Multilayered anode and associated methods and systems
Described herein are multilayer composite foil materials, as well as methods of making and using multilayer composite foil materials. The composite foil materials can comprise different layers of different metals which may have differing activity toward an active metal, such as lithium. The different layers may allow the composite foil material to include layers that are more active towards the active metal, providing for electrochemical activity, and other layers that are less active towards the active metal, and serving as structural layers. The multilayer composite foils are useful as anodes of electrochemical cells, such as lithium ion cells.
1 . A composite foil material exhibiting a hierarchical structure, wherein the hierarchical structure comprises different regions of alternating first layers and second layers, comprising:
a plurality of first layers comprising a first metal, which is a member selected from the group consisting of Al, Si, Zn, Ga, Ag, Cd, In, Sn, Sb, Au, Pb, Bi, and Mg;
a plurality of second layers comprising a second metal, which is a member selected from the group consisting of Cu, Zn, Mg, Fe, Ni, Al, Zr, Hf, Nb, and Mo, wherein the hierarchical structure comprises from 8 to 512 first layers alternating with from 8 to 512 second layers, wherein individual layer thickness is between 0.05 μm to −2 μm, and has an interface density of between 0.5 and 20 μm −1 , wherein at least some different regions of alternating first layers and second layers have different total thicknesses, different layer thicknesses, or different numbers of layers;
an active metal, which is a member selected from the group consisting of lithium, sodium, potassium and magnesium; and
wherein the active metal is less reactive toward the second metal than the first metal.
2 . The composite foil material of claim 1 , wherein the active metal is potassium.
3 . The composite foil material of claim 1 , wherein the first layers preferentially uptake and release cations of the active metal as compared to the second layers.
4 . The composite foil material of claim 1 ,
wherein the first layers exhibit uptake of cations of the active metal during electrochemical reactions at a first potential relative to an electrode of the active metal in metallic form, and
wherein the second layers do not exhibit uptake of cations of the active metal in electrochemical reactions at the first potential or wherein the second layers exhibit uptake of cations of the active metal in electrochemical reactions at the first potential at a slower rate than the first layers.
5 . The composite foil material of claim 1 , wherein the active metal is lithium, and wherein the first layers exhibit uptake of lithium cations in electrochemical reactions at a potential of from 0.0 V to 1.5 V relative to Li/Lit.
6 . The composite foil material of claim 5 , wherein the second layers exhibit slower uptake of lithium cations in electrochemical reactions at the potential of from 0.0 V to 1.5 V relative to Li/Li + as compared to the first layers.
7 . The composite foil material of claim 1 , wherein the active metal is sodium.
8 . The composite foil material of claim 1 , wherein the active metal is lithium.
9 . The composite foil material of claim 1 , wherein the first metal comprises a tin-rich alloy, an aluminum-rich alloy, an indium-rich alloy, a zinc-rich alloy, or a lead-rich alloy-.
10 . The composite foil material of claim 1 , wherein the plurality of first layers or the plurality of second layers is alloyed with the active metal.
11 . The composite foil material of claim 1 , which exhibits the hierarchical structure from roll bonding.
12 . The composite foil material of claim 1 , further comprising
a plurality of interlayers, where at least one interlayer is positioned between two first layers, or between two second layers.
13 . The composite foil material of claim 12 , wherein at least one interlayer comprises a metal different from the first metal and the second metal.
14 . An electrochemical cell comprising:
a cathode;
an anode, the anode comprising the composite foil material of claim 1 ; and
an electrolyte between the cathode and the anode.
15 . A method for preparing a composite foil material exhibiting a hierarchical structure comprising different regions of alternating first layers and second layers,
providing a composite foil material comprising:
a plurality of first layers comprising a first metal, which is a member selected from the group consisting of Al, Si, Zn, Ga, Ag, Cd, In, Sn, Sb, Au, Pb, Bi, and Mg; and
a plurality of second layers comprising a second metal, which is a member selected from the group consisting of Cu, Zn, Mg, Fe, Ni, Al, Zr, Hf, Nb, and Mo, wherein the hierarchical structure comprising from 8 to 512 first layers alternate with from 8 to 512 second layers, wherein individual layer thickness is between 0.05 μm to 2 μm, wherein the hierarchical structure comprises different regions of alternating first layers and second layers, and has an interface density of between 0.5 and 20 μm −1 , wherein at least some different regions of alternating first layers and second layers have different total thicknesses, different layer thicknesses, or different numbers of layers; and
subjecting the composite foil material to an electrochemical alloying process with an active metal, which is a member selected from the group consisting of lithium, sodium, potassium and magnesium; and wherein the active metal is less reactive toward the second metal than the first metal.
16 . The method of claim 15 , wherein subjecting the composite foil material to the electrochemical alloying process comprises:
contacting the composite foil material with an electrolyte containing cations of the active metal; and
applying an electric potential to the composite foil material to drive uptake of the active metal by the composite foil material.
17 . The method of claim 15 , wherein subjecting the composite foil material to the electrochemical alloying process comprises:
subjecting the composite foil material to an electrochemical reaction with cations of the active metal at a charging potential and a charging current, wherein the first layers preferentially react with cations of the active metal as compared to the second layers to form a charged composite foil material; and
subjecting the charged composite foil material to a discharge process using a discharge current, wherein the first layers preferentially release cations of the active metal as compared to the second layers to form a discharged composite foil material, wherein the discharge current is greater than or equal to the charging current.
18 . The method of claim 15 , wherein providing the composite foil material comprises:
roll bonding a layer of the first metal and a layer of the second metal to form a first roll-bonded structure; and
overlapping at least two first roll-bonded structures and subjecting to roll bonding to form a second roll-bonded structure.
19 . The method of claim 18 , wherein providing the composite foil material further comprises:
overlapping at least two second roll-bonded structures and subjecting to roll bonding to form a third roll-bonded structure.
20 . The composite foil material of claim 1 , wherein the plurality of first layers or the plurality of second layers, or both the plurality of first layers and the plurality of second layers contain submicron sized layers.
21 . The composite foil material of claim 1 , wherein from 8 to 64 first layers alternate with from 8 to 64 second layers.
22 . The composite foil material of claim 1 , wherein at least some different regions of alternating first layers and second layers have total thicknesses that are the same.
23 . The method of claim 15 , wherein at least some different regions of alternating first layers and second layers have total thicknesses that are the same.