Patent Application
20230050827
The present disclosure relates to lithium ion batteries and related energy storage devices.
Silicon has been proposed for lithium-ion batteries to replace the conventional carbon-based anodes, which have a storage capacity that is limited to ˜370 mAh/g. Silicon readily alloys with lithium and has a much higher theoretical storage capacity (˜3600 to 4200 mAh/g at room temperature) than carbon anodes. However, insertion and extraction of lithium into the silicon matrix causes significant volume expansion (>300%) and contraction. This can result in rapid pulverization of the silicon into small particles and electrical disconnection from the current collector.
The industry has recently turned its attention to nano- or micro-structured silicon to reduce the pulverization problem, i.e., silicon in the form of spaced apart nano- or micro-wires, tubes, pillars, particles and the like. The theory is that making the structures nano-sized avoids crack propagation and spacing them apart allows more room for volume expansion, thereby enabling the silicon to absorb lithium with reduced stresses and improved stability compared to, for example, macroscopic layers of bulk silicon.
Despite research into various approaches batteries based primarily on silicon have yet to make a large market impact due to unresolved problems.
There remains a need for anodes for lithium-based energy storage devices such as Li-ion batteries that are easy to manufacture, robust to handling, high in charge capacity and amenable to fast charging, for example, at least 1C.
In accordance with an embodiment of this disclosure, an anode for an energy storage device includes a current collector. The current collector includes a metal layer and a metal oxide layer provided in a first pattern overlaying the metal layer. The anode further includes a patterned lithium storage structure including a continuous porous lithium storage layer selectively overlaying at least a portion of the first pattern of metal oxide.
In accordance with another embodiment of this disclosure, a method of making an anode for use in an energy storage device includes providing a current collector having a metal layer and a metal oxide layer provided in a first pattern overlaying the metal layer. A continuous porous lithium storage layer is selectively formed by chemical vapor deposition by exposing the current collector to at least one lithium storage material precursor gas.
The present disclosure provides anodes for energy storage devices that may have one or more of at least the following advantages relative to conventional anodes: improved stability at aggressive ≥1C charging rates; higher overall areal charge capacity; higher charge capacity per gram of silicon; improved physical durability; simplified manufacturing process; and more reproducible manufacturing process.
It is to be understood that the drawings are for purposes of illustrating the concepts of the disclosure and may not be to scale.
In
With respect to the continuous porous lithium storage layer, “selectively forms on” may mean that: i) deposition of the first lithium storage material is kinetically or thermodynamically favored on the first pattern 106 of metal oxide relative to deposition on the second pattern 109; or ii) the first lithium storage material preferentially adheres to the first pattern of metal oxide 106 relative to adherence to the second pattern 109; or iii) a combination of (i) and (ii).
As mentioned, the current collector precursor includes an electrically conductive metal layer. In some embodiments, the current collector precursor includes substantially no layers other than the metal layer 103. In some embodiments, the metal layer 103 may be a metal foil (shown). Alternatively, rather than a metal foil, the metal layer 103 may be in the form of a metal mesh. The metal layer may include a single metal, an alloy, or multiple layers of different metals. In some embodiments, the current collector precursor may be a multilayer structure having a substrate and the metal layer provided at one or both surfaces. The substrate may include a polymer, another metal, a ceramic or a multilayer structure of one or more of such materials. In some embodiments, the metal layer may include a transition metal or its alloys. In some embodiments, the metal layer may include titanium (or its alloys), nickel (or its alloys), copper (or its alloys), or stainless steel.
There are numerous methods available for forming a first pattern of a metal oxide layer on a surface the metal layer. In some embodiments, a surface portion of the metal layer is oxidized or otherwise chemically transformed into the metal oxide. In such case, the metal oxide may include the same metal(s) as found in a surface portion of the metal layer. In the case where the current collector precursor includes an insulating substrate and a metal layer, the depth of oxidation should generally not extend all the way through the metal layer, since that may reduce electrical connectivity to the lithium storage layer.
In Step 306 (
Alternatively, instead of etching, the metal oxide may be removed by reducing it back to metallic form, i.e. metal with an oxidation state of 0. For example,
It should be noted that the second pattern (109, 409, 509) may correspond to metallic areas of the current collector, and while not having the metal oxide layer (105, 405, 505), may nevertheless have a small amount of surface oxide. In some embodiments, any such oxide in the second pattern may be less than 25% in thickness relative to the thickness of metal oxide layer in the first pattern, alternatively less than 10%, alternatively less than 5%, alternatively less than 2%.
In some embodiments (not shown in the figures), rather than using a patterned oxidation resistant material 717, pattern-wise oxidation of the metal layer may be performed directly by printing an oxidant in the desired first pattern.
In some embodiments, rather than oxidizing the metal layer, the first pattern of metal oxide may be provided by additive methods over the current collector precursor. For example, as shown in
In some embodiments, a non-patterned metal oxide precursor composition layer may be provided over the current collector precursor and treated to form a metal oxide layer. It may then be patterned, for example, as described with respect to
In some embodiments, a non-patterned metal oxide layer may be provided over the current collector precursor by atomic layer deposition (ALD), CVD, evaporation or sputtering. It may then be patterned, for example, as described with respect to
In some embodiments, first pattern of first metal oxide layer 905 may be provided by deposition of a vaporized metal oxide 955 through a shadow mask 950 onto metal layer 903 to form current collector 901, as shown in
The metal oxide layer may include a mixture of metal oxides having homogeneously or heterogeneously distributed oxide stoichiometries, mixtures of metals or both. The metal oxide layer should be sufficiently electrically conductive (non-insulating) to allow transfer of electrical charge between metal layer and the continuous porous lithium storage layer. The metal oxide layer may include dopants or regions of unoxidized metal that promote electrical conductivity.
In some embodiments, the metal oxide layer includes a transition metal oxide, e.g., an oxide of nickel, titanium or copper. As mentioned, the metal oxide layer may include mixtures of metals. For example, an “oxide of nickel” may optionally include other metals in addition to nickel but in lesser amount. In some embodiments, the metal oxide layer has an average thickness of at least 0.020 μm, alternatively at least 0.030 μm, alternatively at least 0.050 μm, alternatively 0.1 μm, alternatively, at least 0.2 μm, alternatively at least 0.5 μm. In some embodiments, the metal oxide layer has an average thickness in a range of 0.02 μm to 0.03 μm, alternatively 0.03 μm to 0.05 μm, alternatively 0.05 μm to 0.1 μm, alternatively 0.1 μm to 0.2 μm, alternatively 0.2 μm to 0.5 μm, alternatively 0.5 μm to 1 μm, alternatively 1 μm to 2 μm, alternatively 2 μm to 5 μm, alternatively 5 μm to 10 μm, or any combination of contiguous ranges thereof. The metal oxide layer may include a stoichiometric oxide, a non-stoichiometric oxide or regions of both. In some embodiments, the metal within the metal oxide may exist in a single oxidation state. In other embodiments, the metal within the metal oxide layer may exist in multiple oxidation states. In some embodiments the metal oxide layer may have a gradient of oxygen content where the atomic % of oxygen adjacent to the metal layer is lower than the atomic % adjacent to the lithium storage layer.
In some embodiments, the metal oxide is formed in the same chamber as, or in line with, a tool used to deposit the continuous porous lithium storage layer. In some embodiments, the metal oxide layer itself may have some reversible or irreversible lithium storage capacity. In some embodiments, the reversible capacity of the metal oxide layer is lower than that of the continuous porous lithium storage layer. In some embodiments, the metal oxide layer may be porous.
As mentioned previously, in some embodiments the metal oxide may be formed by oxidizing a surface region of a metal layer. This method is amenable to high-volume and low-cost production of current collectors. The oxidation conditions depend upon the metal/metal surface, the target oxide thickness and the desired oxide porosity. Unless otherwise stated, any reference to a particular metal includes alloys of that metal. For example, nickel foil may include pure nickel or any alloy of nickel wherein nickel is the primary component. In some embodiments, an alloyed metal also oxidizes, and the oxide of nickel formed from the alloy may include that corresponding oxidized metal. In some embodiments, the current collector is formed by thermal oxidation of a nickel substrate, e.g., a nickel foil, in ambient air in a furnace brought to a temperature of at least 300° C., alternatively at least 400° C., for example in a range of about 600° C. to about 900° C., or alternatively higher temperatures. The hold time depends upon the selected temperature and the desired thickness/porosity for the metal oxide layer. In some embodiments, the oxidation hold time will be in a range of about 1 minute to about 2 hours, but shorter or longer times are contemplated. A surface pretreatment step may be applied to promote or otherwise control oxidation. Other metals such as copper and titanium may have other operational hold times, temperatures and pretreatments according to their propensity to be oxidized.
As mentioned, the current collector may include two or more sublayers differing in chemical composition. For example, the current collector may include metallic copper foil as a first electrically conductive sublayer, a second electrically conductive sublayer of metallic nickel provided over the copper, and a patterned layer of a nickel oxide over the metallic nickel. Similarly, the metal oxide layer may include two or more sublayers differing in chemical composition. For example, the current collector may include a metallic copper foil, a sublayer of a copper oxide over the copper foil and a sublayer of titanium dioxide over the copper oxide. Such sublayers may be discrete or take the form of a gradient in chemical composition. In some embodiments there may be a gradient or transition zone between the metal layer(s) and the metal oxide layer(s).
Referring again to
The continuous porous lithium storage layer includes a porous material capable of reversibly incorporating lithium. In some embodiments, the continuous porous lithium storage layer includes silicon, germanium or a mixture of both. In some embodiments, the continuous porous lithium storage layer includes antimony or tin. In some embodiments, the continuous porous lithium storage layer is substantially amorphous. In some embodiments, the continuous porous lithium storage layer includes substantially amorphous silicon. Such substantially amorphous storage layers may include a small amount (e.g., less than 20 atomic %) of crystalline material dispersed therein. The continuous porous lithium storage layer may include dopants such as hydrogen, boron, phosphorous or metallic elements. In some embodiments the continuous porous lithium storage layer may include porous substantially amorphous hydrogenated silicon (a-Si:H), having, e.g., a hydrogen content of from 0.1 to 20 atomic %, or alternatively higher. In some embodiments, the continuous porous lithium storage layer may include methylated amorphous silicon. Note that, unless referring specifically to hydrogen content, any atomic % metric used herein for a lithium storage material or layer refers to all atoms other than hydrogen.
In some embodiments, the continuous porous lithium storage layer includes at least 40 atomic % silicon, germanium or a combination thereof, alternatively at least 50 atomic %, alternatively at least 60 atomic %, alternatively at least 70 atomic %, alternatively, at least 80 atomic %, alternatively at least 90 atomic %. In some embodiments, the continuous porous lithium storage layer includes at least 40 atomic % silicon, alternatively at least 50 atomic %, alternatively at least 60 atomic %, alternatively at least 70 atomic %, alternatively, at least 80 atomic %, alternatively at least 90 atomic %, alternatively at least 95 atomic %, alternatively at least 97 atomic %.
In some embodiments, the continuous porous lithium storage layer includes less than 10 atomic % carbon, alternatively less than 5 atomic %, alternatively less than 2 atomic %, alternatively less than 1 atomic %, alternatively less than 0.5 atomic %. In some embodiments, the continuous porous lithium storage layer includes less than 1% by weight of carbon-based binders, graphitic carbon, graphene, graphene oxide, reduced graphene oxide, carbon black, and conductive carbon.
The continuous porous lithium storage layer includes voids or interstices (pores), which may be random or non-uniform with respect to size, shape and distribution. Such porosity does not result in, or a result from, the formation of any recognizable nanostructures such as nanowires, nanopillars, nanotubes, nanochannels or the like. In some embodiments, the pores are polydisperse. In some embodiments, when analyzed by SEM cross section, 90% of pores larger than 100 nm in any dimension are smaller than about 5 μm in any dimension, alternatively smaller than about 3 μm, alternatively smaller than about 2 μm. In some embodiments, the continuous porous lithium storage layer may include some pores that are smaller than 100 nm in any dimension, alternatively smaller than 50 nm in any dimension, alternatively smaller than 20 nm in any dimension. In some embodiments the continuous porous lithium storage layer has an average density in a range of 1.0-1.1 g/cm3, alternatively 1.1-1.2 g/cm3, alternatively 1.2-1.3 g/cm3, alternatively 1.3-1.4 g/cm3, alternatively 1.4-1.5 g/cm3, alternatively 1.5-1.6 g/cm3, alternatively 1.6-1.7 g/cm3, alternatively 1.7-1.8 g/cm3, alternatively 1.8-1.9 g/cm3, alternatively 1.9-2.0 g/cm3, alternatively 2.0-2.1 g/cm3, alternatively 2.1-2.2 g/cm3, alternatively 2.2-2.25 g/cm3, or any combination of contiguous ranges thereof, and includes at least 80 atomic % silicon, alternatively at least 90 atomic % silicon, alternatively at least 95 atomic % silicon.
In some embodiments, the majority of active material (e.g., silicon, germanium or alloys thereof) of the continuous porous lithium storage layer has substantial lateral connectivity across portions of the current collector creating, such connectivity extending around random pores and interstices (as discussed later). Referring to
CVD
CVD generally involves flowing a precursor gas, a gasified liquid in terms of direct liquid injection CVD or gases and liquids into a chamber containing one or more objects, typically heated, to be coated. Chemical reactions may occur on and near the hot surfaces, resulting in the deposition of a thin film on the surface. This is accompanied by the production of chemical by-products that are exhausted out of the chamber along with unreacted precursor gases. As would be expected with the large variety of materials deposited and the wide range of applications, there are many variants of CVD that may be used to form the lithium storage layer, the metal silicide layer, a supplemental layer (see below) or other layer. It may be done in hot-wall reactors or cold-wall reactors, at sub-torr total pressures to above-atmospheric pressures, with and without carrier gases, and at temperatures typically ranging from 100-1600° C. in some embodiments. There are also a variety of enhanced CVD processes, which involve the use of plasmas, ions, photons, lasers, hot filaments, or combustion reactions to increase deposition rates and/or lower deposition temperatures. Various process conditions may be used to control the deposition, including but not limited to, temperature, precursor material, gas flow rate, pressure, substrate voltage bias (if applicable), and plasma energy (if applicable).
As mentioned, the continuous porous lithium storage layer, e.g., a layer of silicon or germanium or both, may in some embodiments be provided by plasma-enhanced chemical vapor deposition (PECVD). The lithium storage material may selectively form and/or adhere to the first pattern of the first metal oxide layer, but forms on or adheres poorly to other areas. Relative to CVD, deposition by PECVD can often be done at lower temperatures and higher rates, which can be advantageous for higher manufacturing throughput. In some embodiments, the PECVD is used to deposit a substantially amorphous silicon layer (optionally doped) over the metal oxide layer. In some embodiments, PECVD is used to deposit a substantially amorphous continuous porous silicon layer over the metal oxide layer.
In some embodiments, relative to conventional lithium storage materials, the continuous porous lithium storage layer may have improved stability at aggressive >1C charging rates; higher overall areal charge capacity; higher charge capacity per gram of active material; improved physical durability; simplified manufacturing process; and more reproducible manufacturing process.
PECVD
In PECVD processes, according to various implementations, a plasma may be generated in a chamber in which the substrate is disposed or upstream of the chamber with plasma effluents fed into the chamber. Various types of plasmas may be used including, but not limited to, capacitively-coupled plasmas, inductively-coupled plasmas, and conductively-coupled plasmas. Any appropriate plasma source may be used, including DC, AC, RF, VHF, combinatorial PECVD and microwave sources may be used.
PECVD process conditions (temperatures, pressures, precursor gases, carrier gasses, dopant gases, flow rates, energies and the like) can vary according to the particular process and tool used, as is well known in the art.
In some implementations, the PECVD process is an expanding thermal plasma chemical vapor deposition (ETP-PECVD) process. In such a process, a plasma generating gas is passed through a direct current arc plasma generator to form a plasma, with a web or other substrate including the current collector optionally in an adjoining vacuum chamber. A silicon source gas is injected into the plasma, with radicals generated. The plasma is expanded via a diverging nozzle and injected into the vacuum chamber and toward the substrate. An example of a plasma generating gas is argon (Ar). In some embodiments, the ionized argon species in the plasma collide with silicon source molecules to form radical species of the silicon source, resulting in deposition onto the current collector. Example ranges for voltages and currents for the DC plasma source are 60 to 80 volts and 40 to 70 amperes, respectively.
Any appropriate silicon source may be used to deposit silicon, including silane (SiH4), dichlorosilane (H2SiCl2), monochlorosilane (H3SiCl), trichlorosilane (HSiCl3), silicon tetrachloride (SiCl4), and diethylsilane. Depending on the gas(es) used, the silicon layer may be formed by decomposition or reaction with another compound, such as by hydrogen reduction. In some embodiments, the gases may include a silicon source such as silane, a noble gas such as helium, argon, neon or xenon, optionally one or more dopant gases.
In some embodiments, the metal layer includes a transition metal or a transition metal layer capable of forming metal silicide structures when subjected to a vaporized silicon source and elevated temperatures. In some embodiments, the metal layer includes nickel or a nickel layer and PECVD silicon deposition conditions are selected to form nickel silicide structures such as nanowires or microwires in the second pattern, for example, by subjecting the nickel-containing electrically conductive layer to a temperature in a range of 450-550° C. As discussed below, the continuous porous lithium storage layer of silicon may concurrently deposit over the first pattern of metal oxide layer along with the metal silicide structures in the second pattern areas. However, to avoid substantial growth of such metal silicide structures in the second pattern, the temperature may be lower, for example, to a range of 150 to 375° C., sufficient to deposit the silicon of the continuous porous lithium storage layer.
The thickness or mass per unit area of the continuous porous lithium storage layer depends on the storage material, desired charge capacity and other operational and lifetime considerations. Increasing the thickness typically provides more capacity. If the continuous porous lithium storage layer becomes too thick, electrical resistance may increase and the stability may decrease, e.g., due to pulverization effects. In some embodiments, the anode may be characterized as having an active silicon areal density of at least 0.2 mg/cm2, alternatively 0.5 mg/cm2, alternatively 1 mg/cm2, alternatively at least 2 mg/cm2, alternatively at least 3 mg/cm2, alternatively at least 5 mg/cm2. In some embodiments, the lithium storage structure may be characterized as having an active silicon areal density in a range of 0.5-1 mg/cm2, alternatively in a range of 1-2 mg/cm2, alternatively in a range of 2-3 mg/cm2, alternatively in a range of 3-5 mg/cm2, alternatively in a range of 5-10 mg/cm2, alternatively in a range of 10-15 mg/cm2, alternatively in a range of 15-20 mg/cm2, or any combination of contiguous ranges thereof. “Active silicon” refers to the silicon in electrical communication with the current collector that is available for reversible lithium storage at the beginning of cell cycling, e.g., after anode “electrochemical formation” discussed later. “Areal density” refers to the surface area of the electrically conductive layer over which active silicon is provided. In some embodiments, not all of the silicon content is active silicon, i.e., some may be tied up in the form of non-active silicides or electrically isolated from the current collector.
In some embodiments the continuous porous lithium storage layer has an average thickness of at least 0.5 μm. In some embodiments, the continuous porous lithium storage layer has an average thickness in a range of about 0.5 μm to about 50 μm. In some embodiments, the continuous porous lithium storage layer comprises at least 80 atomic % amorphous silicon and has a thickness in a range of 0.5 to 1 μm, alternatively 1-2 μm, alternatively 2-5 μm, alternatively 5-10 μm, alternatively 10-20 μm, alternatively 20-30 μm, alternatively 30-40 μm, alternatively 40-50 μm, or any combination of contiguous ranges thereof.
In some embodiments, the continuous porous lithium storage layer includes silicon but does not contain a substantial amount of crystalline silicides, i.e., the presence of silicides is not readily detected by X-Ray Diffraction (XRD). Metal silicides, e.g., nickel silicide, commonly form when silicon is deposited at higher temperatures directly onto metal, e.g., nickel foil. Metal silicides such as nickel silicides often have much lower lithium storage capacity than silicon itself. In some embodiments, the average atomic % of silicide-forming metallic elements within the continuous porous lithium storage layer are on average less than 35%, alternatively less than 20%, alternatively less than 10%, alternatively less than 5%. In some embodiments, the average atomic % of silicide-forming metallic elements within the continuous porous lithium storage layer are in a range of about 0.1 to 10%, alternatively about 0.2 to 5%. In some embodiments, the atomic % of silicide forming metallic elements in the continuous porous lithium storage layer is higher nearer the current collector than away from the current collector.
Patterns According to various embodiments of the present disclosure, the one or more first regions of the continuous porous lithium storage layer may easily be provided in almost any pattern desired, enabling a multitude of potential functionalities.
In
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In
In
It should be noted that both sides of the current collector may optionally include a patterned lithium storage structure, and the two sides may have the same or a different pattern, e.g., to account for differences in stresses when winding. In some embodiments, one side of the current collector includes a patterned lithium storage structure and the other side includes a non-patterned lithium storage layer.
Patterning resolution, i.e., the minimum practical lateral dimension or feature width of the first or second region, may be a function of patterning method, the metal oxide layer thickness and target lithium storage layer thickness. In some embodiments, the feature width is at least 2 μm, alternatively at least 5 μm, alternatively at least 10 μm. In some embodiments, the feature width is in a range of 2 μm to 10 mm, alternatively 5 μm to 5 mm, alternatively 10 μm to 1 mm.
In some embodiments, the one or more first regions (e.g., 113) include substantially all of the anode's active lithium storage material in the form of continuous porous lithium storage layer (e.g., 107). Depending on the total capacity requirement of the battery, the total area of first region(s) (e.g., 113) relative to the total area of the second region(s) (e.g., 114) may be at least 1:1, alternatively at least 2:1, alternatively at least 3:1, alternatively at least 4:1, alternatively at least 5:1, alternatively at least 7:1, alternatively at least 10:1; alternatively at least 15:1, alternatively at least 20:1, alternatively at least 50:1. Higher ratios allow for increased charge capacity per unit area.
As mentioned, the one or more second regions (e.g., 114) or the second pattern (e.g., 109) may provide areas of stress relief when bending or winding the anode and/or contact areas for making electrical connection to the battery cell. However, the second regions/pattern may provide additional functionality or benefits to the anode. In some embodiments a surface portion of the second pattern may be etched, e.g., by electrochemical or chemical oxidation of the metal layer to form recessed portions in the metal layer. For example,
In some other embodiments, a metal may be electrolytically or electrolessly plated over the second pattern to form raised metal structures. For example,
In some embodiments of the present disclosure, the second regions may include lithium storage nanostructures, e.g., nanowires, grown on the current collector in the second pattern not having the metal oxide layer. Methods of growing lithium storage nanowires are well known in the art, including but not limited to CVD and PECVD methods described in U.S. Pat. Nos. 9,325,014 and 8,257,866, the entire contents of which are incorporated by reference for all purposes.
In some embodiments (not shown), most of the continuous porous lithium storage layer 1507 is deposited under a first set of conditions and then followed by a change in conditions to form alloyed nanowires, and optionally lithium storage nanowires, in the second region.
Prior art lithium storage nanowires may have certain disadvantages, one of which is physical robustness to handling (e.g. rubbing) causing nanowires to break off. On the other hand, nanowire structures may be more robust to bending stresses induced during winding than continuous layers of lithium storage material. According to some embodiments of the present disclosure, the first regions may help physically protect the nanowires in the second regions. By providing lithium storage nanowires in the one or more second region, the loss in surface area capacity caused by patterning the continuous porous lithium storage layer can be partially or entirely recovered. Further, the combination of two types of lithium storage structures may provide the anode with a broader range of charging and discharging capabilities and/or increased lifetime.
In some embodiments, the patterned lithium storage structure includes a functional composition in second regions deposited over the second pattern. As shown in
In some embodiments the functional composition may be deposited by wet coating or printing method, including but not limited to, screen printing, inkjet printing, gravure printing, offset printing, flexographic printing, curtain coating, spray coating, spin coating and slot die coating. For example, the functional composition may be coated over the entire anode and substantially removed from the top surface of the continuous porous lithium storage layer 1607A by a doctor blade or squeegee (
In some embodiments, the functional composition may act as a supplemental active lithium storage layer for the anode and may be provided, for example, by coating a slurry containing an active lithium storage material (e.g., graphite or silicon-containing particles), a binder matrix and a solvent. Many other coatable, binder-based lithium storage layers are known in the art and may be used. Such binder-based lithium storage layers generally have lower areal lithium storage capacity than the continuous porous lithium storage layer. However, some may more easily withstand bending stresses during winding or the like and will at least partially offset the loss in surface area capacity caused by patterning the continuous porous lithium storage layer.
In some embodiments where the one or more second regions include active lithium storage materials, e.g., as lithium storage nanowires, a binder-based lithium storage material or the like, the ratio of the total area of first region(s) of continuous porous lithium storage layer (e.g., 1513, 1613A, 1613B) relative to the total area of the second region(s) (e.g., 1514, 1614A, 1614B) may be in range of 50:1 to 20:1, alternatively 20:1 to 10:1, alternatively 10:1 to 5:1, alternatively 5:1 to 2:1, alternatively 2:1 to 1:1, alternatively 1:1 to 1:2, alternatively 1:2 to 1:5, alternatively 1:5 to 1:10, alternatively 1:10 to 1:20, alternatively 1:20 to 1:50, or any combination of contiguous ranges thereof.
In some embodiments, the functional composition includes a polymer comprising a source of lithium ion, e.g., as lithium sulfonate or lithium carboxylate groups or the like. This may be used to supplement the lithium ion present in the electrolyte and reduce possible lithium ion starvation effects due to irreversible losses of lithium in the anode over time. In some embodiments, the functional composition may act to partially confine expansion of the continuous porous lithium storage layer (1607A, 1607B) that may occur during lithiation. Such confinement may help increase lifetime. In some embodiments, the expansion confinement composition may include a polymer or a mixture of a polymer and inorganic particles. In some embodiments, the expansion confinement primarily directed to a lateral expansion (as in
In some embodiments, the functional composition (1632A, 1632B) may include an electrically conductive material, e.g., silver (or other metal) nanowires, metallic particles, a conductive polymer, a conductive metal oxide, carbon nanofibers, carbon nanotubes, or a combination. In some embodiments, the presence of such electrically conductive materials may help enable electrical continuity of the anode after electrochemical cycling and some possible breakdown of the continuous porous lithium storage layer structure. In some embodiments the functional composition may include an electrically conductive material mentioned above, but the conductive materials are sufficiently dilute in a binder or matrix so that the functional composition itself does not readily conduct electrical current at normal battery operating voltages.
In some embodiments, functional composition (1632A, 1632B) may be conductive to lithium ions. In the case where the functional composition 1632B is over continuous porous lithium storage layer 1607B (
In some embodiments, the functional composition may include any combination of materials or functions described above.
In some embodiments, the second region may include lithium storage nanowires grown on the current collector and one or more functional composition according to any of the embodiments described above.
The anode may optionally include various additional layers and features. The current collector may include one or more features to ensure that a reliable electrical connection can be made in the energy storage device. In some embodiments, a supplemental layer is provided over the patterned lithium storage structure. In some embodiments, the supplemental layer is a protection layer to enhance lifetime or physical durability. The supplemental layer may be an oxide formed from the lithium storage material itself, e.g., silicon dioxide in the case of silicon, or some other suitable material. A supplemental layer may be deposited, for example, by ALD, CVD, PECVD, evaporation, sputtering, solution coating, ink jet or any method that is compatible with the anode. In some embodiments the supplemental layer may conformally coat the patterned lithium storage structure. In some embodiments, the top surface of the supplemental layer corresponds to a top surface of the anode.
A supplemental layer should be reasonably conductive to lithium ions and permit lithium ions to move into and out of the patterned lithium storage structure during charging and discharging. In some embodiments, the lithium ion conductivity of a supplemental layer is at least 10−9 S/cm, alternatively at least 10−8 S/cm, alternatively at least 10−7 S/cm, alternatively at least 10'S/cm. In some embodiments, the supplemental layer acts as a solid-state electrolyte.
Some non-limiting examples of materials used in a supplemental layer include metal oxides, nitrides, or oxynitrides, e.g., those containing aluminum, titanium, vanadium, zirconium or tin, or mixtures thereof. The metal oxide, metal nitride or metal oxynitride may include other components such as phosphorous or silicon. The supplemental layer may include a lithium-containing material such as lithium phosphorous oxynitride (LIPON), lithium phosphate, lithium aluminum oxide, (Li,La)xTiyOz, or LixSiyAl2O3. In some embodiments, the supplemental layer includes a metal oxide, metal nitride, or metal oxynitride, and has an average thickness of less than about 100 nm, for example, in a range of about 0.1 to about 10 nm, or alternatively in a range of about 0.2 nm to about 5 nm. LIPON or other solid-state electrolyte materials having superior lithium transport properties may have a thickness of more than 100 nm, but may alternatively, be in a range of about 1 to about 50 nm.
In some embodiments the anode is at least partially prelithiated, i.e., the patterned lithium storage structure and/or the metal oxide layer includes some lithium prior to battery assembly.
Battery Features
The preceding description relates primarily to the anode/negative electrode of a lithium-ion battery (LIB). The LIB typically includes a cathode/positive electrode, an electrolyte and a separator (if not using a solid-state electrolyte). As is well known, batteries can be formed into multilayer stacks of anodes and cathodes with an intervening separator. Alternatively, anode/cathode stacks can be formed into a so-called jelly-roll. Such structures are provided into an appropriate housing having desired electrical contacts.
Cathode
Positive electrode (cathode) materials include, but are not limited to, lithium metal oxides or compounds (e.g., LiCoO2, LiFePO4, LiMnO2, LiNiO2, LiMn2O4, LiCoPO4, LiNixCoyMnzO2, LiNixCoyAlzO2, LiFe2(SO4)3, or Li2FeSiO4), carbon fluoride, metal fluorides such as iron fluoride (FeF3), metal oxide, sulfur, selenium and combinations thereof. Cathode active materials are typically provided on, or in electrical communication with, an electrically conductive cathode current collector.
Current separator The current separator allows ions to flow between the anode and cathode but prevents direct electrical contact. Such separators are typically porous sheets. Non-aqueous lithium-ion separators are single layer or multilayer polymer sheets, typically made of polyolefins, especially for small batteries. Most commonly, these are based on polyethylene or polypropylene, but polyethylene terephthalate (PET) and polyvinylidene fluoride (PVdF) can also be used. For example, a separator can have >30% porosity, low ionic resistivity, a thickness of ˜10 to 50 μm and high bulk puncture strengths. Separators may alternatively include glass materials, ceramic materials, a ceramic material embedded in a polymer, a polymer coated with a ceramic, or some other composite or multilayer structure, e.g., to provide higher mechanical and thermal stability.
Electrolyte
The electrolyte in lithium ion cells may be a liquid, a solid, or a gel. A typical liquid electrolyte comprises one or more solvents and one or more salts, at least one of which includes lithium. During the first few charge cycles (sometimes referred to as formation cycles), the organic solvent and/or the electrolyte may partially decompose on the negative electrode surface to form an SEI (Solid-Electrolyte-Interphase) layer. The SEI is generally electrically insulating but ionically conductive, thereby allowing lithium ions to pass through. The SEI may lessen decomposition of the electrolyte in the later charging cycles.
Some non-limiting examples of non-aqueous solvents suitable for some lithium ion cells include the following: cyclic carbonates (e.g., ethylene carbonate (EC), fluoroethylene carbonate (FEC), propylene carbonate (PC), butylene carbonate (BC) and vinylethylene carbonate (VEC)), vinylene carbonate (VC), lactones (e.g., gamma-butyrolactone (GBL), gamma-valerolactone (GVL) and alpha-angelica lactone (AGL)), linear carbonates (e.g., dimethyl carbonate (DMC), methyl ethyl carbonate (MEC, also commonly abbreviated EMC), diethyl carbonate (DEC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC), methyl butyl carbonate (NBC) and dibutyl carbonate (DBC)), ethers (e.g., tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane (DME), 1,2-diethoxyethane and 1,2-dibutoxyethane), nitriles (e.g., acetonitrile and adiponitrile) linear esters (e.g., methyl propionate, methyl pivalate, butyl pivalate and octyl pivalate), amides (e.g., dimethyl formamide), organic phosphates (e.g., trimethyl phosphate and trioctyl phosphate), organic compounds containing an S═O group (e.g., dimethyl sulfone and divinyl sulfone), and combinations thereof.
Non-aqueous liquid solvents can be employed in combination. Examples of these combinations include combinations of cyclic carbonate-linear carbonate, cyclic carbonate-lactone, cyclic carbonate-lactone-linear carbonate, cyclic carbonate-linear carbonate-lactone, cyclic carbonate-linear carbonate-ether, and cyclic carbonate-linear carbonate-linear ester. In some embodiments, a cyclic carbonate may be combined with a linear ester. Moreover, a cyclic carbonate may be combined with a lactone and a linear ester. In some embodiments, the weight ratio, or alternatively the volume ratio, of a cyclic carbonate to a linear ester is in a range of 1:9 to 10:1, alternatively 2:8 to 7:3.
A salt for liquid electrolytes may include one or more of the following non-limiting examples: LiPF6, LiBF4, LiClO4 LiAsF6, LiN(CF3SO2)2, LiN(C2F5SO2)2, LiCF3SO3, LiC(CF3SO2)3, LiPF4(CF3)2, LiPF3(C2F5)3, LiPF3(CF3)3, LiPF3(iso-C3F7)3, LiPF5(iso-C3F7), lithium salts having cyclic alkyl groups (e.g., (CF2)2(SO2)2xLi and (CF2)3(SO2)2xLi), and combinations thereof. Common combinations include: LiPF6 and LiBF4; LiPF6 and LiN(CF3SO2)2; and LiBF4 and LiN(CF3SO2)2.
In some embodiments, the total concentration of salt in a liquid non-aqueous solvent (or combination of solvents) is at least 0.3 M, alternatively at least 0.7M. The upper concentration limit may be driven by a solubility limit and operational temperature range. In some embodiments, the concentration of salt is no greater than about 2.5 M, alternatively no more than about 1.5 M.
In some embodiments, the battery electrolyte includes a non-aqueous ionic liquid and a lithium salt.
A solid electrolyte may be used without the separator because it serves as the separator itself. It is electrically insulating, ionically conductive, and electrochemically stable. In the solid electrolyte configuration, a lithium containing salt, which could be the same as for the liquid electrolyte cells described above, is employed but rather than being dissolved in an organic solvent, it is held in a solid polymer composite. Examples of solid polymer electrolytes may be ionically conductive polymers prepared from monomers containing atoms having lone pairs of electrons available for the lithium ions of electrolyte salts to attach to and move between during conduction, such as polyvinylidene fluoride (PVDF) or chloride or copolymer of their derivatives, poly(chlorotrifluoroethylene), poly(ethylene-chlorotrifluoro-ethylene), or poly(fluorinated ethylene-propylene), polyethylene oxide (PEO) and oxymethylene linked PEO, PEO-PPO-PEO crosslinked with trifunctional urethane, poly(bis(methoxy-ethoxy-ethoxide))-phosphazene (MEEP), triol-type PEO crosslinked with difunctional urethane, poly((oligo)oxyethylene)methacrylate-co-alkali metal methacrylate, polyacrylonitrile (PAN), polymethylmethacrylate (PMMA), polymethylacrylonitrile (PMAN), polysiloxanes and their copolymers and derivatives, acrylate-based polymer, other similar solvent-free polymers, combinations of the foregoing polymers either condensed or cross-linked to form a different polymer, and physical mixtures of any of the foregoing polymers. Other less conductive polymers that may be used in combination with the above polymers to improve the strength of thin laminates include: polyester (PET), polypropylene (PP), polyethylene naphthalate (PEN), polyvinylidene fluoride (PVDF), polycarbonate (PC), polyphenylene sulfide (PPS), and polytetrafluoroethylene (PTFE). Such solid polymer electrolytes may further include a small amount of organic solvents listed above. The polymer electrolyte may be an ionic liquid polymer. Such polymer-based electrolytes can be coated using any number of conventional methods such as curtain coating, slot coating, spin coating, inkjet coating, spray coating or other suitable method.
Additives may be included in the electrolyte to serve various functions. For example, additives such as polymerizable compounds having an unsaturated double bond may be added to stabilize or modify the SEI. Certain amines or borate compounds can act as cathode protection agents. Lewis acids can be added to stabilize fluorine-containing anion such as PF6. Safety protection agents include those to protect overcharge, e.g., anisoles, or act as fire retardants, e.g., alkyl phosphates.
In some embodiments, the original, non-cycled anode may undergo structural or chemical changes during electrochemical charging/discharging, for example, from normal battery usage or from an earlier “electrochemical formation step”. As is known in the art, an electrochemical formation step is commonly used to form an initial SEI layer and involves relatively gentle conditions of low current and limited voltages. The modified anode prepared in part from such electrochemical charging/discharging cycles may still have excellent performance properties, despite such structural and/or chemical changes relative to the original, non-cycled anode
Current Collector 1 (with Metal Oxide Layer)
Current collectors having a metal oxide layer (a nickel oxide) over an electrically conductive metal layer (nickel) were prepared by placing nickel foil in a muffle furnace (heated air) and holding the foil at 700° C. for 30 minutes then cooled to room temperature. The metal oxide thickness was approximately 0.7 to 1.2 microns. Although not patterned, Current Collector 1 is representative of some embodiments of the present disclosure having a first pattern of metal oxide layer.
The same kind of nickel foil as used for Current Collector 1 was simply cleaned with an IPA wipe and not subjected to any oxidation treatments. Although not patterned, Current Collector 2 is representative of some embodiments of the present disclosure having a second pattern of areas not occupied by the metal oxide.
Anode 1A
Current Collector 1 was placed in a high-density plasma-enhanced chemical vapor deposition tool (HDPECVD) and exposed to silane gas at 180° C. for 60 minutes. A continuous porous lithium storage layer formed at a loading of about 0.7 mg/cm′ of active silicon. When tested in a half cell, Anode 1A was found to have good cycle life and lithium storage capacity.
Anode 1B
Current Collector 2 was placed in a high-density plasma-enhanced chemical vapor deposition tool (HDPECVD) and an attempt was made to deposit amorphous silicon using the same conditions as in Anode 1A but for 40 minutes. However, no adherent layer of silicon formed on Current Collector 2 under these conditions. Some poorly adhered, dusty silicon deposit was easily brushed off. No electrochemical testing was conducted.
Taken together, Anode 1A and 1B show that anodes according to certain embodiments of the present disclosure having patterned lithium storage structures may be readily prepared. Anode 1A shows that a continuous lithium storage layer can be deposited on a metal oxide layer and result in an anode with good cycle life and lithium storage capacity. Anode 2A shows that an amorphous silicon layer does not deposit on a metal layer. As a result, a continuous porous lithium storage layer would not deposit on the metal. Hence, embodiments having a first pattern of a metal oxide layer and a continuous porous lithium storage layer and a second pattern of areas not occupied by the metal oxide or the continuous porous lithium storage layer can be formed.
Silicon was concurrently deposited over Current Collector 1 and Current Collector 2 using expanding thermal PECVD to form corresponding Anode 2A (from Current Collector 1) and Anode 2B (from Current Collector 2). The formation gases were silane at about 0.20 slm (standard liters per minute) and hydrogen at about 0.20 slm, along with an argon carrier gas at about 2 slm. The process pressure was about 0.145 mbar. For at least a portion of the deposition, the temperature was higher than that for Example 1 (about 450 to 550° C.).
Characterization
ICP-AES analysis showed Anode 2A had about 1.2 mg/cm′ of total silicon and Anode 2B had about 2.4 mg/cm′ of total silicon. In the case of Anode 2B, some of this silicon was in the form of nickel silicide, which has lower lithium storage capacity than amorphous silicon.
Anode 2A had a silvery, metallic appearance, although not mirror-like. In contrast, Anode 2B had a black appearance. Microstructure differences between the anodes are readily apparent as shown in
When tested in half cells, both anodes showed good cycle life and lithium storage capacity.
Taken together, Anode 2A and Anode 2B show that anodes according to certain embodiments of the present disclosure that include patterned lithium storage structures having both continuous porous lithium storage layers and lithium storage nanowires may be readily prepared.
Although the present anodes have been discussed with reference to batteries, in some embodiments the present anodes may be used in hybrid lithium ion capacitor devices. Below are some non-limiting embodiments:
1. An anode for an energy storage device, the anode comprising:
a) a current collector comprising:
b) a patterned lithium storage structure comprising a continuous porous lithium storage layer selectively overlaying at least a portion of the first pattern of metal oxide.
2. The anode of embodiment 1 wherein the continuous porous lithium storage layer has a total content of silicon, germanium, or a combination thereof, of at least 40 atomic %.
3. The anode of embodiment 1 or 2 wherein the continuous porous lithium storage layer includes less than 10 atomic % carbon.
4. The anode according to any of embodiments 1-3, wherein the continuous porous lithium storage layer is substantially free of nanostructures.
5. The anode according to any of embodiments 1-4, wherein the metal layer comprises stainless steel, titanium, nickel, or copper, or a combination thereof.
6. The anode according to any of embodiments 1-5 wherein the metal oxide layer comprises an oxide of nickel, an oxide of copper, an oxide of titanium, or a combination thereof.
7. The anode according to any of embodiments 1-6, wherein the metal oxide layer has an average thickness of at least 0.02 μm.
8. The anode according to any of embodiments 1-7, wherein the continuous porous lithium storage layer comprises amorphous silicon having an active areal density of at least 0.2 mg/cm′ and the total content of silicon is at least 40 atomic %.
9. The anode according to any of embodiments 1-8, wherein the continuous porous lithium storage layer has an average thickness from about 0.5 μm to about 40 μm.
10. The anode according to any of embodiments 1-9, wherein the continuous porous lithium storage layer has an average density from about 1.1 g/cm3 to about 2.25 g/cm3 and comprises at least 40 atomic % amorphous silicon.
11. The anode according to any of embodiments 1-10 further comprising lithium storage nanowires overlaying the metal layer in one or more areas not occupied by the first pattern of metal oxide.
12. The anode of embodiment 11 wherein the lithium storage nanowires comprise a metal silicide and amorphous silicon.
13. The anode according to any of embodiments 1-12 further comprising a functional composition overlaying the metal layer in one or more areas not occupied by the first pattern of metal oxide.
14. The anode of embodiment 13 wherein the functional composition further overlays the continuous porous lithium storage layer.
15. The anode according to embodiment 13 or 14 wherein the functional composition comprises a supplemental lithium storage material.
16. The anode according to embodiment 15 wherein the supplemental lithium storage material comprises silicon-containing particles in a binder matrix.
17. The anode according to any of embodiments 13-16, wherein the functional composition comprises a source of lithium ion.
18. The anode according to any of embodiments 13-17, wherein the functional composition comprises an expansion confinement composition.
19. The anode according to any of embodiments 13-18, wherein the functional composition comprises an electrically conductive material.
20. The anode of embodiment 19 wherein the conductive material includes metal nanowires, metal particles, a conductive polymer, a conductive metal oxide, or combinations thereof.
21. A battery comprising the anode according to any of embodiments 1-20.
22. A method of making an anode for use in an energy storage device, the method comprising:
providing a current collector comprising a metal layer and a metal oxide layer provided in a first pattern overlaying the metal layer; and
selectively forming by chemical vapor deposition, a continuous porous lithium storage layer overlaying the first pattern of metal oxide, wherein the chemical vapor deposition includes exposing the current collector to at least one lithium storage material precursor gas.
23. The method of embodiment 22 wherein the lithium storage material precursor gas comprises silane or germane, and the continuous porous lithium storage layer has a total content of silicon, germanium or a combination thereof of at least 40 atomic %.
24. The method of embodiment 22 or 23, wherein the metal layer comprises stainless steel, titanium, nickel, or copper, or a combination thereof.
25. The method according to any of embodiments 22-24, wherein the first metal oxide layer comprises an oxide of nickel, an oxide of copper, an oxide of titanium, or a combination thereof.
26. The anode according to any of embodiments 22-25, wherein the first metal oxide layer has an average thickness of at least 0.02 μm.
27. The method according to any of embodiments 22-26 further comprising forming by chemical vapor deposition, lithium storage nanowires over the metal layer in one or more areas not occupied by the first pattern of metal oxide.
28. The method of embodiment 27 wherein the lithium storage nanowires comprise a metal silicide and amorphous silicon.
29. The method of embodiment 27 or 28 wherein the lithium storage nanowires are formed in a common step with formation of the continuous porous lithium storage layer.
30. The method according to any of embodiments 22-29 further comprising depositing a functional composition over the metal layer in one or more areas not occupied by the first pattern of metal oxide.
31. The method of embodiment 30 wherein the functional composition is further deposited over the continuous porous lithium storage layer.
32. The method of embodiment 30 or 31 wherein the functional composition is deposited by screen printing, inkjet printing, gravure printing, offset printing, flexographic printing, curtain coating, spray coating, spin coating, or slot die coating.
33. The method according to any of embodiments 30-32, wherein the functional composition comprises a supplemental lithium storage material.
34. The method of embodiment 33 wherein the supplemental lithium storage material comprises silicon-containing particles in a binder matrix.
35. The method according to any of embodiments 32-34, wherein the functional composition comprises a source of lithium ion.
36. The method according to any of embodiments 32-35, wherein the functional composition comprises an expansion confinement composition.
37. The method according to any of embodiments 32-36, wherein the functional composition comprises an electrically conductive material.
38. The method of embodiment 37 wherein the conductive material includes metal nanowires, metal particles, a conductive polymer, a conductive metal oxide, or combinations thereof.
39. The method according to any of embodiments 22-38 further comprising:
providing an electrically conductive current collector precursor comprising a metal layer; and
forming the first pattern of a first metal oxide layer overlaying the metal layer, thereby forming the current collector.
40. The method of embodiment 39, wherein forming the first pattern of a metal oxide comprises oxidation of a surface portion of the metal layer.
41. The method of embodiment 40 further comprising: i) forming a patterned resist over a non-patterned metal oxide; ii) etching or dissolving areas of metal oxide not covered by the patterned resist; and iii) and removing the patterned resist.
42. The method of embodiment 40 further comprising applying a pattern of an oxidation resistant material prior to oxidation.
43. The method of embodiment 39, wherein forming the first pattern of metal oxide comprises depositing a metal oxide or metal oxide precursor over the current collector precursor.
44. The method of embodiment 43 further comprising depositing vaporized metal oxide through a shadow mask.
45. The method of embodiment 43 further comprising printing the metal oxide precursor over the current collector precursor and treating the printed metal oxide precursor to form the first pattern of metal oxide.
46. The method of embodiment 43 further comprising: i) forming a patterned resist over a non-patterned metal oxide; ii) etching or dissolving areas of the metal oxide not covered by the patterned resist; and iii) and removing the patterned resist.
The specific details of particular embodiments may be combined in any suitable manner without departing from the spirit and scope of embodiments of the invention. However, other embodiments of the invention may be directed to specific embodiments relating to each individual aspect, or specific combinations of these individual aspects.
The above description of example embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form described, and many modifications and variations are possible in light of the teaching above.
In the preceding description, for the purposes of explanation, numerous details have been set forth in order to provide an understanding of various embodiments of the present technology. It will be apparent to one skilled in the art, however, that certain embodiments may be practiced without some of these details, or with additional details.
Having described several embodiments, it will be recognized by those of skill in the art that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the invention. Additionally, a number of well-known processes and elements have not been described in order to avoid unnecessarily obscuring the present invention. Additionally, details of any specific embodiment may not always be present in variations of that embodiment or may be added to other embodiments.
Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Each smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed. The upper and lower limits of these smaller ranges may independently be included or excluded in the range, and each range where either, neither, or both limits are included in the smaller ranges is also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.
As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a method” includes a plurality of such methods and reference to “the anode” includes reference to one or more anodes and equivalents thereof known to those skilled in the art, and so forth. The invention has now been described in detail for the purposes of clarity and understanding. However, it will be appreciated that certain changes and modifications may be practice within the scope of the appended claims.
All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety for all purposes. None is admitted to be prior art.
This application is a continuation of U.S. application Ser. No. 17/237,217, filed Apr. 22, 2021, which is a continuation of U.S. application Ser. No. 16/909,008, filed Jun. 23, 2020, now U.S. Pat. No. 11,024,842, which claims the benefit of U.S. Provisional Application No. 62/867,513, filed Jun. 27, 2019, all of which are hereby incorporated by reference herein in their entirety for all purposes.
| Number | Date | Country | |
|---|---|---|---|
| 62867513 | Jun 2019 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 17237217 | Apr 2021 | US |
| Child | 17975196 | US | |
| Parent | 16909008 | Jun 2020 | US |
| Child | 17237217 | US |
