2and less than or equal to about 80 kg/cm2, greater than
or equal to about 15 kg/cm2and less than or equal to about 60 kg/cm2). The tensile
strength in the machine direction may be determined using the standard BCIS 03B 5 Rev
Mar 2010 Method 4.
In some embodiments, the puncture strength (or puncture resistance) of one or
more layers of the battery separator (e.g., the non-woven web and/or the overall battery
separator) described herein may be greater than or equal to about 1 N, greater than or
10 equal to about 1.5 N, greater than or equal to about 2 N, greater than or equal to about 3
N, greater than or equal to about 5 N, greater than or equal to about 8 N, greater than or
equal to about 10 N, greater than or equal to about 12N, or greater than or equal to about
15 N. In some instances, the puncture strength (or puncture resistance) may be less than
or equal to about 20 N, less than or equal to about 18 N, less than or equal to about 15 N,
15 less than or equal to about 12 N, less than or equal to about 10 N, less than or equal to
about 8 N, less than or equal to about 5 N, or less than or equal to about 3 N.
Combinations of the above-referenced ranges are also possible (e.g., greater than or
equal to about 1 N and less than or equal to about 20 N, greater than or equal to about 1.5
N and less than or equal to about 15 N). The puncture strength may be determined using
20 protocol BCIS 03B Rev Mar 2010 Method 9. The puncture resistance may be
determined using BCIS 03B Rev Mar 2010 Method 10.
In some embodiments, the Gurley stiffness of one or more layers of the battery
separator (e.g., the non-woven web and/or the overall battery separator) described
herein, or an additional layer described herein, may be greater than or equal to about 500
25 mg, greater than or equal to about 800 mg, greater than or equal to about 1,000 mg,
greater than or equal to about 1,250 mg, greater than or equal to about 1,500 mg, greater
than or equal to about 1,750 mg, greater than or equal to about 2,000 mg, greater than or
equal to about 2,500 mg, , greater than or equal to about 3,000 mg, greater than or equal
to about 3,500 mg, or greater than or equal to about 4,000 mg. In some instances, the
30 Gurley stiffness may be less than or equal to about 5,000 mg, less than or equal to about
4,500 mg, less than or equal to about 4,000 mg, less than or equal to about 3,500 mg, less
than or equal to about 3,000 mg, less than or equal to about 2,500 mg, less than or equal
to about 2,000 mg, less than or equal to about 1,800 mg, less than or equal to about 1,500
38
mg, less than or equal to about 1,200 mg, or less than or equal to about 1,000 mg.
Combinations of the above-referenced ranges are also possible (e.g., greater than or
equal to about 500 mg and less than or equal to about 5000 mg, greater than or equal to
about 800 to less than or equal to about 1200 mg). The Gurley stiffness may be
determined using TAPPI T543 om-94 in the machine directi5 on.
In some embodiments, a battery separator including a non-woven web and/or
non-planar layers may have enhanced battery performance.
In some embodiments, a battery comprising a battery separator and/or one or
more layers of the battery separator (e.g., the non-woven web)described herein may have
10 a relatively low electrical resistance. For instance, in some embodiments, the electrical
resistance may be less than or equal to about 1 cm2, less than or equal to about 0.8
cm2, less than or equal to about 0.6 cm2, less than or equal to about 0.4 cm2, less
than or equal to about 0.2 cm2, less than or equal to about 0.1 cm2, less than or equal
to about 0.08 cm2, less than or equal to about 0.06 cm2, less than or equal to about
0.04 cm2, less than or equal to about 0.02 cm215 , less than or equal to about 0.01
cm2, less than or equal to about 0.008 cm2, or less than or equal to about 0.005
cm2. In certain embodiments, the electrical resistance may be greater than or equal to
about 0.001 cm2, greater than or equal to about 0.003 cm2, greater than or equal to
about 0.005 cm2, greater than or equal to about 0.008 cm2, greater than or equal to
about 0.01 cm2, greater than or equal to about 0.05 cm220 , greater than or equal to
about 0.08 cm2, greater than or equal to about 0.1 cm2, greater than or equal to
about 0.3 cm2, greater than or equal to about 0.5 cm2, or greater than or equal to
about 0.8 cm2. Combinations of the above-referenced ranges are also possible (e.g.,
greater than about 0.001 cm2 and less than or equal to about 1 cm2, greater than
about 0.01 cm2 and less than or equal to about 0.5 cm225 ). Other ranges are also
possible. The electrical resistance may be measured according to the standard IS 6071-
1986 or standard BCIS-03B method 3.
In some embodiments, the electrical resistance per thickness of the battery
separator may be less than or equal to about 0.15 (cm2)/mm, less than or equal to
about 0.12 (cm2)/mm, less than or equal to about 0.1 (cm230 )/mm, less than or equal
to about 0.09 (cm2)/mm, less than or equal to about 0.08 (cm2)/mm, less than or
equal to about 0.07 (cm2)/mm, less than or equal to about 0.06 (cm2)/mm, less than
or equal to about 0.05 (cm2)/mm, less than or equal to about 0.04 (cm2)/mm, or less
39
than or equal to about 0.03 (cm2)/mm. In certain embodiments, the electrical resistance
may be greater than or equal to about 0.02 (cm2)/mm, greater than or equal to about
0.03 (cm2)/mm, greater than or equal to about 0.04 (cm2)/mm, greater than or equal
to about 0.05 (cm2)/mm, greater than or equal to about 0.06 (cm2)/mm, greater than
or equal to about 0.07 (cm2)/mm, greater than or equal to about 0.08 (cm2)/5 mm,
greater than or equal to about 0.09 (cm2)/mm, greater than or equal to about 0.1
(cm2)/mm, or greater than or equal to about 0.12 (cm2)/mm. Combinations of the
above-referenced ranges are also possible (e.g., greater than about 0.02 (cm2)/mm and
less than or equal to about 0.07 (cm2)/mm, greater than about 0.02 (cm2)/mm and
less than or equal to about 0.04 (cm210 )/mm). Other ranges are also possible. The
electrical resistance may be measured according to the standard IS 6071-1986 or
standard BCIS-03B method 3.
In some embodiments, loss of capacity of a battery including a battery separator
and/or one or more layers of the battery separator (e.g., the non-woven web)described
15 herein, after 18 weeks of cyclic testing (1530 cycles) with a 17% depth of discharge
partial state of charge (i.e., PSOC), may be less than 30% of 20 hour capacity, less than
25% of 20 hour capacity, less than 20% of 20 hour capacity, less than 18% of 20 hour
capacity, less than 15% of 20 hour capacity, less than 12% of 20 hour capacity, or less
than 10% of 20 hour capacity. The 17% depth of discharge PSOC may be measured
20 according to the VRLA SLI Batteries (AGM) Requirements and test, VDA Requirement
Specification AGM: 2010-03 Method 9.9.3, e.g., using a European H8 size battery, 100
AH capacity.
In some embodiments, a battery described herein at 50% state of charge and
0°C, and including a battery separator and/or one or more layers of the battery separator
25 (e.g., the non-woven web)described herein, may accept (i.e., have a charge acceptance
of) greater than or equal to about 5 A per 100 AH of capacity, greater than or equal to
about 10 A per 100 AH of capacity, greater than or equal to about 15 A per 100 AH of
capacity, greater than or equal to about 20 A per 100 AH of capacity, greater than or
equal to about 25 A per 100 AH of capacity, greater than or equal to about 35 A per 100
30 AH of capacity, greater than or equal to about 40 A per 100 AH of capacity, or greater
than or equal to about 45 A per 100 AH of capacity, e.g., after 10 minutes of charging at
14.4 V. In some instances, the charge acceptance may be less than or equal to about 50
A per 100 AH of capacity, less than or equal to about 45 A/ per 100 AH of capacity, less
40
than or equal to about 40 A per 100 AH of capacity, less than or equal to about 35 A per
100 AH of capacity, less than or equal to about 30 A per 100 AH of capacity, less than or
equal to about 25 A per 100 AH of capacity, less than or equal to about 20 A per 100 AH
of capacity, or less than or equal to about 15 A per 100 AH of capacity. Combinations of
the above-referenced ranges are also possible. The charge acceptance (i.e., effecti5 ve
amount of charge being accepted by the battery during charging) may be measured
according to the VRLA SLI Batteries (AGM) Requirements and test, VDA Requirement
Specification AGM: 2010-03 Method 9.5, e.g., using a European H8 size battery, 100
AH capacity.
10 In some embodiments, the dynamic charge acceptance (i.e., the charge
acceptance at different states of charge) of a battery including a battery separator
described herein may be 1 A/AH of total battery capacity (20 hr) at greater than or equal
to about 10% state of charge, at greater than or equal to about 15% state of charge, at
greater than or equal to about 20% state of charge, at greater than or equal to about 25%
15 state of charge, at greater than or equal to about 30% state of charge, at greater than or
equal to about 35% state of charge, at greater than or equal to about 40% state of charge,
at greater than or equal to about 50% state of charge, at greater than or equal to about
60% state of charge, or at greater than or equal to about at 75% state of charge. In some
instances, the dynamic charge acceptance may be 1 A/AH of total battery capacity (20
20 hr) at less than or equal to about at 80% state of charge, at less than or equal to about
70% state of charge, at less than or equal to about 60% state of charge, at less than or
equal to about 50% state of charge, at less than or equal to about 45% state of charge, at
less than or equal to about 40% state of charge, at less than or equal to about 35% state
of charge, at less than or equal to about 30% state of charge, at less than or equal to about
25 25% state of charge, at less than or equal to about 20% state of charge, or at less than or
equal to about 15% state of charge. Combinations of the above-referenced ranges are
also possible. The dynamic charge acceptance may be measured according to VRLA
SLI Batteries (AGM) Requirements and test, VDA Requirement Specification AGM:
2010-03 Method 9.6.
30 It should be appreciated that although some of the parameters and characteristics
noted above are described with respect to non-woven webs, the same parameters and
characteristics (including the values and ranges for such parameters and characteristics)
may also be applied to a battery separator including the non-woven web.
41
In some embodiments, a separator described herein may be used in a battery (e.g.,
lead acid battery). The battery may comprise a negative plate, a positive plate, and a
battery separator (e.g., including a non-woven web described herein) disposed between
the negative and positive plates.
It is to be understood that the other components of the battery that are 5 not
explicitly discussed herein can be conventional battery components. Positive plates and
negative plates can be formed of conventional lead acid battery plate materials. For
example, in container formatted batteries, plates can include grids that include a
conductive material, which can include, but is not limited to, lead, lead alloys, graphite,
carbon, carbon foam, titanium, ceramics (such as Ebonex®10 ), laminates and composite
materials. The grids are typically pasted with active materials. The pasted grids are
typically converted to positive and negative battery plates by a process called
"formation." Formation involves passing an electric current through an assembly of
alternating positive and negative plates with separators between adjacent plates while the
15 assembly is in a suitable electrolyte (e.g., to convert pasted oxide to active materials).
As a specific example, positive plates may contain lead dioxide as the active
material, and negative plates may contain lead as the active material. Plates can also
contain one or more reinforcing materials, such as chopped organic fibers (e.g., having
an average length of 0.125 inch or more), chopped glass fibers, metal sulfate(s) (e.g.,
20 nickel sulfate, copper sulfate), red lead (e.g., a Pb304-containing material), litharge,
paraffin oil, and/or expander(s). In some embodiments, an expander contains barium
sulfate, carbon black and lignin sulfonate as the primary components. The components
of the expander(s) can be pre- mixed or not pre-mixed. Expanders are commercially
available from, for example, Hammond Lead Products (Hammond, IN) and Atomized
25 Products Group, Inc. (Garland, TX).
An example of a commercially available expander is the Texex® expander
(Atomized Products Group, Inc.). In certain embodiments, the expander(s), metal
sulfate(s) and/or paraffin are present in positive plates, but not negative plates. In some
embodiments, positive plates and/or negative plates contain fibrous material or other
30 glass compositions.
A battery can be assembled using any desired technique. For example, separators
may be wrapped around plates (e.g., positive electrode, negative electrode). The positive
plates, negative plates and separators are then assembled in a case using conventional
42
lead acid battery assembly methods. The battery separators may be used, for example, as
a leaf separator, as shown illustratively in FIGs. 4A and 4C, or an envelope separator
(i.e., the separator is sealed on three sides) as shown illustratively in FIGs. 4B and FIG.
4D. FIG. 4 is a schematic diagram showing a cross-section of a battery separator 120
and a plate 125. The thickness 130 and overall thickness 135 of each separator as 5 the
terms are used herein are also shown in FIGs. 4A-4D. In certain embodiments,
separators are compressed after they are assembled in the case, i.e., the thickness of the
separators are reduced after they are placed into the case. An electrolyte (e.g., sulfuric
acid) is then disposed in the case. It should be understood that the shapes (e.g., planar,
10 non-planar) of the battery separators shown in FIG. 4 are non-limiting and the battery
separators described herein may have any suitable shape. That is, the battery separators
may be planar as shown in FIGs. 4C-4D or non-planar as shown in FIGs. 4A-4B, and
non-planar battery separators may have the same or a different shape as separator 120
shown illustratively in FIGs. 4A-D. In some embodiments, a combination of planar and
15 non-planar layers may be used in separator.
The electrolyte can include other compositions. For example, the electrolyte can
include liquids other than sulfuric acid, such as a hydroxide (e.g., potassium hydroxide).
In some embodiments, the electrolyte includes one or more additives, including but not
limited to a mixture of an iron chelate and a magnesium salt or chelate, organic polymers
20 and lignin and/or organic molecules, and phosphoric acid. In some embodiments, the
electrolyte is sulfuric acid. In some embodiments, the specific gravity of the sulfuric
acid is between 1.21 g/cm3 and 1.32 g/cm3, or between 1.28 g/cm3 and 1.31 g/cm3. In
certain embodiments the specific gravity of the sulfuric acid is 1.26 g/cm3. In certain
embodiments the specific gravity of the sulfuric acid is about 1.3 g/cm3.
25 In some embodiments, the battery separators (including the non-woven webs
described herein) may be used in lead acid batteries including valve-regulated batteries
(e.g., absorbent glass mat batteries) and flooded batteries. For example, in some
embodiments, the battery separators may be used in flooded battery applications. In
some such embodiments, the battery separator may be a enveloped separator that is
30 wrapped around one or more plate (e.g., positive plate(s), positive and negative plate(s)).
In some such embodiments, the battery separator may comprise a non-woven web
bonded to a web/layer including glass fibers and resin. In some such cases, the battery
separator may be wrapped around the plate, such that the glass layer faces and/or is in
43
contact with the plate. In other cases, the battery separator may be wrapped around the
plate, such that the glass layer is on a side opposite the plate. The glass layer may serve
to stabilize the active material in the electrode(s) and minimize shedding. In certain
embodiments, the battery separator does not include a web including glass fibers and
resin. In some such embodiments, the glass fibers in a non-woven web described herei5 n
may serve to stabilize the active material in the electrode(s) and minimize shedding. In
some embodiments in which a battery separator described herein is used in a flooded
battery, the plates may include a glass layer embedded on to the plate that serves to
decrease shedding of the plate and/or may comprise carbon based additives that increase
10 the conductance of the plate (e.g., graphene, graphite) and/or have a high surface area
(e.g., greater than or equal to about 500 m2/g and less than or equal to about 5,000 m2/g).
An enveloped battery separator, as described herein, may be wrapped around such a
plate. In some embodiments, a carbon-impregnated non-woven web may be positioned
adjacent to the plate. In some embodiments, a battery separator may be used in a flooded
15 battery comprising various additives in the electrolyte solution.
As described herein, a non-woven web may form all or part of a battery separator.
In some embodiments, one or more additional layers or components are included with
the non-woven web (e.g., disposed adjacent to the non-woven web, contacting one or
both sides of the non-woven web). In some instances, an additional layer is a fibrous
20 layer. Non-limiting examples of fibrous additional layers include a meltblown layer, a
wet laid layer (e.g., a glass fiber wet laid layer), a spunbond layer, an extruded layer, or
an electrospun layer. In some embodiments, multiple non-woven webs in accordance
with embodiments may be layered together in forming a multi-layer sheet for use in a
battery separator. In other embodiments, an additional layer may be a non-fibrous layer.
25 For example, the layer may be a polymeric layer formed by an extrusion process (e.g., a
membrane such as a PE membrane). Other configurations are also possible.
In some embodiments two or more layers of a web may be formed separately,
and combined by any suitable method such as lamination, collation, or by use of
adhesives. The two or more layers may be formed using different processes, or the same
30 process. For example, each of the layers may be independently formed by a wet laid
process, a non-wet laid process, or any other suitable process.
In some embodiments, two or more layers may be formed by the same process.
In some instances, the two or more layers may be formed simultaneously.
44
Different layers may be adhered together by any suitable method. For instance,
layers may be adhered by an adhesive and/or melt-bonded to one another on either side.
Lamination and calendering processes may also be used. In some embodiments, an
additional layer may be formed from any type of fiber or blend of fibers via an added
headbox or a coater and appropriately adhered to another layer5 .
A battery separator may include any suitable number of layers, e.g., at least 2, at
least 3, at least 4, at least 5, at least 6, at least 7 layers. In some embodiments, a battery
separator may include up to 10 layers.
Non-woven webs described herein may be produced using suitable processes,
10 such as a wet laid process. In general, a wet laid process involves mixing together fibers
of one or more type; for example, glass fibers of one type may be mixed together with
glass fibers of another type, and/or with fibers of a different type (e.g., synthetic fibers),
to provide a fiber slurry. The slurry may be, for example, an aqueous-based slurry. In
certain embodiments, fibers, are optionally stored separately, or in combination, in
15 various holding tanks prior to being mixed together.
For instance, a first fiber may be mixed and pulped together in one container and
a second fiber may be mixed and pulped in a separate container. The first fibers and the
second fibers may subsequently be combined together into a single fibrous mixture.
Appropriate fibers may be processed through a pulper before and/or after being mixed
20 together. In some embodiments, combinations of fibers are processed through a pulper
and/or a holding tank prior to being mixed together. It can be appreciated that other
components (e.g., inorganic particles) may also be introduced into the mixture.
Furthermore, it should be appreciated that other combinations of fibers types may be
used in fiber mixtures, such as the fiber types described herein.
25 In certain embodiments, two or more layers are formed by a wet laid process.
For example, a first dispersion (e.g., a pulp) containing fibers in a solvent (e.g., an
aqueous solvent such as water) can be applied onto a wire conveyor in a papermaking
machine (e.g., a fourdrinier or, a round former, or a rotoformer) to form first layer
supported by the wire conveyor. A second dispersion (e.g., another pulp) containing
30 fibers in a solvent (e.g., an aqueous solvent such as water) is applied onto the first layer
either at the same time or subsequent to deposition of the first layer on the wire.
Vacuum is continuously applied to the first and second dispersions of fibers during the
above process to remove the solvent from the fibers, thereby resulting in an article
45
containing first and second layers. The article thus formed is then dried and, if
necessary, further processed by using known methods to form multi-layered non-woven
webs.
Any suitable method for creating a fiber slurry may be used. In some
embodiments, further additives are added to the slurry to facilitate processing. 5 . The
temperature may also be adjusted to a suitable range, for example, between 33 ºF and
100 ºF (e.g., between 50 ºF and 85 ºF). In some cases, the temperature of the slurry is
maintained. In some instances, the temperature is not actively adjusted.
In some embodiments, the wet laid process uses similar equipment as in a
10 conventional papermaking process, for example, a hydropulper, a former or a headbox, a
dryer, and an optional converter. A non-woven web can also be made with a laboratory
handsheet mold in some instances. As discussed above, the slurry may be prepared in
one or more pulpers. After appropriately mixing the slurry in a pulper, the slurry may be
pumped into a headbox where the slurry may or may not be combined with other
15 slurries. Other additives may or may not be added. The slurry may also be diluted with
additional water such that the final concentration of fiber is in a suitable range, such as
for example, between about 0.1% and 0.5% by weight.
In some cases, the pH of the fiber slurry may be adjusted as desired. For
instance, fibers of the slurry may be dispersed under acidic or neutral conditions.
20 Before the slurry is sent to a headbox, the slurry may optionally be passed
through centrifugal cleaners and/or pressure screens for removing unfiberized material.
The slurry may or may not be passed through additional equipment such as refiners or
deflakers to further enhance the dispersion of the fibers. For example, deflakers may be
useful to smooth out or remove lumps or protrusions that may arise at any point during
25 formation of the fiber slurry. Fibers may then be collected on to a screen or wire at an
appropriate rate using any suitable equipment, e.g., a fourdrinier, a rotoformer, a
cylinder/round former, or an inclined wire fourdrinier.
As described herein, in some embodiments, a binder resin is added to a preformed
fiber layer (e.g., a pre-formed non-woven web formed by a wet-laid process).
30 For instance, as the fiber layer is passed along an appropriate screen or wire, different
components included in the binder resin (e.g., inorganic particles), which may be in the
form of separate emulsions, are added to the fiber layer using a suitable technique. In
some cases, each component of the binder resin is mixed as an emulsion prior to being
46
combined with the other components and/or fiber layer. The components included in the
resin may be pulled through the fiber layer using, for example, gravity and/or vacuum.
In some embodiments, one or more of the components included in the binder resin may
be diluted with softened water and pumped into the fiber layer. In some embodiments, a
resin may be applied to a fiber slurry prior to introducing the slurry into a headbox. 5 . For
example, the resin may be introduced (e.g., injected) into the fiber slurry and
impregnated with and/or precipitated on to the fibers.
During or after formation of a non-woven web, the non-woven web may be
further processed according to a variety of known techniques. Optionally, additional
10 layers can be formed and/or added to a non-woven web using processes such as
lamination, co-pleating, or collation. For example, in some cases, two layers are formed
into a composite article by a wet laid process, and the composite article is then combined
with a third layer by any suitable process (e.g., lamination, co-pleating, or collation). It
can be appreciated that a non-woven web or a composite article formed by the processes
15 described herein may be suitably tailored not only based on the components of each fiber
layer, but also according to the effect of using multiple fiber layers of varying properties
in appropriate combination to form non-woven webs having the characteristics described
herein.
In some embodiments, a non-woven web can be post-processed such as subjected
20 to a shaping process as described herein.
EXAMPLES
The following examples are intended to illustrate certain embodiments of the
present invention, but are not to be construed as limiting and do not exemplify the full
25 scope of the invention.
EXAMPLE 1
This example describes the mechanical and performance properties of a singlelayer
corrugated battery separator and multi-layer corrugated battery separators. Five
30 multi-layer battery separators including a corrugated layer were formed that varied in the
number and type of additional layers. The battery separators including the corrugated
layer had increased total volume porosity and strength while maintaining a similar
electrical resistance compared to a planar single layer battery separator.
47
The planar battery separator was a non-woven web that contained about 20%
glass fibers, about 20% polyester fibers, about 15% resin, and about 45% precipitated
silica.
The battery separator in Experiment A contained the corrugated version of the
planar non-woven web that was bonded to additional layer 1. The planar layer 5 was
corrugated by passing the planar non-woven web between two heated corrugating rollers.
The two rollers were arranged such that there was an inter-meshing of the teeth of the
rollers which forced the layer into flutes. Additional layer 1 was a wet-laid non-woven
web that contained about 24.5% glass fibers, about 15% polyester fibers, about 10%
10 resin, and about 50.5% precipitated silica using acid resistant copolymer latex.
Additional layer 1 had a basis weight of about 120 g/m2 and thickness of about 0.3 mm.
In Experiment B, the battery separator contained the corrugated non-woven web
of Experiment A bonded to additional layer 2. Additional layer 2 was a wet-laid glass
mat comprising glass fibers and binder resin. The glass mat had a basis weight of 50
g/m2 15 and a thickness of 0.4 mm at 3.5 kPa.
In Experiment C, the battery separator contained the corrugated non-woven web
of Experiment A bonded on both sides to additional layer 1 used in Experiment A.
In Experiment D, the battery separator contained the corrugated non-woven web
of Experiment A bonded on both sides to additional layer 2 used in Experiment B.
20 In Experiment E, the battery separator contained the corrugated non-woven web
of Experiment A bonded on one side to additional layer 2 used in Experiment B and to
additional layer 1 used in Experiment A on the other side.
Various properties of each of the battery separators is shown in Table 1.
Table 1. Properties of Various Battery Separators
Test Units Planar
Separator
A B C D E
Overall Thickness mm 1.6 2.81 3.15 3.18 3.48 5.92
Basis Wt. g/m2 230 313 280 454 311 781
Apparent Density g/m2/mm 143 111 88 143 88 131
Total Porosity % 57 68 66 69 74 73
Resistance ·cm2 0.1 0.102 0.113 0.124 0.105 0.185
Resistance/Thickness ·cm2/mm 0.063 0.036 0.036 0.039 0.030 0.031
Puncture Strength N 7.99 11.54 10.64 16.44 17.7 21.64
48
Each of the battery separators including the corrugated layer had increased total
volume porosity and puncture strength while having a similar electrical resistance as that
for the planar single layer battery separator. Each of the battery separators from
experiments A, B, D, and E had a lower apparent density than the planar single laye5 r
battery separator.
What is claimed is:
49
CLAIMS
1. A battery separator, comprising:
a non-woven web comprising:
a plurality of glass fibers having an average diameter of greater than 5 n or
equal to about 0.1 microns and less than or equal to about 15 microns, wherein
the glass fibers are present in an amount of greater than or equal to about 2 wt.%
and less than or equal to about 95 wt.% of the non-woven web;
a plurality of synthetic fibers, wherein the synthetic fibers are present in
10 the non-woven web in an amount of greater than or equal to about 1 wt.% and
less than or equal to about 80 wt.% of the non-woven web; and
a plurality of inorganic particles, wherein the inorganic particles are
present in an amount of greater than or equal to about 10 wt.% and less than or
equal to about 80 wt.% of the non-woven web,
15 wherein the apparent density of the battery separator is greater than or
equal to about 40 g/m2/mm and less than or equal to about 300 g/m2/mm.
2. A battery separator, comprising:
a non-woven web comprising:
20 a plurality of glass fibers having an average diameter of greater than
or equal to about 0.1 microns;
a plurality of synthetic fibers, wherein the synthetic fibers are present
in an amount of greater than or equal to about 1 wt.% and less than or equal
to about 80 wt.% of the non-woven web; and
25 a plurality of inorganic particles, wherein the inorganic particles are
present in an amount of greater than or equal to about 10 wt.% and less than
or equal to about 80 wt.% of the non-woven web;
wherein the non-woven web is corrugated, embossed, pleated, creped,
or micrexed.
30
3. A battery separator, comprising:
a non-woven web comprising:
We Claim:
50
a plurality of glass fibers having an average diameter of greater than
or equal to about 0.1 microns;
a plurality of synthetic fibers, wherein the synthetic fibers are present
in an amount of greater than or equal to about 1 wt.% and less than or equal
to about 80 wt.% of the non-woven web; 5 and
a plurality of inorganic particles, wherein the inorganic particles are
present in an amount of greater than or equal to about 10 wt.% and less than
or equal to about 80 wt.% of the non-woven web;
an additional layer adjacent the non-woven web, wherein the additional layer is
10 corrugated, embossed, pleated, creped, or micrexed.
4. A battery separator as in any preceding claim, wherein the non-woven web has
undulations.
15 5. A battery separator as in any preceding claim, wherein the non-woven web is
corrugated, embossed, pleated, creped, and/or micrexed.
6. A battery separator as in any preceding claim, wherein the apparent density of the
non-woven web is greater than or equal to about 40 g/m2/mm and less than or equal to
about 300 g/m220 /mm.
7. A battery separator as in any preceding claim, wherein the apparent density of the
battery separator is greater than or equal to about 40 g/m2/mm and less than or equal to
about 300 g/m2/mm.
25
8. A battery separator as in any preceding claim, wherein the separator comprises an
additional layer adjacent the non-woven web, and wherein the additional layer includes
an apparent density of greater than or equal to about 40 g/m2/mm and less than or equal
to about 300 g/m2/mm.
30
9. A battery separator as in any preceding claim, wherein the non-woven web
comprises a plurality of synthetic fibers, wherein the synthetic fibers are present in an
51
amount of greater than or equal to about 5 wt.% and less than or equal to about 50 wt.%
of the non-woven web.
10. A battery separator as in any preceding claim, wherein the non-woven web
comprises a plurality of inorganic particles, wherein the inorganic particles are resista5 nt
to sulfuric acid, and wherein the inorganic particles are present in an amount of greater
than or equal to about 30 wt.% and less than or equal to about 60 wt.% of the non-woven
web.
10 11. A battery separator as in any preceding claim, wherein non-woven web further
comprises a binder resin.
12. A battery separator as in any preceding claim, wherein the volume porosity of the
battery separator is greater than or equal to about 80% and less than or equal to about
15 98%.
13. A battery separator as in any preceding claim, wherein the battery separator is a
lead acid battery separator.
20 14. A battery separator as in any preceding claim, wherein the apparent density of the
non-woven web is greater than or equal to about 80 g/m2/mm and less than or equal to
about 150 g/m2/mm.
15. A battery separator as in any preceding claim, wherein the separator comprises an
25 additional layer adjacent the non-woven web, and wherein the additional layer includes
an apparent density of greater than or equal to about 30 g/m2/mm and less than or equal
to about 500 g/m2/mm.
16. A battery separator as in any preceding claim, wherein the inorganic particles
have a surface area of greater than or equal to about 100 m230 /g and less than or equal to
about 600 m2/g.
52
17. A battery separator as in any preceding claim, wherein the thickness of the
battery separator is greater than or equal to about 0.1 mm and less than or equal to about
3 mm.
18. A battery separator as in any preceding claim, wherein the pore size of the batter5 y
separator is greater than or equal to about 0.2 microns and less than or equal to about 30
microns.
19. A battery separator as in any preceding claim, wherein the puncture strength of
10 the battery separator is greater than or equal to about 1.5 N and less than or equal to
about 15 N.
20. A battery separator as in any preceding claim, wherein the tensile strength of the
battery separator is greater than or equal to about 15 kg/cm2 and less than or equal to
15 about 60 kg/cm2.
21. A lead acid battery comprising the battery separator of any preceding claim.
22. A battery separator as in any preceding claim, wherein the additional layer is
20 selected from the group consisting of a sliver, a roving, a braided layer, a spacer fabric, a
corduroy fabric, a ribbed knit, a porous membrane, a functionalized needle punched and
hydroentangled non-woven web, an extruded layer, and a net.
23. A battery separator as in any preceding claim, wherein the non-woven web or
25 additional layer includes bends having an average amplitude on the order of 0.1-20 times
the thickness of the layer.
24. A battery separator as in any preceding claim, wherein the non-woven web or
additional layer includes bends having a frequency of at least 100 bends/100 mm and
30 less than or equal to 1000 bends/100 mm).
25. A battery separator as in any preceding claim, wherein the non-woven web
comprises a plurality of indentations in a regular pattern.
53
26. A battery separator as in any preceding claim, wherein the non-woven web
comprises a plurality of indentations in an irregular pattern.
27. A battery separator as in any preceding claim, wherein the non-woven web
comprises a plurality of indentations and a frequency of the indentations in 5 the nonwoven
web is at least about 2 indentations/100 mm2.
28. A battery separator as in any preceding claim, wherein the non-woven web
comprises a plurality of indentations and an average depth of the indentations in the non10
woven web is at least about 0.2 times an overall thickness of the non-woven web.
29. A battery separator as in any preceding claim, wherein the non-woven web
comprises a plurality of indentations and an average depth of the indentations in the nonwoven
web is at least about 0.5 times the thickness of the non-woven web.
15
30. A battery separator as in any preceding claim, wherein the non-woven web
comprises a plurality of indentations, and a percent surface area of the non-woven web
that is indented is greater than or equal to about 20%.
20 31. A battery including the battery separator of any preceding claim.