阅读说明：本技术 柔性锂离子电池 (Flexible lithium ion battery ) 是由 A·R·哈鲁特云严 O·A·库兹奈特索夫 E·M·皮格思 于 2019-09-06 设计创作，主要内容包括：本公开涉及由一个或多个自支撑柔性阳极和阴极所制成的柔性电池。该柔性电池中不含粘合剂,其中在弯曲、卷曲或折叠的构型中,电池的输出与扁平构型时的输出基本相同。(The present disclosure relates to flexible batteries made from one or more self-supporting flexible anodes and cathodes. The flexible battery is free of adhesive, wherein in a bent, rolled or folded configuration, the output of the battery is substantially the same as in a flat configuration.)

1. A flexible lithium ion battery, comprising:

an electrolyte comprising a liquid, gel, solid, or combination thereof;

one or more electrodes, the one or more electrodes comprising:

one or more flexible anodes comprising a composite material comprising anode active material particles in a three-dimensional cross-linked network of carbon nanotubes;

one or more flexible cathodes comprising a composite material comprising particles of a cathode active material in a three-dimensional cross-linked network of carbon nanotubes; and one or more flexible separator membranes positioned between the one or more flexible anodes and the one or more flexible cathodes to form a battery; and

wherein the battery is located within a flexible pouch that includes an outer packaging material effective to retain the battery within its interior.

2. The battery of claim 1, wherein the battery has no current collector.

3. The battery of claim 1, wherein the battery is free of a binder.

4. The battery of claim 1, wherein one or more electrodes further comprise a battery tab attached to at least one corresponding protrusion extending from a body of one or more electrodes beyond the separator, or to the body of one or more electrodes at a cut-out of the separator and one or more opposing electrodes.

5. The battery of claim 1, wherein the external packaging material comprises a flexible material, a stretchable material, a twistable material, a wearable material, an implantable material, a biocompatible material, a non-wrinkling material, a waterproof material, a durable material, a thermally insulating material, and any combinations and layers thereof.

6. The battery of claim 1, wherein a concentration of carbon nanotubes on a surface of the respective electrode facing and contacting the separator is between 5-100 wt% carbon nanotubes, a concentration of carbon nanotubes in the bulk portion of the electrode is between 0.5-10 wt% carbon nanotubes, and a concentration of carbon nanotubes on a surface of the respective electrode facing away from and not contacting the separator is between 0-1 wt% carbon nanotubes.

7. The battery of claim 4, wherein two or more battery tabs extend beyond the flexible pouch, the two or more battery tabs effective to provide current flow outside the flexible pouch.

8. The battery of claim 4, further comprising two or more battery tab extensions extending beyond the flexible bag, the two or more battery tab extensions each respectively connected to a battery tab.

9. The battery of claim 1, wherein the battery is folded one or more times along a length or width inside the flexible bag.

10. The flexible lithium ion battery of claim 1, wherein the charge and discharge capacity of the flexible lithium ion battery in the bent, rolled, or folded configuration is 75% -100% of the charge and discharge capacity of the flexible lithium ion battery in the flat configuration.

11. The flexible lithium ion battery of claim 1, wherein the anode active material particles comprise graphite, silicon, natural graphite, artificial graphite, activated carbon, carbon black, high performance powdered graphene, or combinations thereof; and the cathode active material particles comprise lithium metal oxide, metallic lithium, (LiNi)_xMn_yCo_zO₂，x+y+z＝1)、Li(Ni,Mn,Co)O₂Li-Ni-Mn-Co-O or combinations thereof.

12. A method of manufacturing a flexible lithium ion battery, the method comprising:

providing one or more electrodes, each electrode comprising one or more surfaces comprising 5-100 wt% carbon nanotubes;

providing one or more barrier films;

disposing one or more separator films between one or more electrodes, the one or more separator films in contact with the one or more surfaces containing 5-100 wt% carbon nanotubes to form a battery; and

disposing the battery within a flexible pouch comprising an outer potting material effective to retain the battery within its interior.

13. The method of claim 12, wherein the 5-100 wt% carbon nanotubes are effectively adhered to the one or more release films.

14. The method of claim 12, further comprising a surface of the one or more electrodes not in contact with the one or more separator films, the surface containing 0-1 wt% carbon nanotubes, the 0-1 wt% carbon nanotubes effective to provide one or more non-adherent surfaces.

15. The method of claim 14, further comprising pressing the one or more electrodes by contacting one or more surfaces comprising 0-1 wt% carbon nanotubes.

16. The method of claim 14, further comprising disposing one or more isolation films on a surface of the one or more electrodes other than between the one or more electrodes such that one or more isolation films are located on one or more outer surfaces of one or more electrodes.

17. The method of claim 16, further comprising pressing one or more electrodes by contacting one or more separator films on one or more outer surfaces of one or more electrodes.

18. The method of claim 12, further comprising attaching one or more battery tabs to at least one of corresponding protrusions extending from the body of one or more electrodes beyond the separator film or to the body of one or more electrodes at the cut of one or more separator films and the opposing electrode.

19. A method of manufacturing a flexible self-supporting electrode, comprising:

collecting carbon nanotubes with a concentration of 5-100 wt%;

collecting the carbon nano-tube with the concentration of 0.5-10 wt%; and

collecting the carbon nanotubes at a concentration of 0-1 wt% to form a flexible self-supporting electrode comprising 5-100 wt% carbon nanotubes on the first outer surface, a concentration of 0.5-10 wt% carbon nanotubes in the bulk portion, and a concentration of 0-1 wt% carbon nanotubes on the second outer surface.

20. The method of claim 19, further comprising attaching a separator film to the first outer surface comprising 5-100 wt% carbon nanotubes, the 5-100 wt% carbon nanotubes being effectively adhered to the separator film.

21. The method of claim 20, further comprising pressing the flexible self-supporting electrode with a pressing apparatus, the separator film and the 0-1 wt% concentration of carbon nanotubes effective to prevent the electrode from adhering to the pressing apparatus.

Background

With the rapid development of wearable devices, healthcare, cosmetics, wearable medical sensors, and drug delivery devices, portable electronic devices, smart packaging technology, and radio frequency identification technology, etc., in recent years, the development of thin and flexible batteries with high energy density is becoming a fundamental challenge to provide appropriate electrical energy to the respective devices, among other applications. Depending on the device, these batteries need not only to provide a potential suitable for the current electronic equipment (voltage range), but should also have an energy from μ Wh to kWh to cover a wide range of applications. However, these new applications require that the battery be flexible, thin, stretchable, rollable, bendable, and foldable, and can cover both tiny and large areas, in addition to the electrical parameters of the battery. These features are difficult to achieve in typical cell designs where the electrodes are printed on current collectors, such as metal foils; also in typical cell designs are cells, such as coin cells, cylindrical cells or prismatic cells, which are encased in a rigid casing. Therefore, new battery designs and materials are needed to power this rapidly growing field of wearable devices.

Disclosure of Invention

The present invention relates to batteries, and in particular to batteries made of flexible materials. In some variations, the present invention relates to a flexible lithium ion battery comprising a flexible anode comprising a composite material comprising particles of anode active material (graphite, silicon, any porous material matching the voltage of a given cathode material, natural graphite, artificial graphite, activated carbon, carbon black, high performance powdered graphene, etc.) in a three-dimensional cross-linked network of carbon nanotubes, the particle size ranging from 1 nanometer to larger; a flexible cathode comprising a composite material comprising cathode active material particles (lithium metal oxide, metallic lithium, etc.) in a three-dimensional cross-linked network of carbon nanotubes; and a flexible separator film positioned between the anode and the cathode, the flexible separator film characterized by a length, a width, a thickness, and at least one edge; wherein the battery is packaged in a pouch-type unit.

In some aspects, the battery has no current collector, and it is assembled without further pressing by disposing a separator between a fully prepared anode and a fully prepared cathode.

In some aspects, the battery has no current collector, and it is assembled by placing the separator film between a pre-pressed anode and a pre-pressed cathode, and optionally connected to tabs and optionally containing embedded tab attachments, and then pressed together.

In some aspects, the battery has no current collector, and it is assembled by disposing a separator between an unpressed anode and an unpressed cathode, wherein the anode and cathode each independently optionally include an embedded battery tab attachment, and then pressing the assembled anode, separator, and cathode.

In some aspects, the battery has no current collector, and it is assembled by disposing a separator between an unpressed first electrode and a prepressed second electrode, and then pressing the assembled anode, separator, and cathode.

In some aspects, the concentration of carbon nanotubes (5-100 wt% nanotubes) on the surface of the respective electrode facing the separator is higher than the concentration in the bulk of the electrode (0.5-10 wt% nanotubes), while the concentration of carbon nanotubes on the surface of the respective electrode distal from the separator will be lower than the concentration in the bulk of the electrode (0-1 wt% nanotubes), and the battery has no current collector.

In some aspects, the total thickness of the electrodes can be reduced by a factor of 1.1 to 5 by pressing, and the battery has no current collector.

In some aspects, one or more of the electrodes further comprises a battery tab attached to at least one of the respective protrusions extending from the electrode body across the separator or attached to the body of the electrode at the cut-outs of the separator membrane and the opposing electrode, and the battery has no current collector.

In some aspects, the battery further comprises one or more embedded battery tab attachments, each battery tab attachment extending from a respective electrode beyond an edge of the separator membrane, and wherein some of the battery tab attachments extend outside of the pouch cell and the battery does not have a current collector. In a multi-cell configuration, the tab attachments from multiple anodes are typically welded together and to a single tab inside the cell package, with only the single tab extending outside the cell package. The same is true for multiple cathodes.

In some aspects, the battery tabs extend across the pouch-type cells to deliver current to the exterior of the battery, and the battery has no current collectors.

In some aspects, the pouch cell is a polymer pouch cell, and the battery has no current collector.

In some aspects, the battery is a single cell configuration, and the battery has no current collectors.

In some aspects, the battery is in a multi-cell configuration and the battery has no current collector.

In some aspects, the battery further comprises a liquid, gel, or solid electrolyte, and the battery has no current collector.

In some aspects (as shown in fig. 3A-3B), one or more electrodes are in contact with a separator film on both faces of the one or more electrodes, wherein both faces of the one or more electrodes exhibit increased nanotube content relative to the nanotube content in the body of the one or more electrodes, and the battery has no current collector. This arrangement may exist in a single cell configuration or a multi-cell configuration, and an additional isolation film layer (fig. 3A) may be added to the exterior of the battery to improve the mechanical integrity of the battery and allow the battery to more easily slide relative to the package during bending, twisting, or similar movements. It is believed that this additional layer holds the electrode material together and prevents or reduces "washing off" of the active material particles from the electrode. In an internal electrode of a multi-cell configuration, this arrangement will always be present. Cells with separator films attached to both outer sides are also easier to handle during battery assembly/packaging.

In some aspects, the battery assembly is either flat packed or folded one or more times before being packed into a pouch-type cell, and the battery has no current collector.

Drawings

Fig. 1A and 1B illustrate schematic diagrams of a unit cell (fig. 1A) configuration and a multi-cell (fig. 1B) configuration according to some aspects of the present disclosure.

Fig. 2A-2D illustrate pouch cells connected to light emitting diode devices, wherein the pouch cells are in a flat (fig. 2A-2B) and a rolled (fig. 2C-2D) configuration, with fig. 2A and 2C in schematic form, and fig. 2B and 2D in photographic form, according to some aspects of the present disclosure.

Fig. 3A and 3B show schematic diagrams of a cell (fig. 3A) and multi-cell (fig. 3B) configuration according to other aspects of the present disclosure.

Fig. 4A and 4B show schematic cross-sectional views of preferred electrode layer structures according to some aspects of the present disclosure, with the separator on both sides (fig. 4A) or only on one side (fig. 4B).

Fig. 5 illustrates a battery in a folded configuration according to some aspects of the present disclosure.

Fig. 6 illustrates some exemplary preferred flexible self-supporting electrode stacking schemes for multi-cell and folded embodiments according to some aspects of the present disclosure.

Fig. 7 illustrates some exemplary preferred flexible self-supporting electrode stacking schemes of multi-cell and folded embodiments according to some aspects of the present disclosure.

Detailed Description

The invention relates to a flexible lithium ion battery, comprising: a flexible anode comprising a composite material comprising particles of an anode active material (graphite, silicon, etc.) in a three-dimensional cross-linked network of carbon nanotubes; a flexible cathode comprising a composite material comprising cathode active material particles (lithium metal oxide, metallic lithium, etc.) in a three-dimensional crosslinked network of carbon nanotubes; and a separator between the anode and the cathode. According to some aspects, the three-dimensional crosslinked network of carbon nanotubes may have a network morphology, a non-woven, an irregular or non-systematic morphology, or a combination thereof. In some aspects, the battery does not have a current collector. In some aspects, the cathode, anode, and separator are encapsulated in a pouch-type unit. Such a bag-type unit housing has suitable flexibility. In some aspects, the pouch cell housing may be a polymer housing.

The electrodes in the cell are not supported by a current collector foil, such as aluminum for the cathode or copper for the anode, and do not contain a binder that can break or flake. Instead, the electrodes are self-supporting. Without wishing to be bound by any particular theory, the presence of the plurality of carbon nanotubes in the carbon nanotube network makes the electrode self-supporting and flexible; and the flexible electrode results in the production of a flexible battery. When connected to light emitting diodes, the batteries in the present disclosure can successfully operate in a wide range of bent, rolled and folded states (angles less than or greater than 180 °) along the respective axes of the batteries in a rectangular pouch-type unit.

The current collector in a lithium ion battery is, for example, a copper foil in the anode or an aluminum foil in the cathode, both of which act as electrical conductors between the electrode and the external circuit and as a support for the coating of electrode material on the current collector, which may span the length and width of the electrode. Cracking of the metal foil and detachment of the active material from the current collector are problems faced by flexible electrodes and flexible batteries. As used herein, "without a current collector" refers to a battery or electrode that does not include a metal current collector or a foil current collector. It should be understood that the battery tab attached to the electrode is not a current collector, and is shown as a non-limiting example in fig. 1A-1B, 3A-3B, and 5. As used herein, a "flexible" electrode is capable of bending without breaking or fracturing. As known to those of ordinary skill in the art, flexibility may depend on one or more chemical and/or material factors, including but not limited to composition and degree of compression.

The term "about" as used herein is defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the term "about" is defined as within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

Further, the thickness of the binderless, collector-free self-supporting electrode can be varied by pressing, which can reduce the total thickness by up to 5 times, for example by about 4 times, about 3 times, about half, about 1.5 times, about 1.1 times, or any range therebetween. For example, a 100 micron thick binderless, collector-free, self-supporting electrode can be pressed to a thickness of 50 microns (i.e., a half reduction in total thickness), or a 500 micron thick binderless, collector-free, self-supporting electrode can be pressed to a thickness of 100 microns (i.e., a 5-fold reduction in total thickness). In some aspects, the pressing operation reduces the overall thickness by half. In some aspects, the pressing reduces the total thickness by a factor of about 1.1 to about 5. In some aspects, the pressing reduces the total thickness by a factor of about 1.5 to about 3. The optimum degree and/or limit of compaction for a given material may be determined by one of ordinary skill in the art. Suitably, the pressing operation does not substantially destroy the active material particles/flakes, i.e. as a general guide, no more than 25% of the particles or flakes are destroyed. For differentThe exact percentage of acceptable particle damage may vary for the formulation of the active material and the different electrode composites, and needs to be determined in each case by one of ordinary skill in the art. For cells containing liquid or gel electrolytes, suitably, sufficient voids remain in the material after pressing to maintain an effective electrolyte pathway, i.e., at least 50% of the surface (preferably 100% of the surface) of each particle or flake of active material is wetted by the electrolyte. A non-limiting example of a liquid electrolyte is LP71 electrolyte (1M LiPF6 in ethylene carbonate/diethyl carbonate/dimethyl carbonate, mixed in a 1: 1 volume ratio). Furthermore, after pressing, the voids are still properly interconnected, i.e. there are no trapped inaccessible voids. As a general guideline, the density of the compacted material should be suitably lower than the bulk density of the active material powder (rather than the density of the active material, which is higher; e.g., for NMC powder, lithium nickel manganese cobalt oxide powder, the bulk density is about 2.35g/cm³And density of NMC itself>3.5g/cm³). Pressing the electrode material to a density near or exceeding the bulk density of the active material powder can result in the electrode material being easily broken and no longer flexible. It should be understood that the characteristics of the outer casing material, such as flexibility, torqueability, wear resistance, are independent of the electrode material contained within the outer casing, for example.

According to aspects of the present disclosure, the pressing operation may improve the flexibility, mechanical strength, and/or electrolyte accessibility of the battery. Pressing also changes the density of the electrode. Suitable Methods and apparatus for pressing Electrodes are known in the art, including but not limited to U.S. patent application No.15/665,171 entitled "Self-stabilizing Electrodes and Methods for Making the same" filed 2017, 7, 31, which is hereby incorporated by reference in its entirety. According to aspects of the present disclosure, a single electrode may be pressed with or without a pouch-type cell, or the entire assembly assembled by a plurality of electrodes separated by a separator may be integrally pressed. In some aspects, the pressing operation reduces the overall thickness by a factor of about 1.1 to about 5. In some aspects, the pressing operation reduces the overall thickness by a factor of about 1.5 to about 3.

As known to those of ordinary skill in the art, pressing or compressing may improve the electrical and/or mechanical contact between the battery tab and the composite, and may also make the composite more mechanically robust. However, excessive compression or pressing hinders the electrolyte from entering the inside of the electrode and complicates the movement of lithium ions into and out of the electrode, thereby deteriorating the dynamic characteristics of the battery. Too much pressure may also cause the electrode to be hard and brittle, and to easily form cracks and disintegrate; this may reduce the battery capacity or destroy the battery completely. Alternatively, too little compression may not provide sufficient crosslinking of the nanotube network, resulting in a mechanically weaker electrode material, insufficient electrical contact within the material (and thus lower conductivity of the material and inefficient accumulation of current from the active material particles), and/or incomplete mechanical trapping of the active material particles within the nanotube network (which may be washed away by the electrolyte). Under-compression may also cause the electrode to thicken, requiring more electrolyte to fully wet the electrode, thus reducing the energy storage density of the battery. Furthermore, over-pressing may cause perforation of the release film, which is not a satisfactory result. In addition, it may be necessary to adjust the distance between the rolls or rollers in a roller press or calender or the distance between the plates of a plate press. It is within the knowledge of one of ordinary skill in the art to determine the optimum press thickness based on the desired characteristics of the electrode. Suitable equipment for pressing electrodes and/or batteries in the present disclosure include, but are not limited to, roller mills and hydraulic presses.

As used herein, "electrode active material" refers to a material that accommodates lithium in an electrode. The term "electrode" refers to an electrical conductor in which ions and electrons are exchanged with an electrolyte and an external circuit. "Positive electrode" and "cathode" are used synonymously in this specification to refer to the electrode in an electrochemical cell that has a higher potential (i.e., is higher than the negative electrode). "negative electrode" and "anode" are used synonymously in this specification to refer to the electrode in an electrochemical cell having a lower potential (i.e., lower than the positive electrode). Cathodic reduction refers to an increase in electrons of a chemical species and anodic oxidation refers to a loss of electrons of a chemical species.

The metal in the lithium metal oxide in the present disclosure may include, but is not limited to, one or more alkali metals, alkaline earth metals, transition metals, aluminum, or post-transition metals, and hydrates thereof. Non-limiting examples of lithium metal oxides include lithiated oxides of nickel, manganese, cobalt, aluminum, magnesium, titanium, and any mixtures thereof. In one illustrative example, the lithium metal oxide is lithium nickel manganese cobalt oxide (LiNi)_xMn_yCo_zO₂X + y + z ═ 1), lithium (Ni, Mn, Co) O₂Or Li-Ni-Mn-Co-O. The lithium metal oxide powder may have a particle size defined in the range of about 1 nanometer to about 100 micrometers, or any integer or subrange therebetween. In one non-limiting example, the lithium metal oxide particles have an average particle size of about 1 μm to about 10 μm

"alkali metal" is a metal of group I of the periodic Table of elements, such as lithium, sodium, potassium, rubidium, cesium or francium.

An "alkaline earth metal" is a metal of group II of the periodic Table of the elements, such as beryllium, magnesium, calcium, strontium, barium or radium.

"transition metals" are metals in the d-block of the periodic Table of the elements, including the lanthanides and actinides. Transition metals include, but are not limited to, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, actinium, thorium, lutetium, uranium, neptunium, americium.

"post-transition metals" include, but are not limited to, gallium, indium, tin, thallium, lead, bismuth, or polonium.

As used herein, a battery "successfully operates" in a bent, rolled or folded configuration, as measured, for example, by connection to an output of a battery device, if the charge-discharge capacity of the battery in the bent, rolled or folded configuration is substantially the same as the charge-discharge capacity (i.e., the capacity in the original or flat state) of the battery prior to bending, rolling or folding. When the charge/discharge C rate is 0.1C, if the capacity at the time of bending, curling or folding is within 75% of the charge/discharge capacity at the time of the original or flat state, the capacity is "substantially the same" as the charge/discharge capacity at the time of the original or flat state. As known to those of ordinary skill in the art, the "C-rate" of 0.1, 1, 10, 100, etc. is a term used in the art of cell characterization. As used herein, "1C rate" means that a constant discharge current will discharge the entire battery within 1 hour, or a constant charge current will charge the battery within 1 hour. The "0.1C rate" referred to herein means that the current is 10 times smaller and the charge/discharge process of the battery takes 10 hours. In practice, the "theoretical capacity" (a × h (or mA × h)) of the battery is first calculated based on the amount of active material and the specific capacity of the material in the battery. After that, the charge and discharge current was calculated by dividing the number of required hours (1 hour is 1C, 5 hours is 0.2C, 10 hours is 0.1C, 0.1 hour is 10C, etc.). The current is then used to measure the charge or discharge capacity of the battery, which is referred to as the charge or discharge capacity at the C-rate. According to some aspects, the charge and discharge capacity of the battery disclosed herein in the bent, rolled, or folded configuration is 75% to 100% of the charge and discharge capacity of the battery in the flat configuration.

In some aspects, the battery is in a unit cell configuration. Fig. 1A shows a schematic of a battery 100 in a single cell configuration according to the present disclosure. In such aspects, the first encapsulation layer 101 is adjacent the anode layer 102, the anode layer 102 is adjacent the isolation layer 103, the isolation layer 103 is adjacent the cathode layer 104, and the cathode layer 104 is adjacent the second encapsulation layer 101. The anode layer 102 and/or the cathode layer 104 may be configured to include points for attaching the battery tabs 105 and 106.

In some aspects, the battery is a multi-cell configuration. Fig. 1B shows a schematic diagram of a battery 110 in a multi-cell configuration according to the present disclosure. In such aspects, a plurality of alternating layers of anodes 102 and cathodes 104 are disposed between the isolation layer 103 and the encapsulation layer 101. Each anode layer 102 and/or cathode layer 104 may be configured to include points for attaching battery tabs. For the anode layer 102, the cell tabs are suitably copper tabs or leads 105. For cathode layer 104, the battery tabs are suitably aluminum tabs or leads 106. In the multi-cell configuration, some of the electrodes inside the multi-cell contact the separator 103 on both sides (fig. 1B, 3B). The number of electrode layers and separator layers in the multi-cell configuration is not particularly limited, and the multi-cell configuration battery 110 may contain more anodes, cathodes, and/or separator layers than shown in fig. 1B, as shown by optional additional layers 111. Battery 110 is similar in some respects to battery 100.

The electrodes in the present disclosure may be fabricated according to any suitable method known to those of ordinary skill in the art. For example, the anode and/or cathode may be prepared using the Methods and apparatus disclosed in U.S. patent application No.15/665,171 entitled "Self-stabilizing Electrodes and Methods for Making the same," attorney docket No. 037110.00687, filed 2017, 31/7, which is hereby incorporated by reference in its entirety. Carbon nanotubes suitable for use in the methods of the present invention include single-walled nanotubes, few-walled nanotubes and multi-walled nanotubes. In some aspects, the carbon nanotubes are single-walled nanotubes. The few-walled and multi-walled nanotubes can be synthesized, characterized, co-precipitated, and collected using any suitable method and apparatus known to those of ordinary skill in the art, including methods and apparatus for single-walled nanotubes. The length of the carbon nanotubes may range from about 50 nanometers to about 10 centimeters or more.

Suitable separator materials include those known to those of ordinary skill in the art for use between the anode and cathode of a battery to provide a barrier between the anode and cathode while allowing lithium ion exchange from one side to the other, such as a membrane barrier or separator. Suitable separator materials include, but are not limited to, polymers such as polypropylene, polyethylene and composites thereof, and PTFE. The separator is permeable to lithium ions so that they flow from the cathode side to the anode side and then back during a charge-discharge cycle. The separator is impermeable to the anode and cathode materials, preventing them from mixing, contacting and shorting the cell. The separator may also serve as an electrical insulator for the battery's metal parts (leads, tabs, current collectors, metal parts of the case, etc.) to prevent them from contacting and shorting. The separator can also prevent the flow of electrolyte.

In some aspects, the separator is a thin (15-25 μm) polymer film (three layer composite: polypropylene-polyethylene-polypropylene, currently commercially available) that is positioned between two relatively thick (20-1000 μm) porous electrode plates produced by our technique. The polymer film may be 15-25 μm thick, such as 15-23 μm, 15-21 μm, 15-20 μm, 15-18 μm, 15-16 μm, 16-25 μm, 16-23 μm, 16-21 μm, 16-20, 16-18 μm, 18-25 μm, 18-23 μm, 18-21 μm, 18-20 μm, 20-25 μm, 20-23 μm, 20-21 μm, 21-25 μm, 21-23 μm, 23-25 μm, 15 μm, 16 μm, 17, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 or 25 μm thick, or any integer or subrange therebetween. The two relatively thick porous electrode sheets may each independently be 50-500 μm thick, such as 50-450 μm, 50-400 μm, 50-350 μm, 50-300 μm, 50-250 μm, 50-200 μm, 50-150 μm, 50-100, 50-75 μm, 50-60 μm, 50-55 μm, 55-500 μm, 55-450 μm, 55-400 μm, 55-350 μm, 55-300 μm, 55-250 μm, 55-200 μm, 55-150 μm, 55-100 μm, 55-75 μm, 55-60 μm, 60-500 μm, 60-450 μm, 60-400 μm, 60-350 μm, 60-300 μm, 60-250 μm, 60-200 μm, 60-150 μm, 60-100 μm, 60-75 μm, 75-500, 75-450 μm, 75-400 μm, 75-350 μm, 75-300 μm, 75-250 μm, 75-200 μm, 75-150 μm, 75-100 μm, 100-400 μm, 100-450 μm, 100-400 μm, 100-350 μm, 100-300 μm, 100-250 μm, 100-200 μm, 100-150 μm, 150-500 μm, 150-450 μm, 150-400 μm, 150-350 μm, 150-300 μm, 150-250 μm, 150-200 μm, 200-500 μm, 200-450, 200-400 μm, 200-350 μm, 200-300 μm, 200-250 μm, 250-500 μm, 250-450 μm, 250-400 μm, 250-350 μm, 250-300 μm, 300-500 μm, 300-450 μm, 300-400 μm, 300-350 μm, 350-500 μm, 350-450 μm, 350-400 μm, 400-500 μm, 400-450 μm, 450-500 μm, 50 μm, 55 μm, 60 μm, 75 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, or 500 μm, or any integer or subrange therebetween.

The polymer used in the polymer pouch type cell may be any polymer suitable for use in an electrochemical cell, for example for the purpose of protecting the electrochemical cell from the external environment, or in case a flexible battery is used in a wearable device, and for protecting a user from the electrochemical cell. As is common in the artAs known to those, a pouch-type cell refers to an external packaging material that holds electrodes and separators and electrolyte inside. Non-limiting examples of suitable materials include those known to those of ordinary skill in the art, such as polyethylene (including aluminum with a polyethylene or polypropylene coating: e.g., polyamide (JIS Z1714):0.025mm (+ -0.0025mm), adhesive (polyester-polyurethane): 4-5g/cm²0.040mm (+ -0.004mm) of aluminum foil (JIS A8079, A8021), and 2-3g/cm of adhesive (without urethane adhesive)²0.040mm (+ -0.04mm)) polypropylene, PTFE, PDMS, and others. In various embodiments disclosed herein, for example, the outer casing material may be flexible, stretchable, twistable, wearable, implantable, biocompatible, non-creased or wrinkled, waterproof, durable, thermally insulating, or any combination of these features, or any combination with other suitable features depending on the desired application of the battery. According to some aspects, the outer packaging material may apply sufficient pressure to the electrodes so that the electrodes remain together inside the package and do not slip (between electrodes), peel or separate. In some embodiments, sliding of the electrodes within the outer enclosure may be provided by the inner surface characteristics of the outer enclosure or pouch-type unit without peeling or separating the electrodes therein. In a non-limiting example, all of the outer casing materials described herein can be polymers. Non-limiting examples of biocompatible, wearable and implantable materials are substrates that are harmless to living tissue, hypoallergenic or useful for living cell/tissue growth. Non-limiting examples of thermally insulating materials are materials that have low thermal conductivity and can remain cold or hot on one side of the material while keeping the transfer of cold and heat through the material to a minimum.

According to some aspects, the outer casing material may retain a fixed shape after forming the fixed shape, or the outer casing material may include shape memory, such as, in non-limiting examples, the ability to change from a deformed shape (temporary shape) back to an original (permanent) shape, e.g., under the direction of a temperature change or a stimulus of an applied force. In some embodiments, the outer encapsulant may have an outer, environmentally-facing surface that is different from an inner, cell-facing surface. In non-limiting examples, the outer surface may be textured or smooth. The inner surface may have a different characteristic than the outer surface, in a non-limiting example a smoothness that meets the following requirements: so that the batteries contained therein can be freely moved within the outer casing or within the pouch-type unit, if desired. According to some aspects, the outer packaging material is a multilayer material or is composed of various materials in different areas of the bag for different applications. It should be understood that the terms "bag" and "flexible bag" are used interchangeably herein.

In various embodiments disclosed herein, the shape of the pouch cell may be, for example, a circular, oval, triangular, trapezoidal, polygonal, ergonomically designed shape, or any shape of the flexible battery disclosed herein suitable for various applications. The shape of the bag shown in fig. 2A-2D is one non-limiting example. Batteries contemplated by the present disclosure may be assembled using any suitable method, including methods known to those of ordinary skill in the art

According to some aspects of the present disclosure, a battery tab may be attached to an electrode, wherein a protrusion extending from a body of the respective electrode across a separator and not overlapping another electrode may be attached; or to the body of the respective electrode at the cut-outs of the separator and counter electrode. According to some aspects, the cut-out may effectively form an exposed area for attachment to the flexible electrode. Suitable materials for the battery tab and suitable methods of attachment include those known to those of ordinary skill in the art.

Batteries according to aspects of the invention are assembled by placing a separator between a fully prepared anode and a fully prepared cathode without any further pressing. As used herein, a "fully prepared" anode or cathode is one that has been pressed and attached to a tab. In some aspects, the cells in various aspects of the present disclosure are assembled by placing a separator between a pre-pressed anode and a pre-pressed cathode, and pressing them all together. As used herein, a "pre-stressed" electrode is one that has been press processed but may or may not be connected to a tab or one that has been embedded into a tab attachment. In some aspects, the cell may be assembled by placing a separator between one non-pressed first electrode (anode or cathode) and the pre-pressed electrode (anode or cathode), and then the entire assembly may be pressed together.

Preferably, the concentration or content of carbon nanotubes (5-100 wt% nanotubes) on the electrode surface facing the separator is higher than the concentration of carbon nanotubes (0.5-10 wt% nanotubes) in the electrode body, while the concentration of carbon nanotubes (0-1 wt% nanotubes) on the electrode surface away from the separator is lower than the concentration of carbon nanotubes in the electrode body (fig. 3A-3B). According to some aspects, 0.5-10 wt% of the nanotubes in the electrode body may be 0.5-10 wt% at the central plane or central longitudinal plane of the flat electrode. Those of ordinary skill in the art recognize that composites containing more than about 5% nanotubes are very viscous and can adhere to separator films and stainless steel (which is a typical material for making rollers in roller mills), as well as many other materials. For example, 5% nanotubes, 95% NMC (lithium nickel manganese cobalt oxide, LiNi)_xMn_yCo_zO₂) The composite material (especially freshly made) adheres so strongly to the roll that it is difficult to separate it from the roll without tearing the composite material. However, the same material did not stick to the roller in any appreciable amount after "dusting" the NMC powder. These "boundary layers" may be 2-5 times thicker than the average size of the active material particles/flakes; for example, for NMC particles used in the cathode having an average diameter of about 10 μm, a 20-30 μm thick "boundary layer" containing an increased or decreased nanotube content may be sufficient. According to aspects of the present disclosure, such distribution of carbon nanotubes on or within the electrode will promote adhesion of the electrode to the separator while reducing adhesion to rollers and other elements of the pressing apparatus (for pressing the electrode and pressing the battery). Such a distribution can be achieved by varying the ratio of nanotube aerosol to active material aerosol (i.e., the ratio of the weight of nanotubes deposited per unit time to the weight of active material deposited per the same unit time) during the growth of the electrode materialRate) of the active material (e.g., 100% active material aerosol at the beginning of the synthesis, 97% active material aerosol during most of the synthesis, and 3% nanotube aerosol, 100% nanotube aerosol at the end of the synthesis). For example, according to the present disclosure, a nanotube synthesis reactor may be configured to produce approximately 2 milligrams of atomized nanotubes per hour (amount deposited on the frit/filter). In the same setting, the NMC feeder may be set to atomize about 2 to 600mg of NMC particles per hour (again, the amount precipitated on the same filter). Thus, depending on the NMC feeder settings, a material containing 50% nanotubes (2mg +2mg) to about 0.3% nanotubes (2mg +600mg) can be precipitated. Operating only the nanotube reactor (NMC feeder closed) would produce 100% nanotube material, while operating only the NMC feeder (nanotube reactor closed) would produce 0% nanotube material (100% NMC powder). Suitable Methods for varying the ratio of nanotube aerosol to active nanotube aerosol during this process include, but are not limited to, the Methods disclosed in U.S. patent application No.15/665,171 entitled "Self-stabilizing Electrodes and Methods for Making the same" filed on 31/7, 2017, the entire contents of which are incorporated herein by reference.

The cells may be of any size, i.e. any length, width and height. In some aspects, the thickness of the battery is less than or equal to 10mm, e.g., 5mm, 4.5mm, 3mm, 2.5mm, 1.5mm, 1mm, 0.7mm, 0.5mm, 0.3mm, 0.2mm, 0.1mm, 0.01mm, or any value or range therebetween. In some aspects, the length and width are each independently less than or equal to 10000mm, e.g., 1000mm, 200mm, 150mm, 100mm, 75mm, 50mm, 40mm, 30mm, 25mm, 20mm, 10mm, 1mm, 0.5mm, 0.1mm, or any value or range therebetween.

Fig. 2A-2D illustrate examples of batteries connected to light emitting diode devices according to the present disclosure. In this non-limiting example, a complete pouch cell contains a 3 x 4cm electrode and is connected to a light emitting diode device. The thickness of the cell was 3 mm. In the flat configuration (fig. 2A-2B), the battery 200 operates to power the light emitting diode device as tested through the light output end of the device. After being bent multiple times at various angles and in various directions, the battery 200 is still able to power the light emitting diode device in a rolled configuration to cause it to emit light when the light emitting diode device is powered (fig. 2C-2D). Battery 200 is similar in some respects to battery 100.

It is beneficial for all of the electrodes in the cell 300 of the configuration shown in fig. 3A (e.g., the anode 102 and cathode 104 in fig. 3A), and the internal electrodes 102 and 104 of the cell 310 of the multi-cell configuration shown in fig. 3B, to contact the separator film 103 on both sides, with an increased nanotube content 402 (in the electrode) on both surfaces of the electrodes (i.e., on both sides of the anode 102, both in contact with the separator film 103, and on both sides of the cathode 104, both in contact with the separator film 103) (fig. 4A). In FIG. 4A, the center of the electrode contains a bulk electrode material 401 containing 0.5-10 wt% nanotubes. The band 402 contains electrode material with an increasing content of nanotubes, for example 5-100 wt% nanotubes, in a direction from the center of the electrode outwards towards the separator film 103. Belt 402 contacts release film 103 at its outer edge, and release film 103 extends in direction 405 from the side facing belt 402 to the side facing the roller or press in manufacture. Batteries 300 and 310 are similar in some respects to battery 100.

The difference between fig. 3A-3B and fig. 1A-1B is that additional barrier film layers 103 are added on both outer sides of the battery (single cell or multi-cell configuration) to improve the mechanical integrity of the battery and allow the battery to better slide relative to the package. This additional layer of separator film 103 may even wrap around the assembled cell. All of the electrodes of the batteries shown in fig. 3A and 3B (single cell or multi-cell configuration) will be in the configuration shown in fig. 4A, while the outer electrodes of the batteries shown in fig. 1A-1B will be in the configuration shown in fig. 4B. In fig. 4B, the outer surface of the separator film 103 faces 405 direction, towards the roller or press, and the inner surface faces the strip 402 of electrodes, which have an increased nanotube content, e.g. 5-100 wt% nanotubes. Continuing inward through the ribbon 402, the opposite face of the ribbon 402 faces a region of the body of electrode material 401 containing 0.5-10 wt% nanotubes. The opposite side of the region of the body of electrode material 401 again faces a region 404 of reduced nanotube content, the region 404 containing 0-1 wt% nanotubes. Moving further inward, the opposite side of the reduced nanotube content region 404 faces inward in a direction 405 toward a roller or press.

A battery assembly according to the present disclosure (i.e., an anode, a separator, and a cathode in a single cell configuration; or multiple alternating layers of separator layers, one or more anodes, one or more separators, and one or more cathodes in a multi-cell configuration) may be packaged in a pouch-type cell in a flat state (i.e., as shown in fig. 1A, 1B, and 2A), or folded one or more times before being packaged in a pouch-type cell (as shown in fig. 5). In the pouch type unit cell 500, a battery including a multi-layered structure (the separator 103, the anode 102, the separator 103, the cathodes 1 to 4, and the separator 103) is folded one or more times before being packaged by a pouch type unit made of the packaging layer 101. Electrolyte 107 is also suitably contained in the pouch-type cell during packaging. The anode layer 102 and the cathode layer 104 may each be configured to include points for attaching battery tabs. For the anode layer 102, the battery tab is suitably a copper tab or lead 105. For the cathode layer 104, the battery tabs are suitably aluminum tabs or guides 106. Battery 500 is similar in some respects to battery 100. In some embodiments, additional battery tab extensions may be attached to 105 and/or 106.

Packaging in a pouch-type unit, such as in the packaging layer 101, after pre-folding, may increase battery capacity, but may also reduce battery flexibility. In the folded configuration, one or more additional separator films may be needed to prevent the electrodes from contacting each other (or to prevent any of their electrical leads from contacting each other). In some such aspects, it may be advantageous to include one or two additional separator layers such that the multi-cell configuration alternates, in part, as shown in FIGS. 3A-3B, separator 103, anode 102, separator 103, cathode 104, separator 103. Such an assembly not only simplifies the folded configuration shown in fig. 5, but also makes the battery mechanically stronger, enabling it to withstand additional bending, folding, rolling, flexing and/or wear; because the added spacer helps to slide the battery assembly into the pouch-type cell and, more importantly, allows the battery assembly to slide entirely relative to the enclosure/package during bending, folding, flexing, etc., while minimizing movement of the battery components relative to each other. Such movement of the internal battery components relative to each other can be detrimental to battery performance. For such a configuration of the electrode (cathode or anode or both) material, it is preferable to have a greater concentration of nanotubes on both faces, i.e. on both faces of the electrode in contact with the separator. Since only the separator film will contact the roller or other device, with the increasing concentration of nanotubes on the electrode surface, the electrode will adhere well to both separator films, facilitating assembly and/or pressing of the entire 5-layer cell assembly. In the case where only one additional separator is used, the side of the electrode material that does not contact or face the separator preferably has a reduced nanotube content on the side that does not contact the separator.

According to some aspects, the natural adhesion properties of the nanotubes are used to attach the flexible self-supporting electrode to the separator (or flexible solid electrolyte sheet). This natural adhesion effect can be further enhanced by increasing the nanotube content on the electrode surface facing the separator as shown in fig. 4A-4B and fig. 7. This is an important aspect of flexible batteries, where electrode separation is one of the major mechanisms of battery performance degradation, particularly during battery bending. As used herein, "naturally adhere" refers to the ability of one material to adhere to another material without the addition of an adhesive or binder. Composites containing more than about 5% (wt%) nanotubes are considered by those of ordinary skill in the art to be very viscous and can stick to separator films and stainless steel, which is a typical material used to make rollers for roller mills, as well as many other materials. For example, 5% nanotubes, 95% NMC (lithium nickel manganese cobalt oxide, LiNi)_xMn_yCo_zO₂) The (especially freshly made) composite adheres so strongly to the roll that it is difficult to separate it from the roll without tearing the composite. According to some aspects, by reducing the nanotube content on the surface of the side facing the roller (area of low nanotube content in fig. 4B, 7), undesired adhesion of the flexible self-supporting electrode to some surfaces, for example the roller of a roller mill, is avoided or minimizedOr the surface of a press. For example, if the electrodes stick to the drum, the electrodes can be damaged. In some embodiments, the "growing" electrode material may need to be compacted to increase the mechanical properties of the material and reduce the porosity of the material, thereby reducing the required electrolyte volume to increase the energy density of the battery.

In some embodiments, the cell (e.g., a cathode-separator-anode "sandwich") may be assembled starting with a pre-pressed cathode or pre-pressed anode with a separator membrane disposed between them, or by pressing one or both electrodes directly onto the separator membrane (or solid electrolyte sheet), increasing the adhesion of the electrode to the membrane and combining the two operations in one operation. According to some aspects, the separator film on one or both sides of the electrode (fig. 4A) may also be used as a "non-stick" layer during pressing, and in this case, it is beneficial to increase the nanotube content on both sides of the electrode (fig. 4A). In some embodiments, when an electrode (e.g., an anode) opposite an electrode is on both sides of the electrode (e.g., a cathode), attaching a separator film on both sides of the electrode (fig. 4A) enables a multi-cell and folded cell configuration to prevent the opposite electrodes from touching and shorting. In some embodiments, a preferred stacking scheme for the multiple unit and folded embodiments is shown as 601 in fig. 6. As shown in fig. 6, 602 represents a cathode, 603 represents a separator, and 604 represents an anode. 602 (cathode) and 604 (anode) can be switched. The stacking scheme 601 may be rolled together. In some embodiments, a preferred stacking scheme for the multiple unit and folded embodiments is shown in fig. 7 as 605. As shown in fig. 7, 404 represents a reduced or minimized nanotube content area, for example, to avoid undesirable adhesion of the flexible self-supporting electrode to some surface, such as the surface of a roller or press of a roller mill. The cathode 602 is shown with an increased nanotube content region 402 near the separator 603 and the anode 604 is shown with two increased nanotube content regions 402 near the separator 603. For example, in fig. 7, the cathode and anode may be switched and the configuration 605 may be rolled together.

In some embodiments, to attach Battery tabs to both sides of an Electrode encapsulated with a separator, the Electrode may have an embedded Tab Attachment, the Tab crossing the edge of the separator, or the Electrode itself may have a Tab crossing the edge of the separator and the Tab connected to the Tab of the Electrode, as illustrated in U.S. patent application No.16/123,872 entitled "Method for Embedding a Battery Tab Attachment in a Self-stacking Electrode Without Current Collector or Binder" filed on 6.9.2018, as described in U.S. patent application No.16/123,935 entitled "Method for Battery Tab Attachment to a Self-stacking Electrode" filed on 6.9.2018. Such battery tab attachment locations should not overlap each other to prevent short circuits, or additional portions such as a separator may be added therebetween. In some embodiments, the electrode may include an embedded battery tab attachment, e.g., a protrusion across an edge of the separator membrane as described in U.S. patent application No.16/123,872. For example, as described in U.S. patent application No.16/123,872, a strip, mesh or net of metal foil may be embedded in the electrode material during deposition of the electrode material, with a portion of the strip extending over the edge of the electrode, and optionally over the edge of the separator film. In some embodiments, a pre-fabricated tab may be welded or attached to the protruding portion of the band, or the band itself may be long enough to extend beyond the outer case of the battery and act as a tab to bring current out of the battery. In the latter case, care should be taken to prevent the strip/tab from leaking through the area of the battery compartment. For example, to this end, the preformed tabs are typically deposited with some sealant material thereon.

According to some aspects, the battery tab extension may be attached to the battery tab, which may be located on, within, or embedded in the electrode. The attachment may be made, for example, by brazing, welding, pre-manufactured interlocking components, or by any means known in the art. In some embodiments, the battery tab extension may extend through the flexible pouch to provide electrical current to various devices. To prevent leakage of the battery tabs or battery tab extensions in areas extending through or out of the flexible bag, these areas may be sealed using a joint or sealant. In some aspects, the durability of the flexible lithium ion battery is maintained over time by bending of the seal or joint into various configurations. In various embodiments, the battery tab extension may comprise a flexible conductive material.

This written description uses examples to disclose the invention, including the preferred embodiment, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims. One of ordinary skill in the art may mix and match various aspects of the various embodiments described, as well as other known equivalents for each such aspect, to construct other embodiments and techniques in accordance with the principles of the application.

According to some aspects, disclosed herein is a flexible lithium ion battery comprising: an electrolyte; one or more electrodes, the electrodes comprising: one or more flexible anodes comprising carbon nanotubes; and one or more flexible cathodes comprising carbon nanotubes; one or more flexible separator membranes between the one or more flexible anodes and one or more flexible cathodes; to form a battery; and wherein the battery is within a flexible pouch comprising an outer packaging material for retaining the battery within the interior thereof. In some embodiments, the one or more electrodes further comprise a battery tab attached to at least one of the respective protrusions extending from the main body of the one or more electrodes through the separator membrane or attached to the main body of the one or more electrodes at the incision of the battery. The concentration of carbon nanotubes on the surface of each electrode facing and in contact with the separator may be 5-100 wt% carbon nanotubes, the concentration of carbon nanotubes in the bulk of the electrodes may be 0.5-10 wt% carbon nanotubes, and the concentration of carbon nanotubes on the surface of each electrode facing away from and not in contact with the separator may be 0-1 wt% carbon nanotubes.

According to some aspects, a method of manufacturing a flexible lithium ion battery is disclosed, the method comprising: providing one or more electrodes, each electrode comprising one or more surfaces comprising 5-100 wt% carbon nanotubes; providing one or more barrier films; disposing one or more separator films between the one or more electrodes, the one or more separator films in contact with one or more surfaces comprising 5-100 wt% carbon nanotubes to form a battery; the battery is disposed in a flexible bag that includes an outer packaging material that can retain the battery within its interior. In some embodiments, the method may further comprise a surface of the one or more electrodes not in contact with the one or more separator films, the surface comprising 0-1 wt% carbon nanotubes, the 0-1 wt% carbon nanotubes effective to provide the one or more non-stick surfaces. In some embodiments, the method may further comprise disposing one or more separator films on a surface of the one or more electrodes, rather than between the one or more electrodes, such that the one or more separator films are located on one or more outer surfaces of the one or more electrodes. According to some aspects, a method of manufacturing a flexible self-supporting electrode comprises: collecting carbon nanotubes with a concentration of 5-100 wt%; collecting the carbon nano-tube with the concentration of 0.5-10 wt%; collecting carbon nanotubes at a concentration of 0-1 wt% to form a flexible self-supporting electrode comprising 5-100 wt% carbon nanotubes on a first outer surface, a concentration of carbon nanotubes in the bulk of 0.5-10 wt%, and a concentration of carbon nanotubes on a second outer surface of 0-1 wt%.

While the aspects described herein have been described in conjunction with the exemplary aspects described above, various alternatives, modifications, variations, improvements, and/or substantial equivalents, whether known or that are or may be presently unforeseen, may become apparent to those having at least ordinary skill in the art. Accordingly, the exemplary aspects as set forth above are intended to be illustrative, not limiting. Various changes may be made without departing from the spirit and scope of the disclosure. Accordingly, the present disclosure is intended to embrace all known or later-developed alternatives, modifications, variations, improvements and/or substantial equivalents.

Thus, the claims are not intended to be limited to the aspects shown herein, but is to be accorded the full scope consistent with the claims, wherein reference to an element in the singular is not intended to mean "one and only one". Unless specifically stated otherwise, the term "one or more" is used. All structural and functional equivalents to the elements of the various aspects described throughout this disclosure that are known or later come to be known to those of ordinary skill in the art are expressly incorporated herein by reference and are intended to be encompassed by the claims. Moreover, nothing disclosed herein is intended to be dedicated to the public regardless of whether such disclosure is explicitly recited in the claims. Any claim element should not be construed as a means plus function unless the element is explicitly recited using the phrase "means for … …".

Furthermore, the word "exemplary" is used herein to mean "serving as an example, instance, or illustration. Any aspect described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other aspects. The term "some" means one or more unless explicitly stated otherwise. Combinations such as "at least one of a, B, or C", "at least one of a, B, and C", and "a, B, C, or any combination thereof" include a, B, and/or C, and may include multiples of a, multiples of B, or multiples of C. In particular, combinations such as "at least one of a, B or C", "at least one of a, B and C" and "a, B, C or any combination thereof" may be a only, B only, C only, a and B, a and C, B and C or a and B and C, wherein any such combination may contain one or more of a, B or C. Nothing disclosed herein is intended to be dedicated to the public regardless of whether such disclosure is explicitly recited in the claims.

The examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to make and use the invention, and are not intended to limit the scope of what the inventors regard as their invention nor are they intended to represent that the experiments below are all or the only experiments performed. Efforts have been made to ensure accuracy with respect to numbers used (e.g., amounts, sizes, etc.) but some experimental error and deviation should be accounted for.

Moreover, all references, such as patent documents, throughout this application, include issued or granted patents or equivalents; patent application publications; non-patent literature documents or other source material; are all incorporated by reference herein in their entirety, similar to their individual incorporation by reference.

It will be appreciated that various embodiments of the above-disclosed and other features and functions, or alternatives or variations thereof, may be desirably combined into many other different systems or applications. Also that various presently unforeseen or unanticipated alternatives, modifications, variations or improvements therein may be subsequently made by those skilled in the art which are also intended to be encompassed by the following claims.

The novel features believed characteristic of the disclosure are set forth in the appended claims. In the following description, like parts are marked throughout the specification and drawings with the same reference numerals, respectively. The drawings are not necessarily to scale and certain drawings may be shown exaggerated or in generalized form in the interest of clarity and conciseness. The disclosure itself, however, as well as a preferred mode of use, further objectives and improvements thereof, will best be understood by reference to the following detailed description of an illustrative aspect of the disclosure when read in conjunction with the accompanying drawings.