CN117941087A

CN117941087A - Aluminum-based negative electrode for lithium ion battery

Info

Publication number: CN117941087A
Application number: CN202280062370.0A
Authority: CN
Inventors: M·麦多维尔; T·陈; D·马祖姆达; V·孙达拉姆; F·J·金特罗科尔特斯; D·姜; 王聪诚
Original assignee: Novelis Inc Canada; Georgia Tech Research Corp
Current assignee: Novelis Inc Canada; Georgia Tech Research Corp
Priority date: 2021-09-15
Filing date: 2022-09-09
Publication date: 2024-04-26

Abstract

A composite material is described having at least one layer comprising an alloy of Al and at least one other component, or at least one layer comprising a first plurality of particles and a second plurality of particles. The first plurality of particles may be selected from at least one of Al particles and Al alloy particles. The second plurality of particles may be selected from at least one of metal particles and non-metal particles, wherein the metal particles are selected from at least one of zinc, silicon, bismuth, copper, germanium, indium, antimony, tin, magnesium, or combinations thereof, and the non-metal particles are selected from at least one of carbon, lithium titanium oxide, titanium dioxide 、MoO、MoS₂、Co₂O₄、MnO₂、Fe₂O₃、Fe₃O₄、FeS、CuO, or combinations thereof. The composite material is useful as a current collector and an active material.

Description

Aluminum-based negative electrode for lithium ion battery

Cross Reference to Related Applications

The present application claims the benefit and priority of U.S. provisional application No. 63/261,216 filed on 9 and 15 of 2021 and U.S. provisional application No. 63/362,691 filed on 8 of 2022, which are incorporated herein by reference in their entirety.

Technical Field

The present disclosure relates to aluminum-based cathodes for electrochemical cells, and more particularly to aluminum current collectors for use in electrodes of electrochemical cells.

Background

In a conventional Lithium Ion Battery (LIB), copper is used as a negative current collector, and aluminum (Al) is used as a positive current collector. The anode comprises an active anode material and a separate current collector, wherein the active anode material (typically graphite or a mixture of graphite and silicon) is deposited on the current collector, typically by slot die coating or knife coating, in the form of a wet film, followed by drying and curing to form the LIB anode. While current technology does enable functional devices, the increasing demand for reduced energy costs ($/kWh) along with enhanced mileage (miles/charge) for Electric Vehicles (EVs) requires continued technical enhancement of battery materials. Al is not typically used as a current collector on the negative side in lithium ion batteries because lithium can reactively alloy Al at the negative potential. Therefore, if Al is used as a negative electrode current collector in a lithium ion battery, improvements are needed.

Disclosure of Invention

The term "embodiment" and similar terms are intended to refer broadly to all subject matter of the present disclosure and the following claims. Statements containing these terms should not be construed as limiting the subject matter described herein or limiting the meaning or scope of the appended claims. The various embodiments of the disclosure encompassed herein are defined by the following claims rather than by the summary of the invention. This summary is a high-level overview of various aspects of the present disclosure and introduces some concepts that are further described in the detailed description that follows. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in isolation to determine the scope of the claimed subject matter. The subject matter should be understood by reference to the entire specification of the present disclosure, any or all of the accompanying drawings, and appropriate portions of each claim.

In some aspects, a composite material is disclosed having at least one layer comprising a first plurality of particles and a second plurality of particles. The first plurality of particles may be selected from at least one of Al particles and Al alloy particles, and the second plurality of particles may be selected from at least one of metal particles and non-metal particles, wherein the metal particles are selected from at least one of zinc, silicon, bismuth, copper, germanium, indium, antimony, tin, magnesium, or combinations thereof, and the non-metal particles are selected from at least one of carbon, lithium titanium oxide, titanium dioxide 、MoO、MoS₂、Co₂O₄、MnO₂、Fe₂O₃、Fe₃O₄、FeS、CuO, or combinations thereof. In some aspects, unlike a composite material having at least one layer comprising discrete particles, the at least one layer comprises an alloy of Al and another metal, such as at least one of zinc, silicon, bismuth, copper, germanium, indium, antimony, tin, magnesium, or a combination thereof.

In some aspects, a device is disclosed that includes: a first electrochemical cell electrode comprising a composite material. The composite material comprises at least one layer and may be one or both of a current collector and an electrode active material. The composite material may include at least one layer having: a first plurality of particles selected from at least one of Al particles and Al alloy particles; and a second plurality of particles selected from at least one of metal particles and non-metal particles, wherein the metal particles are selected from at least one of zinc, silicon, bismuth, copper, germanium, indium, antimony, tin, magnesium, or combinations thereof, and the non-metal particles are selected from at least one of carbon, lithium titanium oxide, titanium dioxide 、MoO、MoS₂、Co₂O₄、MnO₂、Fe₂O₃、Fe₃O₄、FeS、CuO, or combinations thereof. In some aspects, the device may comprise a composite material comprising at least one layer having an alloy of Al with another metal, such as at least one of zinc, silicon, bismuth, copper, germanium, indium, antimony, tin, magnesium, or combinations thereof. The device may also include a second electrochemical cell electrode; and an electrolyte between the first electrochemical cell electrode and the second electrochemical cell electrode.

In some aspects, methods of making a composite are disclosed. The method may include mixing the first plurality of particles and the second plurality of particles to form a homogeneous mixture. The first plurality of particles may be selected from at least one of Al particles and Al alloy particles, and the second plurality of particles may be selected from at least one of metallic particles and non-metallic particles, wherein the metallic particles are selected from at least one of zinc, silicon, bismuth, copper, germanium, indium, antimony, tin, magnesium, or combinations thereof. The non-metallic particles may be selected from at least one of carbon, lithium titanium oxide, titanium dioxide 、MoO、MoS₂、Co₂O₄、MnO₂、Fe₂O₃、Fe₃O₄、FeS、CuO, or a combination thereof. The method may also include mechanically, thermally, or thermomechanically treating the mixture to form a composite material. In some aspects, when at least one layer of the composite comprises an alloy of Al and another metal, the method includes forming the alloy.

Other objects and advantages will become apparent from the following detailed description of non-limiting examples.

Drawings

The specification makes reference to the following drawings wherein the same reference numerals are used in different drawings to designate the same or similar components.

Fig. 1A and 1B provide schematic cross-sectional views of exemplary composite materials comprising a plurality of Al particles and a plurality of metallic or non-metallic particles.

Fig. 2 provides a graph showing the voltage of a pure Al foil over time.

Fig. 3A and 3B provide schematic cross-sectional views of exemplary composite substrates.

Fig. 4 provides a schematic cross-sectional view of an exemplary electrochemical cell.

Fig. 5 provides a graph showing the voltage change over time of a pure Al foil that engages 80% capacity to hold Li.

Fig. 6A provides a graph showing the voltage over time of an exemplary inai composite foil that is bonded to 100% capacity to hold Li.

Fig. 6B provides a plot of the cycle specific capacity of the example of fig. 6A.

Fig. 7 provides constant current cycling data for half cells comprising Al foil working electrodes.

Fig. 8 provides electron microscopy images of an exemplary composite material comprising 65% Al and 35% Sn, and x-ray microscopy analysis showing the distribution of Al and Sn in the composite material.

Fig. 9 provides constant current cycling data for an exemplary half cell comprising a composite working electrode comprising 65% Al and 35% Sn.

Fig. 10 provides charge and discharge curves for an exemplary half-cell comprising a composite working electrode comprising 65% Al and 35% Sn.

Fig. 11 provides electron microscopy images of an exemplary composite material containing 51% Al and 49% Zn, and x-ray microscopy analysis showing the distribution of Al and Zn in the composite material.

Fig. 12 provides constant current cycling data for an exemplary half cell comprising a composite working electrode comprising 51% Al and 49% Zn.

Fig. 13 provides charge and discharge curves for an exemplary half-cell comprising a composite working electrode comprising 51% Al and 49% Zn.

Fig. 14 provides electron microscopy images of an exemplary composite material comprising 99% Al and 1% Si, and x-ray microscopy analysis showing the distribution of Al and Si in the composite material.

Fig. 15 provides constant current cycling data for an exemplary half cell comprising a composite working electrode comprising 99% Al and 1% Si.

Fig. 16 provides charge and discharge curves for an exemplary half-cell comprising a composite working electrode comprising 99% Al and 1% Si.

Detailed Description

Described herein are composite materials comprising a plurality of Al or Al alloy particles and a plurality of non-Al particles, which may be metallic or non-metallic, distributed throughout the composite material. The particles may be uniformly or unevenly distributed. The composite material may be a current collector, which may also be used as an active negative electrode material. The composite material may comprise at least one layer and a plurality of Al or Al alloy particles, and the plurality of non-Al particles may be present in one or more layers. In some aspects, unlike a composite material having at least one layer comprising discrete particles, the at least one layer comprises an alloy of Al and another metal, such as at least one of zinc, silicon, bismuth, copper, germanium, indium, antimony, tin, magnesium, or a combination thereof. Advantageously, at least one layer comprising an alloy or discrete particles allows for enhanced volumetric (Wh/l) and gravimetric (Wh/kg) energy density due to at least partial or, in some embodiments, complete elimination of the separate active negative electrode layer. The composite material may thus additionally provide cost reduction due to elimination of processes related to deposition and development of the active negative electrode layer and simplified manufacturing.

In aspects where the at least one layer comprises discrete particles, the non-Al particles are selected from metallic and/or non-metallic particles, which may be uniformly distributed in the Al particles. The inclusion of non-Al particles can limit mechanical degradation during cyclic charge and discharge that would otherwise occur with Al or Al alloy particles alone. The same theory can be applied to at least one layer of an alloy comprising Al and another metal. The composite material may be used, for example, in electronic applications, such as current collectors or electrodes for batteries, electrochemical cells, capacitors, supercapacitors, and the like.

In the case of lithium or LIB, al is generally used as a current collector on the positive electrode side. Although Al is light in weight, low in cost and good in conductivity, copper is generally used as a current collector on the negative electrode side. Copper is typically used as a current collector on the negative side because it is non-reactive at the negative potential and provides good conductivity. On the other hand, al may be reactive at a common potential on the negative side, resulting in Al being alloyed by lithium. This alloying of Al by lithium may degrade or damage the Al negative electrode current collector to a level that renders a battery having the Al negative electrode current collector inoperable. In some cases, al used as a positive electrode current collector may suffer from some corrosion or degradation, although the normal amount is low, which may not affect the operability of the battery.

Despite these difficulties, al can be used as a current collector on the positive as well as the negative side of an electrochemical cell. By providing a composite of Al with an alloy of another metal or Al particles in combination with non-Al particles, an Al current collector can be obtained that prevents or limits corrosion, degradation, while still achieving good overall stability and cycling. The Al-containing metal composites and/or alloys as described herein may serve the dual function of an active negative electrode material and a current collector in a lithium ion battery. Composite materials may be included to avoid mechanical degradation of the Al component during specific capacity cycling.

Definition and description:

As used herein, the terms "invention," "the invention," "this invention," and "the invention" are intended to broadly refer to all subject matter of this patent application and the appended claims. Statements containing these terms should not be construed as limiting the subject matter described herein, or as limiting the meaning or scope of the patent claims that follow.

In this specification, reference may be made to alloys identified by AA size and other related designations, such as "series" or "1xxx". For an understanding of the numerical labeling system most commonly used for naming and identifying Al and its alloys, see both "International Alloy Designations and Chemical Composition Limits for Wrought Al and Wrought Al Alloys" or "Registration Record of Al Association Alloy Designations and Chemical Compositions Limits for Al Alloys in the Form of Castings and Ingot" issued The Al Association.

As used herein, the thickness of the plate is typically greater than about 15mm. For example, a plate may refer to an Al product having a thickness greater than about 15mm, greater than about 20mm, greater than about 25mm, greater than about 30mm, greater than about 35mm, greater than about 40mm, greater than about 45mm, greater than about 50mm, or greater than about 100 mm.

As used herein, the thickness of a sauter board (shate) (also referred to as a sheet board) is typically about 4mm to about 15mm. For example, the sauter board can have a thickness of about 4mm, about 5mm, about 6mm, about 7mm, about 8mm, about 9mm, about 10mm, about 11mm, about 12mm, about 13mm, about 14mm, or about 15mm.

As used herein, sheet generally refers to an Al alloy product having a thickness of less than about 4 mm. For example, the sheet may have a thickness of less than about 4mm, less than about 3mm, less than about 2mm, less than about 1mm, less than about 0.5mm, or less than about 0.3mm (e.g., about 0.2 mm). The term sheet also encompasses Al alloy products, which may be referred to as foils, which may have a thickness of at most 500 μm, such as from about 1 μm to about 500 μm.

As used herein, terms such as "cast metal product," "cast Al alloy product," and the like are interchangeable and refer to a product produced by direct chill casting (including direct chill co-casting) or semi-continuous casting, continuous casting (including, for example, by use of a twin belt caster, twin roll caster, block caster, or any other continuous caster), electromagnetic casting, hot top casting, or any other casting method.

All ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a specified range of "1 to 10" should be considered to include any and all subranges between (and including 1 and 10) the minimum value of 1 and the maximum value of 10; that is, all subranges start with a minimum value of 1 or more (e.g., 1 to 6.1) and end with a maximum value of 10 or less (e.g., 5.5 to 10). Unless otherwise indicated, when referring to the compositional amount of an element, the expression "up to" means that the element is optional and includes zero percent composition of the particular element. All compositional percentages are weight percent (wt%) unless otherwise indicated.

As used herein, the meaning of "a," "an," and "the" includes singular and plural referents unless the context clearly dictates otherwise.

Method for producing Al alloy products

Al alloy products described herein (such as Al sheet metal and Al foil) may be prepared by casting using any suitable casting method known to those skilled in the art. As some non-limiting examples, the casting process may include a Direct Chill (DC) casting process or a Continuous Casting (CC) process. The continuous casting system may include a pair of moving opposing casting surfaces (e.g., moving opposing belts, rolls, or blocks), a casting cavity between the pair of moving opposing casting surfaces, and a molten metal injector. The molten metal injector may have an end opening from which molten metal may exit the molten metal injector and be injected into the casting cavity.

The cast ingot, cast billet, or other cast product may be processed by any suitable means. Such treatment steps include, but are not limited to, homogenization, hot rolling, cold rolling, solution heat treatment, and optionally pre-aging steps.

Briefly, in the homogenization step, the cast product is heated to a temperature of about 400 ℃ to about 500 ℃. For example, the cast product may be heated to a temperature of about 400 ℃, about 410 ℃, about 420 ℃, about 430 ℃, about 440 ℃, about 450 ℃, about 460 ℃, about 470 ℃, about 480 ℃, about 490 ℃, or about 500 ℃. The product is then soaked (i.e., maintained at a specified temperature) for a period of time to form a homogenized product. In some examples, the total time of the homogenization step (including the heating and soaking stages) may be up to 24 hours. For example, in the homogenization step, the product may be heated to up to 500 ℃ and soaked for a total time of up to 18 hours.

After the homogenization step, a hot rolling step may be performed. The homogenized product may be cooled to a temperature of 300 c to 450 c before hot rolling begins. For example, the homogenized product may be cooled to a temperature of 325 ℃ to 425 ℃ or 350 ℃ to 400 ℃. The homogenized product may then be hot rolled at a temperature of 300 ℃ to 450 ℃ to form a hot rolled plate, hot rolled sauter plate, or hot rolled sheet having a gauge of 3mm to 200mm (e.g., ,3mm、4mm、5mm、6mm、7mm、8mm、9mm、10mm、15mm、20mm、25mm、30mm、35mm、40mm、45mm、50mm、55mm、60mm、65mm、70mm、75mm、80mm、85mm、90mm、95mm、100mm、110mm、120mm、130mm、140mm、150mm、160mm、170mm、180mm、190mm、200mm or any value therebetween).

Optionally, the cast product may be a continuous cast product, which may be cooled to a temperature of 300 ℃ to 450 ℃. For example, the continuous casting product may be cooled to a temperature of 325 ℃ to 425 ℃ or 350 ℃ to 400 ℃. The continuously cast product may then be hot rolled at a temperature of 300 ℃ to 450 ℃ to form a hot rolled plate, hot rolled sauter plate, or hot rolled sheet having a gauge of 3mm to 200mm (e.g., ,3mm、4mm、5mm、6mm、7mm、8mm、9mm、10mm、15mm、20mm、25mm、30mm、35mm、40mm、45mm、50mm、55mm、60mm、65mm、70mm、75mm、80mm、85mm、90mm、95mm、100mm、110mm、120mm、130mm、140mm、150mm、160mm、170mm、180mm、190mm、200mm or any value therebetween). During hot rolling, the temperature and other operating parameters may be controlled such that the temperature of the hot rolled product as it leaves the hot rolling mill does not exceed 470 ℃, does not exceed 450 ℃, does not exceed 440 ℃ or does not exceed 430 ℃.

Cast, homogenized or hot rolled products may be cold rolled into thinner products, such as cold rolled sheets, using a cold rolling mill. The cold rolled product may have a gauge of about 0.5mm to 10mm, for example about 0.7mm to 6.5 mm. Optionally, the cold rolled product may have a gauge of 0.5mm、1.0mm、1.5mm、2.0mm、2.5mm、3.0mm、3.5mm、4.0mm、4.5mm、5.0mm、5.5mm、6.0mm、6.5mm、7.0mm、7.5mm、8.0mm、8.5mm、9.0mm、9.5mm or 10.0 mm. In the case of foil, the cold rolled sheet may have a gauge of about 1 μm to 500 μm, such as 10 μm to 100 μm. Cold rolling may be performed to produce a final gauge thickness that represents a gauge reduction of at most 85% (e.g., at most 10%, at most 20%, at most 30%, at most 40%, at most 50%, at most 60%, at most 70%, at most 80%, or at most 85%) or more compared to the gauge prior to starting cold rolling.

Subsequently, the cast, homogenized or rolled product may be subjected to a solution heat treatment step. The solution heat treatment step may be any suitable treatment of the sheet material that results in solutionizing of the soluble particles. The cast, homogenized, or rolled product may be heated to a Peak Metal Temperature (PMT) of up to 590 ℃ (e.g., 400 ℃ to 590 ℃) and soaked under PMT for a period of time to form a hot product. For example, the cast, homogenized, or rolled product may be soaked at 480 ℃ for a soaking time of up to 30 minutes (e.g., 0 seconds, 60 seconds, 75 seconds, 90 seconds, 5 minutes, 10 minutes, 20 minutes, 25 minutes, or 30 minutes). After heating and soaking, the hot product is rapidly cooled at a rate of greater than 200 ℃/s to a temperature of 500 ℃ to 200 ℃ to form a heat treated product. In one example, the hot product is cooled at a quench rate of greater than 200 ℃/sec at a temperature of 450 ℃ to 200 ℃. Optionally, the cooling rate may be faster in other cases.

After quenching, the heat treated product may optionally be subjected to a pre-ageing treatment by reheating prior to winding. The pre-ageing treatment may be carried out at a temperature of about 70 ℃ to about 125 ℃ for a period of up to 6 hours. For example, the pre-ageing treatment may be conducted at a temperature of about 70 ℃, about 75 ℃, about 80 ℃, about 85 ℃, about 90 ℃, about 95 ℃, about 100 ℃, about 105 ℃, about 110 ℃, about 115 ℃, about 120 ℃, or about 125 ℃. Optionally, a pre-ageing treatment may be performed for about 30 minutes, about 1 hour, about 2 hours, about 3 hours, about 4 hours, about 5 hours, or about 6 hours. The pre-ageing treatment may be performed by passing the heat treated product through heating means, such as means emitting radiant heat, convective heat, inductive heat, infrared heat, etc.

Methods of using the disclosed Al alloy products

The Al alloy products described herein are useful in electronic applications. For example, the Al alloy products and methods described herein can be used to make components of electronic devices, including batteries, mobile phones, and tablet computers. In some examples, the Al alloy products can be used to prepare current collectors and electrodes for use in electrochemical cells, capacitors, or batteries, which can be used in mobile phones, tablet computers, and the like.

Metal alloy

Methods of treating Al alloys and the resulting treated Al alloys are described herein. In some examples, the Al alloys used in the methods described herein may include a 1xxx series Al alloy, a 2xxx series Al alloy, a 3xxx series Al alloy, a 4xxx series Al alloy, a 5xxx series Al alloy, a 6xxx series Al alloy, a 7xxx series Al alloy, or an 8xxx series Al alloy.

As non-limiting examples, exemplary 1 xxx-series Al alloys may include AA1100、AA1100A、AA1200、AA1200A、AA1300、AA1110、AA1120、AA1230、AA1230A、AA1235、AA1435、AA1145、AA1345、AA1445、AA1150、AA1350、AA1350A、AA1450、AA1370、AA1275、AA1185、AA1285、AA1385、AA1188、AA1190、AA1290、AA1193、AA1198 or AA1199.

Non-limiting exemplary 2xxx series Al alloys may include AA2001、A2002、AA2004、AA2005、AA2006、AA2007、AA2007A、AA2007B、AA2008、AA2009、AA2010、AA2011、AA2011A、AA2111、AA2111A、AA2111B、AA2012、AA2013、AA2014、AA2014A、AA2214、AA2015、AA2016、AA2017、AA2017A、AA2117、AA2018、AA2218、AA2618、AA2618A、AA2219、AA2319、AA2419、AA2519、AA2021、AA2022、AA2023、AA2024、AA2024A、AA2124、AA2224、AA2224A、AA2324、AA2424、AA2524、AA2624、AA2724、AA2824、AA2025、AA2026、AA2027、AA2028、AA2028A、AA2028B、AA2028C、AA2029、AA2030、AA2031、AA2032、AA2034、AA2036、AA2037、AA2038、AA2039、AA2139、AA2040、AA2041、AA2044、AA2045、AA2050、AA2055、AA2056、AA2060、AA2065、AA2070、AA2076、AA2090、AA2091、AA2094、AA2095、AA2195、AA2295、AA2196、AA2296、AA2097、AA2197、AA2297、AA2397、AA2098、AA2198、AA2099 or AA2199.

Non-limiting exemplary 3xxx series Al alloys may include AA3002、AA3102、AA3003、AA3103、AA3103A、AA3103B、AA3203、AA3403、AA3004、AA3004A、AA3104、AA3204、AA3304、AA3005、AA3005A、AA3105、AA3105A、AA3105B、AA3007、AA3107、AA3207、AA3207A、AA3307、AA3009、AA3010、AA3110、AA3011、AA3012、AA3012A、AA3013、AA3014、AA3015、AA3016、AA3017、AA3019、AA3020、AA3021、AA3025、AA3026、AA3030、AA3130 or AA3065.

Non-limiting exemplary 4xxx series Al alloys may include AA4004、AA4104、AA4006、AA4007、AA4008、AA4009、AA4010、AA4013、AA4014、AA4015、AA4015A、AA4115、AA4016、AA4017、AA4018、AA4019、AA4020、AA4021、AA4026、AA4032、AA4043、AA4043A、AA4143、AA4343、AA4643、AA4943、AA4044、AA4045、AA4145、AA4145A、AA4046、AA4047、AA4047A or AA4147.

Non-limiting exemplary 5xxx series Al alloys may include AA5182、AA5183、AA5005、AA5005A、AA5205、AA5305、AA5505、AA5605、AA5006、AA5106、AA5010、AA5110、AA5110A、AA5210、AA5310、AA5016、AA5017、AA5018、AA5018A、AA5019、AA5019A、AA5119、AA5119A、AA5021、AA5022、AA5023、AA5024、AA5026、AA5027、AA5028、AA5040、AA5140、AA5041、AA5042、AA5043、AA5049、AA5149、AA5249、AA5349、AA5449、AA5449A、AA5050、AA5050A、AA5050C、AA5150、AA5051、AA5051A、AA5151、AA5251、AA5251A、AA5351、AA5451、AA5052、AA5252、AA5352、AA5154、AA5154A、AA5154B、AA5154C、AA5254、AA5354、AA5454、AA5554、AA5654、AA5654A、AA5754、AA5854、AA5954、AA5056、AA5356、AA5356A、AA5456、AA5456A、AA5456B、AA5556、AA5556A、AA5556B、AA5556C、AA5257、AA5457、AA5557、AA5657、AA5058、AA5059、AA5070、AA5180、AA5180A、AA5082、AA5182、AA5083、AA5183、AA5183A、AA5283、AA5283A、AA5283B、AA5383、AA5483、AA5086、AA5186、AA5087、AA5187 or AA5088.

Non-limiting exemplary 6xxx series Al alloys may include AA6101、AA6101A、AA6101B、AA6201、AA6201A、AA6401、AA6501、AA6002、AA6003、AA6103、AA6005、AA6005A、AA6005B、AA6005C、AA6105、AA6205、AA6305、AA6006、AA6106、AA6206、AA6306、AA6008、AA6009、AA6010、AA6110、AA6110A、AA6011、AA6111、AA6012、AA6012A、AA6013、AA6113、AA6014、AA6015、AA6016、AA6016A、AA6116、AA6018、AA6019、AA6020、AA6021、AA6022、AA6023、AA6024、AA6025、AA6026、AA6027、AA6028、AA6031、AA6032、AA6033、AA6040、AA6041、AA6042、AA6043、AA6151、AA6351、AA6351A、AA6451、AA6951、AA6053、AA6055、AA6056、AA6156、AA6060、AA6160、AA6260、AA6360、AA6460、AA6460B、AA6560、AA6660、AA6061、AA6061A、AA6261、AA6361、AA6162、AA6262、AA6262A、AA6063、AA6063A、AA6463、AA6463A、AA6763、A6963、AA6064、AA6064A、AA6065、AA6066、AA6068、AA6069、AA6070、AA6081、AA6181、AA6181A、AA6082、AA6082A、AA6182、AA6091 or AA6092.

Non-limiting exemplary 7xxx series Al alloys may include AA7011、AA7019、AA7020、AA7021、AA7039、AA7072、AA7075、AA7085、AA7108、AA7108A、AA7015、AA7017、AA7018、AA7019A、AA7024、AA7025、AA7028、AA7030、AA7031、AA7033、AA7035、AA7035A、AA7046、AA7046A、AA7003、AA7004、AA7005、AA7009、AA7010、AA7011、AA7012、AA7014、AA7016、AA7116、AA7122、AA7023、AA7026、AA7029、AA7129、AA7229、AA7032、AA7033、AA7034、AA7036、AA7136、AA7037、AA7040、AA7140、AA7041、AA7049、AA7049A、AA7149、7204、AA7249、AA7349、AA7449、AA7050、AA7050A、AA7150、AA7250、AA7055、AA7155、AA7255、AA7056、AA7060、AA7064、AA7065、AA7068、AA7168、AA7175、AA7475、AA7076、AA7178、AA7278、AA7278A、AA7081、AA7181、AA7185、AA7090、AA7093、AA7095 or AA7099.

Non-limiting exemplary 8xxx series Al alloys may include AA8005、AA8006、AA8007、AA8008、AA8010、AA8011、AA8011A、AA8111、AA8211、AA8112、AA8014、AA8015、AA8016、AA8017、AA8018、AA8019、AA8021、AA8021A、AA8021B、AA8022、AA8023、AA8024、AA8025、AA8026、AA8030、AA8130、AA8040、AA8050、AA8150、AA8076、AA8076A、AA8176、AA8077、AA8177、AA8079、AA8090、AA8091 or AA8093.

Composite material

As described herein, al and metal alloys and/or Al particles and non-Al particles may provide Al alloy products described herein, such as foils, sheets, or coatings, to produce composite materials or composite substrates, such as electronic substrates, which may be suitable for use as current collectors or devices incorporating such current collectors (such as electrodes, electrochemical cells, or capacitors). In some examples, the composite may be provided as a metal or metal alloy sheet or metal alloy foil, but is generally referred to herein as a layer in the context of a composite substrate. For use as a composite substrate, the Al and metal alloys or Al particles and non-Al particles may comprise a metal or metal alloy foil. In some aspects, the composite material may include at least one layer, such as 1 layer, 2 layers, 3 layers, and the like. In some aspects, each layer may include Al particles and non-Al particles as described herein. In some aspects, each layer may include Al and a metal alloy as described herein. In some aspects, the composite material comprises only Al and the metal alloy, i.e., does not comprise a layer having discrete particles. In a still further aspect, the composite comprises at least one layer comprising discrete particles as described herein, and comprises at least one layer comprising Al and a metal alloy as described herein. The layers may each contain the same or different Al and metal alloys or Al particles and non-Al particles, or different ratios thereof. In other embodiments, some layers may comprise Al particles and non-Al particles as described herein, while other layers may have different compositions.

Composite materials comprising non-Al particles may be used to prevent or limit corrosion, degradation or alloying of Al particles, such as in current collector applications of electrochemical cells or capacitors. In some examples, non-Al particles may be used to block or prevent the transport of certain materials, such as limiting the contact of those materials with Al particles. In some examples, contacting the Al particles with lithium atoms and/or lithium ions may be detrimental, resulting in corrosion, reaction, and/or alloying of the Al alloy with lithium.

Although the use of Al as the current collector of the negative electrode in a lithium or lithium ion battery is generally undesirable because corrosion, reaction, and/or alloying may occur at the negative electrode potential, current collectors comprising a composite material comprising Al and a metal alloy or Al and non-Al particles as described herein may limit Al particles within the composite material from being contacted, corroded, reacted, and/or alloyed by lithium or lithium ions while still allowing substantial transport of current through the Al and metal alloy or Al particles and/or allowing transport of lithium atoms or lithium ions to the Al and metal alloy or particles. The lithium atoms or lithium ions are at least one of absorbed, stored, or released by the composite materials described herein.

Fig. 1A provides an example of a composite material 100, shown schematically in cross section, that contains a uniform distribution 105 of Al particles and non-Al particles. Region a of fig. 1A, shown in more detail in fig. 1B, schematically illustrates the uniform distribution of Al particles 110 and non-Al particles 115. The uniform distribution of Al particles 110 and non-Al particles 115 extends through the thickness t ₁ of the composite material 100. Composite 100 is an active negative current collector that functions as an active negative material that allows electrons to flow through the device to an external circuit while allowing reversible absorption/emission of lithium ions released from the positive electrode, and is a negative current collector that conducts electrons in a monolithic composite or composite substrate into and out of the device.

However, several aspects may optionally be used for the conductive composite. As one example, the composite material is electrically conductive. Exemplary composites may have a conductivity of 10 ⁵ S/m to 10 ⁸ S/m and/or a resistivity of 10 ^-8 Ω -m to 10 ^-6 Ω -m. Such conductivity and/or resistivity may be sufficient to allow electrons to conduct through the composite material to Al and metal alloys or Al particles distributed therein, where substantial conduction may occur.

As another example, it is advantageous that the composite is free or substantially free of defects that allow lithium atoms or lithium ions to be transported to Al and metal alloys or Al particles, such as through the thickness t ₁ of the composite. As used herein, the phrase "substantially free" refers to a situation in which there is no complete absence of a condition, but such absence does not cause damage nor result in failure, degradation, or lack of availability. For example, a composite that is substantially free of defects may include some defects, but the included defects do not inhibit the composite from sufficiently conducting electricity. Exemplary defects may include, but are not limited to, voids, channels, cracks, grown defects, nodular defects, grooves, or crystalline defects, such as dislocations, stacking faults, or grain boundaries. In some cases, the defect may be filled, covered, or otherwise sealed or effectively removed by depositing a conductive sub-layer on the surface of the composite material that includes the defect.

A composite material, such as composite material 100, may be produced by mixing a plurality of Al particles 110 and a plurality of non-Al particles 115. The first plurality of Al particles 110 may have an average particle size of 10nm to 100 μm. Exemplary particle sizes may be about 10nm to about 100 μm, such as about 10nm to 50nm, 10nm to 100nm, 10nm to 500nm, 10nm to 1 μm, 10nm to 10 μm, 10nm to 50 μm, 10nm to 100 μm, 50nm to 100nm, 50nm to 500nm, 50nm to 1 μm, 50nm to 10 μm, 50nm to 50 μm, 50nm to 100 μm, 100nm to 500nm, 100nm to 1 μm, 100nm to 5 μm, 100nm to 10 μm, 100nm to 50 μm, 100nm to 100 μm, 500nm to 1 μm, 500nm to 5 μm, 500nm to 10 μm, 500nm to 50 μm, 500nm to 100 μm, 1 μm to 5 μm, 1 μm to 10 μm, 1 μm to 100 μm, 5 μm to 10 μm, 5 μm to 50 μm, 5 μm to 100 μm, 100 μm to 100 μm, 10 μm or 50 μm to 100 μm.

The second plurality of Al particles 115 may have an average particle size of 10nm to 100 μm. Exemplary particle sizes may be about 10nm to about 100 μm, such as about 10nm to 50nm, 10nm to 100nm, 10nm to 500nm, 10nm to 1 μm,10 nm to 10 μm,10 nm to 50 μm,10 nm to 100 μm, 50nm to 100nm, 50nm to 500nm, 50nm to 1 μm, 50nm to 10 μm, 50nm to 50 μm, 50nm to 100 μm, 100nm to 500nm, 100nm to 1 μm, 100nm to 5 μm, 100nm to 10 μm, 100nm to 50 μm, 100nm to 100 μm, 500nm to 1 μm, 500nm to 5 μm, 500nm to 10 μm, 500nm to 50 μm, 500nm to 100 μm,1 μm to 5 μm,1 μm to 10 μm,1 μm to 100 μm, 5 μm to 10 μm, 5 μm to 50 μm, 5 μm to 100 μm, 100 μm to 100 μm,10 μm or 50 μm to 100 μm.

A composite (e.g., composite 100) may be produced by mixing a plurality of Al particles 110 and a plurality of non-Al particles 115 such that the composition of the composite comprises 1 wt% to 99 wt% Al metal or alloy based on the total weight of the composite. Exemplary Al metal or alloy contents may be from about 1 wt% to about 99 wt%, such as 1 wt% to 5 wt%, 1 wt% to 10 wt%, 1 wt% to 15 wt%, 1 wt% to 20 wt%, 1 wt% to 25 wt%, 1 wt% to 30 wt%, 1 wt% to 35 wt%, 1 wt% to 40 wt%, 1 wt% to 45 wt%, 1 wt% to 50 wt%, 1 wt% to 55 wt%, 1 wt% to 60 wt%, 1 wt% to 65 wt%, 1 wt% to 70 wt%, 1 wt% to 75 wt%, 1 wt% to 80 wt%, 1 wt% to 85 wt%, 1 wt% to 90 wt%, 1 wt% to 95 wt%, 1 wt% to 99 wt%, 5 wt% to 10 wt%, 5 wt% to 15 wt%, 5 wt% to 20 wt%, 5 wt% to 25 wt%, 5 wt% to 30 wt%, and the like. 5 to 35 wt%, 5 to 40 wt%, 5 to 45 wt%, 5 to 50 wt%, 5 to 55 wt%, 5 to 60 wt%, 5 to 65 wt%, 5 to 70 wt%, 5 to 75 wt%, 5 to 80 wt%, 5 to 85 wt%, 5 to 90 wt%, 5 to 95 wt%, 5 to 99 wt%, 10 to 15 wt%, 10 to 20 wt%, 10 to 25 wt%, 10 to 30 wt%, 10 to 35 wt%, 10 to 40 wt%, 10 to 45 wt%, 10 to 50 wt%, 10 to 55 wt%, 10 to 60 wt%, and, 10 to 65 wt%, 10 to 70 wt%, 10 to 75 wt%, 10 to 80 wt%, 10 to 85 wt%, 10 to 90 wt%, 10 to 95 wt%, 10 to 99 wt%, 15 to 20 wt%, 15 to 25 wt%, 15 to 30 wt%, 15 to 35 wt%, 15 to 40 wt%, 15 to 45 wt%, 15 to 50 wt%, 15 to 55 wt%, 15 to 60 wt%, 15 to 65 wt%, 15 to 70 wt%, 15 to 75 wt%, 15 to 80 wt%, 15 to 85 wt%, 15 to 90 wt%, 15 to 95 wt%, 15 to 99 wt%, 20 to 25 wt%, and 20 to 30 wt%, 20 to 35 wt%, 20 to 40 wt%, 20 to 45 wt%, 20 to 50 wt%, 20 to 55 wt%, 20 to 60 wt%, 20 to 65 wt%, 20 to 70 wt%, 20 to 75 wt%, 20 to 80 wt%, 20 to 85 wt%, 20 to 90 wt%, 20 to 95 wt%, 20 to 99 wt%, 25 to 30 wt%, 25 to 35 wt%, 25 to 40 wt%, 25 to 45 wt%, 25 to 50 wt%, 25 to 60 wt%, 25 to 65 wt%, 25 to 70 wt%, 25 to 75 wt%, 25 to 80 wt%, 25 to 85%, 25 to 90%, 25 to 95%, 25 to 99%, 30 to 35%, 30 to 40%, 30 to 45%, 30 to 50%, 30 to 55%, 30 to 60%, 30 to 65%, 30 to 70%, 30 to 75% by weight 30 to 80 wt%, 30 to 85 wt%, 30 to 90 wt%, 30 to 95 wt%, 30 to 99 wt%, 35 to 40 wt%, 35 to 45 wt%, 35 to 50 wt%, 35 to 55 wt%, 35 to 60 wt%, 35 to 65 wt%, 35 to 70 wt%, 35 to 75 wt%, 35 to 80 wt%, 35 to 85 wt%, 35 to 90 wt%, 35 to 95 wt%, 35 to 99 wt%, 40 to 45 wt%, 40 to 50 wt%, 40 to 55 wt%, 40 to 60 wt%, 40 to 65 wt%, 40 to 70 wt%, 40 to 75 wt%, 40 to 80 wt%, 40 to 85 wt%, 40 to 90 wt%, 40 to 95 wt%, 40 to 99 wt%, 45 to 50 wt%, 45 to 55 wt%, 45 to 60 wt%, 45 to 65 wt%, 45 to 75 wt%, 45 to 80 wt%, 45 to 85 wt%, 45 to 90 wt%, 45 to 95 wt%, 45 to 99 wt%, 50 to 55 wt%, 50 to 60 wt%, 50 to 65 wt%, 50 to 70 wt%, 50 to 75 wt%, 50 to 80 wt%, 50 to 85 wt%, 50 to 90 wt%, 50 to 95 wt%, 50 to 99 wt%, 55 to 60 wt%, 55 to 65 wt%, 55 to 70 wt%, 55 to 75 wt%, 55 to 80 wt%, 55 to 85 wt%, 55 to 90 wt%, 55 to 95 wt%, 55 to 99 wt%, 60 to 80 wt%, 60 to 85 wt%, 60 to 75 wt%, 60 to 80 wt%, 60 to 85 wt%, 60 to 70 wt%, 55 to 80 wt%, 55 to 85 wt%, 90 wt%, 55 to 95 wt%, 60 to 65 wt%, 60 to 70 wt%, 60 to 75 wt%, and 60 to 85 wt%; 60 to 90 wt%, 60 to 95 wt%, 60 to 99 wt%, 65 to 70 wt%, 65 to 75 wt%, 65 to 80 wt%, 65 to 85 wt%, 65 to 90 wt%, 65 to 95 wt%, 65 to 99 wt%, 70 to 75 wt%, 70 to 80 wt%, 70 to 85 wt%, 70 to 90 wt%, 70 to 95 wt%, 70 to 99 wt%, 75 to 80 wt%, 75 to 85 wt%, 75 to 90 wt%, 75 to 95 wt%, 75 to 99 wt%, 80 to 85 wt%, 80 to 90 wt%, 80 to 95 wt%, 80 to 99 wt%, 85 to 90 wt%, and 90 to 90 wt%, 85 to 95 wt%, 85 to 99 wt%, 90 to 95 wt%, 90 to 99 wt%, or 95 to 99 wt%. In some embodiments, the composite comprises 45 wt% to 90 wt% Al metal or alloy. In other embodiments, the composite comprises 40 wt% to 70 wt%, 45 wt% to 65 wt%, or 50 wt% to 55 wt% Al metal or alloy. In some embodiments, the composite composition comprises 53 wt% Al metal or alloy. The balance of the composite composition comprises one or more non-Al metal or alloy components. Combinations of Al metal and Al alloys are also contemplated.

In other words, the composition of the composite comprises from 1 wt% to 99 wt% of the non-Al metal or alloy, based on the total weight of the composite. Exemplary non-Al metal or alloy contents may be from about 1 wt% to about 99 wt%, such as 1 wt% to 5 wt%, 1 wt% to 10 wt%, 1 wt% to 15 wt%, 1 wt% to 20 wt%, 1 wt% to 25 wt%, 1 wt% to 30 wt%, 1 wt% to 35 wt%, 1 wt% to 40 wt%, 1 wt% to 45 wt%, 1 wt% to 50 wt%, 1 wt% to 55 wt%, 1 wt% to 60 wt%, 1 wt% to 65 wt%, 1 wt% to 70 wt%, 1 wt% to 75 wt%, 1 wt% to 80 wt%, 1 wt% to 85 wt%, 1 wt% to 90 wt%, 1 wt% to 95 wt%, 1 wt% to 99 wt%, 5 wt% to 10 wt%, 5 wt% to 15 wt%, 5 wt% to 20 wt%, 5 wt% to 25 wt%, 5 wt% to 30 wt%, and the like. 5 to 35 wt%, 5 to 40 wt%, 5 to 45 wt%, 5 to 50 wt%, 5 to 55 wt%, 5 to 60 wt%, 5 to 65 wt%, 5 to 70 wt%, 5 to 75 wt%, 5 to 80 wt%, 5 to 85 wt%, 5 to 90 wt%, 5 to 95 wt%, 5 to 99 wt%, 10 to 15 wt%, 10 to 20 wt%, 10 to 25 wt%, 10 to 30 wt%, 10 to 35 wt%, 10 to 40 wt%, 10 to 45 wt%, 10 to 50 wt%, 10 to 55 wt%, 10 to 60 wt%, and, 10 to 65 wt%, 10 to 70 wt%, 10 to 75 wt%, 10 to 80 wt%, 10 to 85 wt%, 10 to 90 wt%, 10 to 95 wt%, 10 to 99 wt%, 15 to 20 wt%, 15 to 25 wt%, 15 to 30 wt%, 15 to 35 wt%, 15 to 40 wt%, 15 to 45 wt%, 15 to 50 wt%, 15 to 55 wt%, 15 to 60 wt%, 15 to 65 wt%, 15 to 70 wt%, 15 to 75 wt%, 15 to 80 wt%, 15 to 85 wt%, 15 to 90 wt%, 15 to 95 wt%, 15 to 99 wt%, 20 to 25 wt%, and 20 to 30 wt%, 20 to 35 wt%, 20 to 40 wt%, 20 to 45 wt%, 20 to 50 wt%, 20 to 55 wt%, 20 to 60 wt%, 20 to 65 wt%, 20 to 70 wt%, 20 to 75 wt%, 20 to 80 wt%, 20 to 85 wt%, 20 to 90 wt%, 20 to 95 wt%, 20 to 99 wt%, 25 to 30 wt%, 25 to 35 wt%, 25 to 40 wt%, 25 to 45 wt%, 25 to 50 wt%, 25 to 60 wt%, 25 to 65 wt%, 25 to 70 wt%, 25 to 75 wt%, 25 to 80 wt%, 25 to 85%, 25 to 90%, 25 to 95%, 25 to 99%, 30 to 35%, 30 to 40%, 30 to 45%, 30 to 50%, 30 to 55%, 30 to 60%, 30 to 65%, 30 to 70%, 30 to 75% by weight 30 to 80 wt%, 30 to 85 wt%, 30 to 90 wt%, 30 to 95 wt%, 30 to 99 wt%, 35 to 40 wt%, 35 to 45 wt%, 35 to 50 wt%, 35 to 55 wt%, 35 to 60 wt%, 35 to 65 wt%, 35 to 70 wt%, 35 to 75 wt%, 35 to 80 wt%, 35 to 85 wt%, 35 to 90 wt%, 35 to 95 wt%, 35 to 99 wt%, 40 to 45 wt%, 40 to 50 wt%, 40 to 55 wt%, 40 to 60 wt%, 40 to 65 wt%, 40 to 70 wt%, 40 to 75 wt%, 40 to 80 wt%, 40 to 85 wt%, 40 to 90 wt%, 40 to 95 wt%, 40 to 99 wt%, 45 to 50 wt%, 45 to 55 wt%, 45 to 60 wt%, 45 to 65 wt%, 45 to 75 wt%, 45 to 80 wt%, 45 to 85 wt%, 45 to 90 wt%, 45 to 95 wt%, 45 to 99 wt%, 50 to 55 wt%, 50 to 60 wt%, 50 to 65 wt%, 50 to 70 wt%, 50 to 75 wt%, 50 to 80 wt%, 50 to 85 wt%, 50 to 90 wt%, 50 to 95 wt%, 50 to 99 wt%, 55 to 60 wt%, 55 to 65 wt%, 55 to 70 wt%, 55 to 75 wt%, 55 to 80 wt%, 55 to 85 wt%, 55 to 90 wt%, 55 to 95 wt%, 55 to 99 wt%, 60 to 80 wt%, 60 to 85 wt%, 60 to 75 wt%, 60 to 80 wt%, 60 to 85 wt%, 60 to 70 wt%, 55 to 80 wt%, 55 to 85 wt%, 90 wt%, 55 to 95 wt%, 60 to 65 wt%, 60 to 70 wt%, 60 to 75 wt%, and 60 to 85 wt%; 60 to 90 wt%, 60 to 95 wt%, 60 to 99 wt%, 65 to 70 wt%, 65 to 75 wt%, 65 to 80 wt%, 65 to 85 wt%, 65 to 90 wt%, 65 to 95 wt%, 65 to 99 wt%, 70 to 75 wt%, 70 to 80 wt%, 70 to 85 wt%, 70 to 90 wt%, 70 to 95 wt%, 70 to 99 wt%, 75 to 80 wt%, 75 to 85 wt%, 75 to 90 wt%, 75 to 95 wt%, 75 to 99 wt%, 80 to 85 wt%, 80 to 90 wt%, 80 to 95 wt%, 80 to 99 wt%, 85 to 90 wt%, and 90 to 90 wt%, 85 to 95 wt%, 85 to 99 wt%, 90 to 95 wt%, 90 to 99 wt%, or 95 to 99 wt%. In some embodiments, the composite composition comprises 10 wt% to 55 wt% of the non-Al metal or alloy, based on the total weight of the composite. In some embodiments, the composite composition comprises 40 wt% to 70 wt% non-Al metal or alloy, 45 wt% to 65 wt%, 45 wt% to 50 wt% or 47 wt% non-Al metal or alloy, such as 47 wt% indium. Combinations of non-Al metals and non-Al alloys are also contemplated.

The ratio of Al metal or Al alloy to non-Al metal or alloy may range from 1:99 to 99:1, 1:95 to 95:1, 1:90 to 90:1, 1:85 to 85:1, 1:80 to 80:1, 1:75 to 75:1, 1:70 to 70:1, 1:65 to 65:1, 1:60 to 60:1, 1:55 to 55:1, 1:50 to 50:1, 1:45 to 45:1, 1:40 to 40:1, 1:35 to 35:1, 1:30 to 30:1, 1:25 to 25:1, 1:20 to 20:1, 1:15 to 15:1, 1:10 to 10:1, 1:5 to 5:1, 1:3 to 3:1, 1:2 to 2:1, or about 1:1).

It is also beneficial for the composite material to comprise a first plurality of Al particles and a second plurality of non-Al particles, each of the plurality of particles optionally being uniformly distributed, and each of the plurality of particles having a high purity, such as having a impurity level of 15% or less, 10% or less, 5% or less, 1% or less, 0.1% or less, or 0.01% or less. For example, oxygen may be considered an impurity in the composite material. In some embodiments, the composite material may have an oxygen content of 50 atomic% or less. In some embodiments, the first plurality of Al particles and the second plurality of non-Al particles each have a purity of 90 wt% or greater. In other embodiments, the first plurality of Al particles and the second plurality of non-Al particles each have a purity of 95 wt.% or greater. In other embodiments, the first plurality of Al particles and the second plurality of non-Al particles each have a purity of 99 wt.% or more. The alloy of Al and the other metal may have the same purity as the discrete particles.

The composite material (such as composite material 100) may have an average thickness t ₁ of 10nm to 150 μm. Exemplary thicknesses may be from about 10nm to about 150 μm, such as 10nm to 50nm, 10nm to 100nm, 10nm to 500nm, 10nm to 1 μm, 10nm to 10 μm, 10nm to 50 μm, 10nm to 100 μm, 10nm to 150 μm, 50nm to 100nm, 50nm to 500nm, 50nm to 1 μm, 50nm to 10 μm, 50nm to 50 μm, 50nm to 100 μm, 50nm to 150 μm, 100nm to 500nm, 100nm to 1 μm, 100nm to 5 μm, 100nm to 10 μm, 100nm to 50 μm, 100nm to 100 μm, 100 μm to 150 μm 500nm to 1 μm, 500nm to 5 μm, 500nm to 10 μm, 500nm to 50 μm, 500nm to 100 μm, 500nm to 150 μm, 1 μm to 5 μm, 1 μm to 10 μm, 1 μm to 50 μm, 1 μm to 100 μm, 1 μm to 150 μm, 5 μm to 10 μm, 5 μm to 50 μm, 5 μm to 100 μm, 5 μm to 150 μm, 10 μm to 50 μm, 10 μm to 100 μm, 10 μm to 150 μm, 50 μm to 100 μm, or 50 μm to 150 μm.

The composite materials described herein may comprise multiple components/layers. At least one component is a plurality of Al particles present in an amount of at least 10 wt.%. The other component is a plurality of non-Al particles, i.e. particles that do not include Al. Materials that may be used for the second plurality of non-Al particles include particles that do not form alloys with lithium. In other words, in some embodiments, it may be useful to exclude metals that form alloys with lithium for non-Al particles. For example, the non-Al particles may not include Al, zinc, magnesium, silicon, germanium, tin, indium, antimony, and/or carbon. In other embodiments, these non-Al particles may be specifically included.

Non-Al particles that may be used in the composite material may include materials that do not react with lithium at potentials of 0V to 5V relative to Li/L ⁱ⁺. The composite material may be characterized as having a specific capacity of 450mAh/g to 1000mAh/g for at least 14 cycles (120 hours). In some examples, the composite may be characterized as having an area capacity of greater than or about 2mAh/cm ². The composite material may be characterized as having a percent lithiation of 50% to 100%. In some cases, when these non-Al particles are used or included in a composite, such particles may be attacked by lithium atoms or lithium ions and cause the lithium atoms or lithium ions to reach the Al particles and corrode, alloy with, or otherwise degrade the Al-containing composite. Specific materials that may be used for the non-Al particles may be selected from at least one of metal particles and non-metal particles. The metal particles may be selected from at least one of zinc, silicon, bismuth, copper, germanium, indium, antimony, tin, magnesium, or combinations thereof. The non-metallic particles may be selected from at least one of carbon, lithium titanium oxide, titanium dioxide 、MoO、MoS₂、Co₂O₄、MnO₂ Fe₂O₃、Fe₃O₄、FeS、CuO, or a combination thereof. The composite material is useful as a current collector and an active material.

Fig. 2 is a graph showing the voltage change over time of a comparative pure Al foil in a half Al cell paired with a Li counter electrode. As shown, the shorter the specific capacity cycle as Al is consumed.

As described above, the composite materials described herein may be used as electronic substrates, such as for current collectors or as electrode assemblies in electrochemical cells and capacitors. Fig. 3A provides a schematic cross-sectional view of an exemplary device corresponding to electrode 300. Electrode 300 may be a component of an electrochemical cell (e.g., a primary electrochemical cell or a secondary electrochemical cell). The electrode 300 includes a composite material 305 as a negative electrode current collector or a positive electrode current collector and an active material 310. The active material 310 may correspond to a material that undergoes an electrochemical reaction during charge or discharge of an electrochemical cell. In various embodiments, the active material 310 may correspond to a positive electrode active material or a negative electrode active material. Exemplary materials for electrode active material 310 include lithium ion battery negative electrode active materials, such as intercalation materials, e.g., graphite. In some cases, a metallic lithium anode active material may be used, such as for primary batteries. Exemplary materials for electrode active material 310 include lithium ion battery positive electrode active materials, such as lithium-based materials, including lithium cobalt oxide, lithium iron phosphate, lithium manganese oxide, lithium nickel manganese cobalt oxide, lithium nickel cobalt Al oxide, and the like.

Fig. 3B provides a schematic cross-sectional view of an exemplary device corresponding to electrode 350, which electrode 350 may be a component of an electrochemical cell (e.g., a primary electrochemical cell or a secondary electrochemical cell). Electrode 350 includes a composite 355 that is either a negative current collector or a positive current collector, which also serves as an active material. Advantageously, electrode 350 does not require a separate active material.

Fig. 4 shows a schematic cross-sectional view of an exemplary device corresponding to an electrochemical cell 400. Electrochemical cell 400 includes a first electrode 402, which may correspond to a negative electrode in some examples; and a second electrode 406, which in some examples may correspond to a positive electrode. The first electrode 402 of the electrochemical cell 400 includes a composite material 405 comprising a plurality of Al particles uniformly distributed with a plurality of non-Al particles as described herein. The composite 405 of the electrode 402 serves as a first current collector and a first active material, such as a negative active material. The second electrode 406 of the electrochemical cell 400 includes a second current collector 410 and a second active material 415, such as a positive active material. Electrochemical cell 400 also includes a separator and/or electrolyte, as shown by assembly 435. The separator and/or electrolyte may be used to prevent the first electrode active material and the second electrode active material 415 of the composite 405 from contacting each other while still allowing ions to pass through during charge or discharge. Exemplary membranes may be or include non-reactive porous materials such as polymeric membranes, e.g., polypropylene, poly (methyl methacrylate), or polyacrylonitrile. Examples of electrolytes may be or include organic solvents such as ethylene carbonate, dimethyl carbonate or diethyl carbonate, or solid or ceramic electrolytes. The electrolyte may include dissolved lithium salts such as LiPF ₆、LiBF₄ or LiClO ₄, as well as other additives.

In addition, the electrochemical cell 400 may be used or employed as a component of other devices, such as portable electronic devices, mobile phones, tablet computers, and the like. For example, the first current collector of the composite material 405 of the negative electrode 402 and the second current collector 410 of the positive electrode 406 of the electrochemical cell 400 may be positioned in direct or indirect communication with an electronic device or circuitry of an electronic device and receive or provide current.

Methods of making the composite are also described herein. The method includes mixing a plurality of Al particles and a plurality of non-Al particles to form a homogeneous mixture. The non-Al particles may be indium particles or other non-Al particles described herein. The mixture may be mechanically, thermally, or thermomechanically treated to form a composite material. The plurality of Al particles and the plurality of non-Al particles are optionally uniformly distributed throughout the composite. Mechanical, thermal, or thermo-mechanical treatment of the mixture may include rolling, power treatment, and/or chemical vapor deposition. The composite material may comprise or correspond to an electronic substrate, a current collector, a capacitor, a supercapacitor, a current collector for an electrochemical cell, a current collector for a lithium-ion electrochemical cell, or a combination thereof.

Composite materials can also be made with engineered structures. By engineering the structure, the structure may include additional space and microporosity. Without being bound by theory, such additional space and/or microporosity may compensate for volume changes within the composite. Such engineered structures may be formed using a variety of methods including powder metallurgy, forming microporous or nanoporous structures by additive manufacturing, using metal foam, forming perforations by laser or deep etching, or other methods.

The embodiments disclosed herein will be used to further illustrate aspects of the invention, but at the same time should not be construed as limiting the invention in any way. On the contrary, it is to be clearly understood that resort may be had to various other embodiments, modifications, and equivalents thereof which, after reading the description herein, may suggest themselves to those skilled in the art without departing from the spirit of the present invention. The examples and embodiments described herein may also utilize conventional procedures, unless otherwise indicated. Some of the procedures are described herein for illustrative purposes.

Example 1 electrochemical cell testing of half cells

To test the effectiveness of the different conductive protective layers, half cells were composed of a composite material as the working electrode, lithium metal as the counter electrode, and a separator soaked with electrolyte between the composite material and the lithium metal. The composite material includes a plurality of Al particles having a plurality of non-Al particles uniformly distributed therein. Various composites were tested. Cyclic voltammograms are obtained by controlling the applied voltage or current with a potentiostat to determine which protective layers improve the stability of the Al alloy as a current collector at low potentials, similar to those at the negative side of a lithium-ion electrochemical cell.

Fig. 5 provides a graph 500 showing the voltage versus time of a sample comparative pure Al foil that is joined at 80% capacity to retain Li. The Al foil thickness was 7. Mu.m.

Fig. 6A provides a graph 600 showing the voltage over time of an exemplary inai composite foil that is bonded to 100% capacity to hold Li. An LiPF ₆ Electrochemical Cell (EC) was used to pair the InAl foil with Li and separated by DEC and FEC electrolytes and a C/5 circulation rate and a mass of 0.81mg (theoretical area capacity of 4.32mAh/cm ²). The example of fig. 6A shows the performance maintained over time compared to the comparative Al foil in fig. 5. Fig. 6B provides a graph 650 showing the cyclic specific capacity of the example of fig. 6A for a minimum specific capacity loss over 14 cycles. Each cycle was about 8 hours and 14 cycles corresponded to about 120 hours.

Example 2-understanding electrochemical behavior of multicomponent aluminum-based foil as negative electrode for lithium ion batteries

Alloy cathodes are promising materials for next generation lithium batteries. The inherent properties of aluminum, such as high capacity, light weight, earth abundance, and low cost, make it a competitive alloy negative electrode candidate in lithium batteries. In addition, aluminum-based foils can be easily manufactured and offer the advantage of potentially simplifying the battery manufacturing process. However, the use of Al cathodes may experience capacity fade during charging and discharging.

To improve cycle performance, aluminum alloys and composite foil structures were fabricated to investigate their reversibility of Li storage in Li-ion batteries. Alloy foils including al—sn, al—zn, and al—in, having Al contents ranging from 50 atomic% to 99 atomic%, were prepared, and the electrochemical behavior of these materials as negative electrodes of Li-ion batteries was studied. Using these materials, the effect of composition, structure and morphology on the cycle performance of the alloy foil was studied using a battery-related capacity measure (area capacity >2mAh/cm ², where foil thickness <50 microns). The results show that the composition of the foils can play an important role in determining the electrochemical cycling capabilities of these foils. In addition, foil handling characteristics are also important in determining the achievable specific capacity, rate behavior and cycle life of these foil cathodes. This effort indicates the prospect of foil-based alloy cathodes and provides guidance for engineering strategies to improve performance.

Example 3-benchmarking electrochemical degradation behavior of aluminum foil cathodes for lithium ion batteries

Aluminum is an attractive candidate for replacing graphite cathodes in lithium ion batteries because of its high specific capacity (e.g., up to or about 990mAh g ^-1), and the direct use of aluminum foil as the cathode structure may eliminate the need for a slurry coating process. However, achieving highly reversible lithiation and delithiation of aluminum can be affected by volume changes during conversion, slow lithium ion transport through the surface oxide layer, and poor initial coulombic efficiency (Coulombic efficiency), which can all lead to degradation during cycling. Research has focused on understanding the basic electrochemical reactions and material transformation behavior of aluminum, but has not focused on how different aluminum alloy compositions behave and degrade under electrochemical cycling conditions.

Comprehensive electrochemical tests were performed to benchmark the performance of three different aluminum alloy foils under different cycling conditions. For a constant thickness foil, the foil composition was found to exhibit a power law dependence of cycle life on the lithiated area capacity per cycle, revealing that degradation can be significantly accelerated when high area capacity is used per cycle. Furthermore, it was found that the composition of the aluminum alloy strongly influences the coulombic efficiency of the first 10 cycles, wherein higher purity foils exhibit higher coulombic efficiencies. Finally, ex situ scanning electron microscopy and in situ (operando) optical microscopy reveal different reaction mechanisms and mechanical degradation behavior between different alloys. Based on an understanding of these various parameters, it was determined how a full cell with an aluminum anode could cycle hundreds of cycles at a relatively low area capacity. The improvement in the understanding of the behaviour of the negative foil electrode paves the way for work intended to design aluminium-based foils with enhanced stability.

Example 4 aluminium foil half cell

The test half-cell with a 30 μm thick Al foil working electrode and Li counter electrode was subjected to constant current cycling. The electrolyte placed between the Al and Li electrodes was 1M LiPF ₆ in a 50:50 mixture (by volume) of Ethylene Carbonate (EC) and diethyl carbonate (DEC) with 10% fluoroethylene carbonate. The cell was cycled using a current density of 0.2mA/cm ² in the first two cycles and then 1mA/cm ² in the subsequent cycles. A graph of constant current cycle data is shown in fig. 7.

Example 5-Al-Sn alloy half cell

A composite of 65% Al and 35% Sn was made into a foil. An electron microscopic image of the foil is shown in fig. 8, as well as an x-ray microscopic analysis showing the distribution of Al and Sn in the composite.

A composite foil (30 μm thick) was used as a working electrode in a test half cell with a Li counter electrode. The half-cells were subjected to constant current cycling. The electrolyte placed between the working electrode and the Li electrode was 1M LiPF ₆ in a 50:50 mixture (by volume) of Ethylene Carbonate (EC) and diethyl carbonate (DEC) with 10% fluoroethylene carbonate. The cell was cycled using a current density of 0.2mA/cm ² in the first two cycles and then 1mA/cm ² in the subsequent cycles. A graph of constant current cycle data is shown in fig. 9. Fig. 10 shows a graph of several charge and discharge curves for an exemplary half-cell.

Example 6-Al-Zn alloy half cell

A composite of 51% Al and 49% Zn was made into foil. An electron micrograph of the foil is shown in fig. 11, as well as an x-ray microscopic analysis showing the distribution of Al and Zn in the composite.

A composite foil (30 μm thick) was used as a working electrode in a test half cell with a Li counter electrode. The half-cells were subjected to constant current cycling. The electrolyte placed between the working electrode and the Li electrode was 1M LiPF ₆ in a 50:50 mixture (by volume) of Ethylene Carbonate (EC) and diethyl carbonate (DEC) with 10% fluoroethylene carbonate. The cell was cycled using a current density of 0.2mA/cm ² in the first two cycles and then 1mA/cm ² in the subsequent cycles. A graph of constant current cycle data is shown in fig. 12. Fig. 13 shows a graph of several charge and discharge curves for an exemplary half-cell.

Example 7-Al-Si alloy half cell

A composite of 99% Al and 1% Si was made into a foil. An electron microscopic image of the foil is shown in fig. 14, as well as an x-ray microscopic analysis showing the distribution of Al and Si in the composite.

A composite foil (30 μm thick) was used as a working electrode in a test half cell with a Li counter electrode. The half-cells were subjected to constant current cycling. The electrolyte placed between the working electrode and the Li electrode was 1M LiPF ₆ in a 50:50 mixture (by volume) of Ethylene Carbonate (EC) and diethyl carbonate (DEC) with 10% fluoroethylene carbonate. The cell was cycled using a current density of 0.2mA/cm ² in the first two cycles and then 1mA/cm ² in the subsequent cycles. A graph of constant current cycle data is shown in fig. 15. Fig. 16 shows a graph of several charge and discharge curves for an exemplary half-cell.

Illustrative aspects

As used below, any reference to a series of aspects (e.g., "aspects 1-4") or a set of non-enumerated aspects (e.g., "any preceding or subsequent aspect") should be understood to be a separate reference to each of those aspects (e.g., "aspects 1-4" should be understood to be "aspects 1, 2, 3, or 4").

Aspect 1 is a composite comprising at least one layer, the at least one layer comprising: a first plurality of particles selected from at least one of Al particles and Al alloy particles; and a second plurality of particles selected from at least one of metal particles and non-metal particles, wherein the metal particles are selected from at least one of zinc, silicon, bismuth, copper, germanium, indium, antimony, tin, magnesium, or combinations thereof, and the non-metal particles are selected from at least one of carbon, lithium titanium oxide, titanium dioxide 、MoO、MoS₂、Co₂O₄、MnO₂、Fe₂O₃、Fe₃O₄、FeS、CuO, or combinations thereof.

Aspect 2 is the composite of any preceding or subsequent aspect, wherein the composite allows for the transport of lithium atoms or lithium ions to the Al particles.

Aspect 3 is the composite of any preceding or subsequent aspect, wherein the lithium atoms or lithium ions are at least one of absorbed, stored, or released by the composite.

Aspect 4 is the composite of any preceding or subsequent aspect, comprising from 1 to 99 weight percent of an Al metal or alloy, based on the total weight of the composite.

Aspect 5 is the composite of any preceding or subsequent aspect, comprising 40 to 70 wt% Al metal or alloy.

Aspect 6 is the composite of any preceding or subsequent aspect, wherein the first plurality of particles has an average particle size of 10nm to 100 μιη and the second plurality of particles has an average particle size of 10nm to 100 μιη.

Aspect 7 is the composite of any preceding or subsequent aspect, wherein the first plurality of particles and the second plurality of particles each have a purity of 90 wt% or greater.

Aspect 8 is the composite of any preceding or subsequent aspect, wherein the second plurality of particles are metal particles.

Aspect 9 is the composite of any preceding or subsequent aspect, wherein the second plurality of particles are non-metallic particles.

Aspect 10 is the composite of any preceding or subsequent aspect, wherein the composite collects lithium at a potential of 0V to 5V relative to Li/li+.

Aspect 11 is the composite of any preceding or subsequent aspect, characterized by having a specific capacity of 450mAh/g to 1000mAh/g in at least 14 cycles (120 hours).

Aspect 12 is the composite of any preceding or subsequent aspect, characterized by a percent lithiation of 50% to 100% and a specific capacity of 450mAh/g to 1000mAh/g in at least 14 cycles (120 hours).

Aspect 13 is the composite of any preceding or subsequent aspect, having an oxygen content of 50 atomic% or less.

Aspect 14 is the composite of any preceding or subsequent aspect, wherein the composite forms a substrate having a thickness of 10nm to 150 μm.

Aspect 15 is the composite of any preceding or subsequent aspect, wherein the first plurality of particles selected from at least one of Al particles and Al alloy particles are in powder form.

Aspect 16 is the composite of any preceding or subsequent aspect, wherein the second plurality of particles selected from at least one of metallic particles and non-metallic particles are in powder form.

Aspect 17 is the composite of any preceding or subsequent aspect, wherein the Al metal or alloy comprises an Al alloy sheet or Al alloy foil having a thickness of 10nm to 100 μm.

Aspect 18 is the composite of any preceding or subsequent aspect, wherein the second plurality of particles comprises a metal or metal alloy sheet or metal alloy foil having a thickness of 10nm to 100 μm.

Aspect 19 is the composite of any preceding or subsequent aspect, comprising or corresponding to an electronic substrate, a current collector, a capacitor, a supercapacitor, a current collector for an electrochemical cell, a current collector for a lithium-ion electrochemical cell, or a combination thereof.

Aspect 20 is a composite of any preceding or subsequent aspect, comprising or exhibiting a microporous or nanoporous structure.

Aspect 21 is the composite of any preceding or subsequent aspect, comprising or corresponding to an active negative electrode for a lithium-ion electrochemical cell.

Aspect 22 is a device, comprising: a first electrochemical cell electrode comprising a composite material having at least one layer, wherein the composite material is one or both of a current collector and an electrode active material, wherein the at least one layer comprises: a first plurality of particles selected from at least one of Al particles and Al alloy particles; and a second plurality of particles selected from at least one of metal particles and non-metal particles, wherein the metal particles are selected from at least one of zinc, silicon, bismuth, copper, germanium, indium, antimony, tin, magnesium, or combinations thereof, and the non-metal particles are selected from at least one of carbon, lithium titanium oxide, titanium dioxide 、MoO、MoS₂、Co₂O₄、MnO₂、Fe₂O₃、Fe₃O₄、FeS、CuO, or combinations thereof; a second electrochemical cell electrode; and an electrolyte between the first electrochemical cell electrode and the second electrochemical cell electrode.

Aspect 23 is the device of any preceding or subsequent aspect, wherein the electrode active material comprises a lithium ion positive electrode active material or a lithium ion negative electrode active material.

Aspect 24 is the device of any preceding or subsequent aspect, including or corresponding to an electrochemical cell, a battery, a portable electronic device, or a combination thereof.

Aspect 25 is the apparatus of any preceding or subsequent aspect, further comprising: electronics circuitry in direct or indirect electrical communication with the first electrochemical cell electrode or the second electrochemical cell electrode and drawing or receiving current from the first electrochemical cell electrode or the second electrochemical cell electrode.

Aspect 26 is the device of any preceding or subsequent aspect, the composite comprising or corresponding to the composite of any preceding or subsequent aspect.

Aspect 27 is a method of making a composite material having at least one layer, the method comprising: mixing a first plurality of particles and a second plurality of particles to form a homogeneous mixture, the first plurality of particles being selected from at least one of Al particles and Al alloy particles, and the second plurality of particles being selected from at least one of metal particles and non-metal particles, wherein the metal particles are selected from at least one of zinc, silicon, bismuth, copper, germanium, indium, antimony, tin, magnesium, or combinations thereof, and the non-metal particles are selected from at least one of carbon, lithium titanium oxide, titanium dioxide 、MoO、MoS₂、Co₂O₄、MnO₂、Fe₂O₃、Fe₃O₄、FeS、CuO, or combinations thereof; the mixture is mechanically, thermally or thermomechanically treated to form at least one layer of the composite material.

Aspect 28 is the method of any preceding or subsequent aspect, wherein the mechanically, thermally, or thermomechanically treating the mixture comprises rolling, power treatment, and/or chemical vapor deposition.

Aspect 29 is the method of any preceding or subsequent aspect, the composite comprising or corresponding to the composite of any preceding or subsequent aspect.

Aspect 30 is a composite comprising at least one layer comprising: an alloy comprising Al and at least one additional component comprising at least one of zinc, silicon, bismuth, copper, germanium, indium, antimony, tin, magnesium, or a combination thereof.

Aspect 31 is the composite of any preceding or subsequent aspect, wherein the composite allows for the transport of lithium atoms or lithium ions to the Al.

Aspect 32 is the composite of any preceding or subsequent aspect, wherein lithium atoms or lithium ions are at least one of absorbed, stored, or released by the composite.

Aspect 33 is the composite of any preceding or subsequent aspect, comprising from 1 wt% to 99 wt% of the alloy, based on the total weight of the composite.

Aspect 34 is the composite of any preceding or subsequent aspect, comprising 40 wt% to 70 wt% of the alloy.

Aspect 35 is the composite of any preceding or subsequent aspect, wherein the composite collects lithium at a potential of 0V to 5V relative to Li/li+.

Aspect 36 is the composite of any preceding or subsequent aspect, characterized by having a specific capacity of 450mAh/g to 1000mAh/g in at least 14 cycles (120 hours).

Aspect 37 is the composite of any preceding or subsequent aspect, characterized by a percent lithiation of 50% to 100% and a specific capacity of 450mAh/g to 1000mAh/g in at least 14 cycles (120 hours).

Aspect 38 is the composite of any preceding or subsequent aspect, having an oxygen content of 50 atomic% or less.

Aspect 39 is the composite of any preceding or subsequent aspect, wherein the composite forms a substrate having a thickness of 10nm to 150 μm.

Aspect 40 is the composite of any preceding or subsequent aspect, wherein the alloy comprises an Al alloy sheet or Al alloy foil having a thickness of 10nm to 100 μm.

Aspect 41 is the composite of any preceding or subsequent aspect, comprising or corresponding to an electronic substrate, a current collector, a capacitor, a supercapacitor, a current collector for an electrochemical cell, a current collector for a lithium-ion electrochemical cell, or a combination thereof.

Aspect 42 is a composite of any preceding or subsequent aspect, comprising or exhibiting a microporous or nanoporous structure.

Aspect 43 is the composite of any preceding or subsequent aspect, comprising or corresponding to an active negative electrode for a lithium-ion electrochemical cell.

Aspect 44 is a device comprising: a first electrochemical cell electrode comprising a composite material having at least one layer, wherein the composite material is one or both of a current collector and an electrode active material, wherein the at least one layer comprises: an alloy comprising Al and at least one additional component comprising at least one of zinc, silicon, bismuth, copper, germanium, indium, antimony, tin, magnesium, or a combination thereof; a second electrochemical cell electrode; and an electrolyte between the first electrochemical cell electrode and the second electrochemical cell electrode.

Aspect 45 is the device of any preceding or subsequent aspect, wherein the electrode active material comprises a lithium ion positive electrode active material or a lithium ion negative electrode active material.

Aspect 46 is the device of any preceding or subsequent aspect, including or corresponding to an electrochemical cell, a battery, a portable electronic device, or a combination thereof.

Aspect 47 is the apparatus of any preceding or subsequent aspect, further comprising: electronics circuitry in direct or indirect electrical communication with the first electrochemical cell electrode or the second electrochemical cell electrode and drawing or receiving current from the first electrochemical cell electrode or the second electrochemical cell electrode.

Aspect 48 is the device of any preceding or subsequent aspect, wherein the composite comprises a microporous or nanoporous structure.

Aspect 49 is the device of any preceding or subsequent aspect, the composite comprising or corresponding to the composite of any preceding or subsequent aspect.

All patents and publications cited herein are incorporated by reference in their entirety. The foregoing description of the embodiments, including the illustrated embodiments, has been presented only for the purposes of illustration and description and is not intended to be exhaustive or to be limited to the precise forms disclosed. Numerous modifications, adaptations and uses of the invention will be apparent to those skilled in the art.

Claims

1. A composite material comprising at least one layer, the at least one layer comprising:

A first plurality of particles selected from at least one of Al particles and Al alloy particles; and

A second plurality of particles selected from at least one of metal particles and non-metal particles, wherein the metal particles are selected from at least one of zinc, silicon, bismuth, copper, germanium, indium, antimony, tin, magnesium, or combinations thereof, and the non-metal particles are selected from at least one of carbon, lithium titanium oxide, titanium dioxide 、MoO、MoS₂、Co₂O₄、MnO₂、Fe₂O₃、Fe₃O₄、FeS、CuO, or combinations thereof.

2. The composite material of claim 1, wherein the composite material allows lithium atoms or lithium ions to be transported to the Al particles.

3. The composite material of claim 2, wherein the lithium atoms or lithium ions are at least one of absorbed, stored, or released by the composite material.

4. The composite material of claim 1, comprising 1 to 99 wt% Al metal or alloy, based on the total weight of the composite material.

5. The composite material of claim 4, comprising 40 to 70 wt% Al metal or alloy.

6. The composite material of claim 1, wherein the first plurality of particles have an average particle size of 10nm to 100 μιη and the second plurality of particles have an average particle size of 10nm to 100 μιη.

7. The composite material of claim 1, wherein the first and second pluralities of particles each have a purity of 90 wt% or greater.

8. The composite material of claim 1, wherein the second plurality of particles are metal particles.

9. The composite material of claim 1, wherein the second plurality of particles are non-metallic particles.

10. The composite of claim 1, wherein the composite collects lithium at a potential of 0V to 5V relative to Li/Li ⁺.

11. The composite of claim 1, having a specific capacity of 450mAh/g to 1000mAh/g for at least 14 cycles (120 hours).

12. The composite of claim 1, having a percent lithiation of 50% to 100% and a specific capacity of 450mAh/g to 1000mAh/g in at least 14 cycles (120 hours).

13. The composite material of claim 1, having an oxygen content of 50 atomic percent or less.

14. The composite of claim 1, wherein the composite forms a substrate having a thickness of 10nm to 150 μm.

15. The composite material of claim 1, wherein the first plurality of particles selected from at least one of Al particles and Al alloy particles are in powder form.

16. The composite material of claim 1, wherein the second plurality of particles selected from at least one of metallic particles and non-metallic particles are in powder form.

17. The composite material of claim 4, wherein the Al metal or alloy comprises an Al alloy sheet or Al alloy foil having a thickness of 10nm to 100 μm.

18. The composite material of claim 4, wherein the second plurality of particles comprises a metal or metal alloy sheet or metal alloy foil having a thickness of 10nm to 100 μm.

19. The composite material of claim 1, comprising or corresponding to an electronic substrate, a current collector, a capacitor, a supercapacitor, a current collector for an electrochemical cell, a current collector for a lithium-ion electrochemical cell, or a combination thereof.

20. The composite material of claim 1, comprising or exhibiting a microporous or nanoporous structure.

21. The composite material of claim 1, comprising or corresponding to an active negative electrode for a lithium-ion electrochemical cell.

22. A device, comprising:

A first electrochemical cell electrode comprising a composite material having at least one layer, wherein the composite material is one or both of a current collector and an electrode active material, wherein the at least one layer comprises:

A second plurality of particles selected from at least one of metal particles and non-metal particles, wherein the metal particles are selected from at least one of zinc, silicon, bismuth, copper, germanium, indium, antimony, tin, magnesium, or combinations thereof, and the non-metal particles are selected from at least one of carbon, lithium titanium oxide, titanium dioxide 、MoO、MoS₂、Co₂O₄、MnO_2、Fe₂O₃、Fe₃O₄、FeS、CuO, or combinations thereof;

A second electrochemical cell electrode; and

An electrolyte between the first electrochemical cell electrode and the second electrochemical cell electrode.

23. The device of claim 22, wherein the electrode active material comprises a lithium ion positive electrode active material or a lithium ion negative electrode active material.

24. The device of claim 22, comprising or corresponding to an electrochemical cell, a battery, a portable electronic device, or a combination thereof.

25. The device of claim 22, further comprising:

Electronics circuitry in direct or indirect electrical communication with the first electrochemical cell electrode or the second electrochemical cell electrode and drawing or receiving current from the first electrochemical cell electrode or the second electrochemical cell electrode.

26. The device of claim 22, the composite comprising or corresponding to the composite of any one of claims 1-21.

27. A method of preparing a composite material having at least one layer, the method comprising:

Mixing a first plurality of particles and a second plurality of particles to form a homogeneous mixture, the first plurality of particles being selected from at least one of Al particles and Al alloy particles, and the second plurality of particles being selected from at least one of metal particles and non-metal particles, wherein the metal particles are selected from at least one of zinc, silicon, bismuth, copper, germanium, indium, antimony, tin, magnesium, or combinations thereof, and the non-metal particles are selected from at least one of carbon, lithium titanium oxide, titanium dioxide 、MoO、MoS₂、Co₂O₄、MnO₂、Fe₂O₃、Fe₃O₄、FeS、CuO, or combinations thereof; and

The mixture is mechanically, thermally or thermomechanically treated to form at least one layer of the composite material.

28. The method of claim 27, wherein the mechanically, thermally, or thermomechanically treating the mixture comprises rolling, power treatment, and/or chemical vapor deposition.

29. A method according to claim 27, the composite comprising or corresponding to the composite of any one of claims 1 to 21.

30. A composite material comprising at least one layer, the at least one layer comprising: an alloy comprising Al and at least one additional component comprising at least one of zinc, silicon, bismuth, copper, germanium, indium, antimony, tin, magnesium, or a combination thereof.

31. The composite material of claim 30, wherein the composite material allows lithium atoms or lithium ions to be transported to the Al.

32. The composite material of claim 30, wherein lithium atoms or lithium ions are at least one of absorbed, stored, or released by the composite material.

33. The composite material of claim 30, comprising 1 to 99 weight percent of the alloy, based on the total weight of the composite material.

34. The composite material of claim 30, comprising 40 to 70 wt% of the alloy.

35. The composite of claim 30, wherein the composite collects lithium at a potential of 0V to 5V relative to Li/Li ⁺.

36. The composite of claim 30, having a specific capacity of 450mAh/g to 1000mAh/g for at least 14 cycles (120 hours).

37. The composite of claim 30, having a percent lithiation of 50% to 100% and a specific capacity of 450mAh/g to 1000mAh/g in at least 14 cycles (120 hours).

38. The composite material of claim 30, having an oxygen content of 50 atomic percent or less.

39. The composite of claim 30, wherein the composite forms a substrate having a thickness of 10nm to 150 μm.

40. The composite material of claim 30, wherein the alloy comprises an Al alloy sheet or an Al alloy foil having a thickness of 10nm to 100 μm.

41. The composite material of claim 30, comprising or corresponding to an electronic substrate, a current collector, a capacitor, a supercapacitor, a current collector for an electrochemical cell, a current collector for a lithium-ion electrochemical cell, or a combination thereof.

42. The composite material of claim 30, comprising or exhibiting a microporous or nanoporous structure.

43. The composite material of claim 30, comprising or corresponding to an active negative electrode for a lithium-ion electrochemical cell.

44. A device, comprising:

An alloy comprising Al and at least one additional component comprising at least one of zinc, silicon, bismuth, copper, germanium, indium, antimony, tin, magnesium, or a combination thereof;

A second electrochemical cell electrode; and

45. The device of claim 44, wherein the electrode active material comprises a lithium ion positive electrode active material or a lithium ion negative electrode active material.

46. The device of claim 44, comprising or corresponding to an electrochemical cell, a battery, a portable electronic device, or a combination thereof.

47. The apparatus of claim 44, further comprising:

48. The device of claim 44, wherein the composite material comprises a microporous or nanoporous structure.

49. The device of claim 44, wherein the composite material comprises or corresponds to the composite material of any one of claims 30-43.