LAYERED ELECTRODE MATERIALS AND METHODS FOR RECHARGEABLE ZINC BATTERIES

Abstract

Layered electrode materials, positive electrodes, rechargeable zinc batteries, and methods are provided. A layered electrode material for use in a rechargeable zinc battery includes a plurality of active metal slab layers in a layered configuration. The active metal slab layer includes a plurality of redox active metal centers and a closely-packed anionic sublattice. A plurality of interlamellar spaces separate adjacent active metal slab layers in the layered configuration. The interlamellar space includes at least one pillar species. The layered electrode material has a combined average metal oxidation state in a range of +3 to +4 in an initial charged state. The layered electrode material accepts solvated zinc cations via intercalation into the interlamellar space upon reduction.

Claims

1. A layered electrode material for use in a rechargeable zinc battery, the layered electrode material comprising: a plurality of active metal slab layers in a layered configuration, wherein an active metal slab layer comprises: a plurality of redox active metal centers, M; and a closely-packed anionic sublattice; a plurality of interlamellar spaces, wherein an interlamellar space separates adjacent active metal slab layers in the layered configuration, and wherein the interlamellar space comprises at least one pillar species; wherein the layered electrode material has a combined average metal oxidation state in a range of +3 to +4 in an initial charged state; and wherein the layered electrode material accepts solvated zinc cations via intercalation into the interlamellar space upon reduction.

2. The layered electrode material of claim 1, wherein at least one of the redox active metal centers comprises manganese.

3. The layered electrode material of claim 1, wherein the redox active metal centers comprise at least one of chromium, iron, nickel, and cobalt.

4. The layered electrode material of claim 1, wherein the at least one pillar species comprises water molecules.

5-6. (canceled)

7. The layered electrode material of claim 1, wherein the at least one pillar species comprises a cationic pillar species.

8-9. (canceled)

10. The layered electrode material of claim 1, wherein the anionic sublattice comprises a single layer.

11. The layered electrode material of claim 1, wherein the anionic sublattice comprises a plurality of layers.

12. (canceled)

13. The layered electrode material of claim 1, wherein the anionic sublattice comprises an anionic species comprising at least one of an oxide, a sulfide, a fluoride, a hydroxide, a borate, a phosphate, a sulfate, a silicate, and an aluminate.

14. The layered electrode material of claim 1, wherein the anionic sublattice comprises a combination of two or more anionic species.

15-17. (canceled)

18. The layered electrode material of claim 7, wherein the cationic pillar species comprises at least one cationic species or other ions which include an element selected from a group consisting of hydrogen, ammonium, tetraalkylammonium, alkali metals, alkaline earth metals, d-block metals, and f-block metals.

19. (canceled)

20. The layered electrode material of claim 1, wherein adjacent slab layers have a d-spacing between 7 angstroms and 20 angstroms.

21. A composite positive electrode for use in a rechargeable zinc battery comprising the layered electrode material of claim 1.

22. The composite positive electrode of claim 21, further comprising at least one conductive additive, and at least one binder.

23. A rechargeable zinc battery comprising the layered electrode material of claim 1.

24. (canceled)

25. The layered electrode material of claim 1, wherein the layered electrode material is synthesized using a wet chemistry or solid-state process.

26-32. (canceled)

33. The composite positive electrode of claim 22, wherein the layered electrode material, the at least one conductive additive, and the at least one binder form a homogeneous mixture created by dry mixing.

34. The composite positive electrode of claim 22, wherein the layered electrode material, the at least one conductive additive, and the at least one binder form a homogenous mixture created by slurry mixing in a solvent.

35-38. (canceled)

39. A rechargeable zinc battery comprising: a positive electrode comprising a layered electrode material, wherein the layered electrode material comprises: a plurality of active metal slab layers in a layered configuration, wherein an active metal slab layer comprises: a plurality of redox active metal centers, M; and a closely-packed anionic sublattice; a plurality of interlamellar spaces, wherein an interlamellar space separates adjacent active metal slab layers in the layered configuration, and wherein the interlamellar space comprises at least one pillar species; wherein the layered electrode material has a combined average metal oxidation state in a range of +3 to +4 in an initial charged state; and wherein the layered electrode material accepts solvated zinc cations via intercalation into the interlamellar space upon reduction; a negative electrode comprising zinc; an electrolyte for ionically coupling the negative electrode to the positive electrode, wherein the electrolyte comprises a zinc salt dissolved in water; and a separator disposed between the positive electrode and the negative electrode, wherein the separator is wetted by the electrolyte.

40. The rechargeable zinc battery of claim 39, wherein the negative electrode comprises zinc metal.

41-42. (canceled)

43. The rechargeable zinc battery of claim 39, wherein the electrolyte includes zinc ions in a range from 0.1 molar to 4 molar.

44. (canceled)

45. The rechargeable zinc battery of claim 39, wherein the electrolyte has a pH value between 1 and 7.

46. (canceled)

47. The rechargeable zinc battery of claim 39, wherein the rechargeable zinc battery has an average discharge voltage in the range of 1-3 V.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0058] The drawings included herewith are for illustrating various examples of articles, methods, and apparatuses of the present specification. In the drawings:

[0059] FIG. 1 is a side view of a zinc metal secondary cell, according to an embodiment;

[0060] FIG. 2 is a diagrammatic representation of solvation of a zinc cation, according to an embodiment;

[0061] FIG. 3A is a crystal structure representation of a layered electrode material, according to an embodiment;

[0062] FIG. 3B is a crystal structure representation of the layered electrode material of FIG. 3A after zinc intercalation, according to an embodiment;

[0063] FIG. 4 is a crystal structure representation of electrolytic manganese dioxide;

[0064] FIG. 5 is a crystal structure representation of a layered electrode material comprising birnessite, according to an embodiment;

[0065] FIG. 6 is a crystal structure representation of a layered electrode material comprising buserite, according to an embodiment;

[0066] FIG. 7 is a graph illustrating X-ray diffraction (XRD) patterns for layered -NiOOH and an aluminum-stabilized, hydrated layered -phase of NiOOH (Ni.sub.0.8Al.sub.0.2(CO.sub.3).sub.0.1OOH.0.66H.sub.2O), according to an embodiment;

[0067] FIG. 8 is a graph illustrating X-ray diffraction (XRD) patterns for synthetic layered hydrate -phases of MnO.sub.2, of general formula A.sub.0.2MnO.sub.2.1.2H.sub.2O wherein the cationic pillar species A.sup.+ is either potassium, tetramethylammonium or tetrabutylammonium, according to an embodiment;

[0068] FIG. 9 is a is a schematic diagram of a zinc battery, according to an embodiment;

[0069] FIG. 10 is a graph illustrating galvanostatic cycling of a zinc metal battery using birnessite as the positive electrode material, including a charge/discharge voltage response over time and an evolution of specific capacity over cycle number, according to an embodiment;

[0070] FIG. 11A is a scanning electron microscope image for a hydrated layered K.sub.0.26Ni.sub.1/3Mn.sub.1/3Co.sub.1/3O.sub.2.nH.sub.2O synthesized from LiNi.sub.1/3Mn.sub.1/3Co.sub.1/3O.sub.2, according to an embodiment;

[0071] FIG. 11B is a graph illustrating n X-ray diffraction pattern for a hydrated layered K.sub.0.26Ni.sub.1/3Mn.sub.1/3Co.sub.1/3O.sub.2.nH.sub.2O synthesized from LiNi.sub.1/3Mn.sub.1/3Co.sub.1/3O.sub.2, according to an embodiment;

[0072] FIG. 12 is a graph illustrating a first galvanostatic discharge/charge voltage profile of a zinc metal battery using a hydrated layered K.sub.0.26Ni.sub.1/3Mn.sub.1/3Co.sub.1/3O.sub.2.nH.sub.2O as the positive electrode material, according to an embodiment;

[0073] FIG. 13 is a graph illustrating galvanostatic cycling of a zinc metal battery using LiNi.sub.1/3Mn.sub.1/3Co.sub.1/3O.sub.2 as the positive electrode material, according to an embodiment;

[0074] FIG. 14A is a scanning electron microscope image for a hydrated layered Na.sub.0.3Ni0.sub.2.0.7H.sub.2O, according to an embodiment;

[0075] FIG. 14B is a graph illustrating an X-ray diffraction pattern for a hydrated layered Na.sub.0.3Ni0.sub.2.0.7H.sub.2O, according to an embodiment; and

[0076] FIG. 15 is a graph illustrating a first galvanostatic discharge profile of a zinc metal battery using the Na.sub.0.3NiO.sub.2.0.7H.sub.2O as the positive electrode, according to an embodiment.

DETAILED DESCRIPTION

[0077] Various apparatuses or processes will be described below to provide an example of each claimed embodiment. No embodiment described below limits any claimed embodiment and any claimed embodiment may cover processes or apparatuses that differ from those described below. The claimed embodiments are not limited to apparatuses or processes having all of the features of any one apparatus or process described below or to features common to multiple or all of the apparatuses described below.

[0078] As used herein, the term about, when used in reference to a pH value, means the pH value given +/0.5 unless otherwise stated. When the term about is used in reference to a pH range, it is understood that the forgoing definition of about is to be applied to both the lower limit and upper limit of the range.

[0079] As used herein, the term about, when used in reference to a molar concentration (molar) value, means the molar value +/0.1 molar, unless otherwise stated. When the term about is used in reference to a molar range, it is understood that the forgoing definition of about is to be applied to both the lower limit and upper limit of the range.

[0080] As used herein, the term between, when used in reference to a range of values such as a molar range or a pH range, means the range inclusive of the lower limit value and upper limit value, unless otherwise stated. For example, a pH range of between 4 to 6 is taken to include pH values of 4.0 and 6.0.

[0081] The present disclosure relates generally to improving the performance of secondary electrochemical cells that use intercalation of zinc ions within a layered material to store and deliver energy. Intercalation refers to the reversible inclusion or insertion of zinc ions in a crystal structure of the electrode material. Electrode materials disclosed herein are capable of intercalating solvated Zn.sup.2+ during discharge of a zinc metal battery. The electrode materials may include various transition metals and transition metal oxides. The layered materials may include various design features that improve performance of the zinc battery over conventional zinc batteries. In particular, the layered materials may improve voltage, capacity, charge/discharge rate, and energy efficiency of the zinc battery.

[0082] Various transition metals may be used to provide increased voltage as compared to existing zinc metal batteries (e.g. those using vanadium). One example of a transition metal that can increase the voltage of a zinc metal battery compared to vanadium (as used in known cells) is manganese. Various structures of manganese dioxide (MnO.sub.2) have been examined in zinc metal batteries in mild (pH 4-6) aqueous electrolytes. In particular, U.S. Pat. No. 6,187,475 to Ahanyang Seung-Mo Oh and Kunpo Sa-Heum Kim describes a zinc-ion battery. The zinc-ion battery includes an electrolytic manganese dioxide positive electrode. In rechargeable ZnMnO.sub.2 batteries using mild aqueous electrolytes, the Mn.sup.4+ is reduced to Mn.sup.3+ during discharge and Mn.sup.3+ is oxidized back to Mn.sup.4+ during charge. The average discharge voltage is around 1.4 V. Various proposed mechanisms have been suggested for this reversible reaction including intercalation/deintercalation of Zn.sup.2+ or H.sup.+ from water, and several different conversion reactions resulting in phase transformations of the initial MnO.sub.2 phase. Ideally, the structure of a positive electrode of a zinc-ion battery would not be converted to a different phase during cycling of the battery.

[0083] The layered materials disclosed herein may include one or more transition metals. The transition metal may be manganese. The layered material may be a hydrated, layered manganese oxide. The hydrated, layered manganese oxide may be chalcophanite (ZnMn.sub.3O.sub.7.3H.sub.2O) or from the birnessite group. The hydrated, layered manganese oxide may accommodate solvated zinc cations via a reversible intercalation/deintercalation mechanism while maintaining its original layered structure.

[0084] The transition metal of the layered material may be nickel, iron, cobalt, or chromium. The transition metal may provide increased voltages in zinc metal batteries. The transition metal includes a basal-plane spacing sufficient to fit or accommodate solvated Zn.sup.2+ cations. Transition metals nickel, iron, cobalt, and chromium have been used extensively in Li-ion batteries as positive electrode materials (e.g. LiFePO.sub.4 (LFP), LiCoO.sub.2 (LCO), LiNi.sub.0.33Co.sub.0.33Mn.sub.0.33O.sub.2 (NMC), and LiNi.sub.0.8Co.sub.0.15Al.sub.0.05O.sub.2 (NCA)), albeit to intercalate/deintercalate Li.sup.+ rather than Zn.sup.2+ and using non-aqueous electrolytes instead of aqueous electrolytes. Of these Li-ion positive electrode materials, LCO, NMC, and NCA are layered structures, but possess basal-plane spacings (4.6 to 4.8 ) that are too small to fit solvated Zn.sup.2+ cations.

[0085] Referring now to FIG. 1, shown therein is a secondary electrochemical cell 100, according to an embodiment. The cell 100 can be used for the storage and delivery of electrical energy.

[0086] The cell 100 may be used in a rechargeable zinc-ion battery. The rechargeable zinc-ion battery may be used for the delivery of electrical energy by the intercalation of solvated zinc ions into the interlayer space of the layered materials disclosed/described herein upon discharge. The rechargeable zinc-ion battery may be used for the storage of electrical energy by the deintercalation of the solvated zinc ions upon charge. The rechargeable zinc-ion battery may have an average discharge voltage in the range of 1-3 V.

[0087] The secondary cell 100 includes a zinc metal negative electrode 10, an aqueous electrolyte, a positive electrode 20, and a separator 3.

[0088] The negative electrode 10 includes a first face 11 and a second face 12. The negative electrode 10 includes a zinc metal layer 2.

[0089] The negative electrode 10 includes a current collector 1 for collecting current. The current collector 1 includes a first face 13 and a second face 14. The zinc metal layer 2 is adhered to the first face 13 and the second face 14 of the current collector 1. The current collector 1 may be an electrically conductive metal foil.

[0090] In an embodiment, the negative electrode 10 may be formed using a slurry casting or rolling of a paste or dough containing zinc metal onto a metal foil substrate (current collector 1).

[0091] The positive electrode 20 includes a first face 15 and a second face 16.

[0092] The positive electrode 20 reacts reversibly with Zn.sup.2+ cations. The positive electrode 20 includes an active material 4 that electrochemically reacts with Zn.sup.2+ in the electrolyte in a reversible manner. Reversible refers to the ability to recover at least 90% of electrical charge stored in the material upon charging the cell 100.

[0093] The active material 4 may be a layered material (for example, layered material 300 of FIG. 3). The active layer 4 may be a hydrated layered active material. The layered material may include a transition metal. The layered material may include a transition metal oxide. The transition metal may be manganese (Mn), chromium (Cr), iron (Fe), nickel (Ni), or cobalt (Co). The layered material may include various design features such as slab layer composition, interlamellar space composition, and d-spacing that improve performance of the zinc battery over conventional zinc batteries. The layered material may improve voltage, capacity, charge/discharge rate, and energy efficiency of the zinc battery 100.

[0094] The positive electrode 20 includes a current collector 5 for collecting current. The current collector 5 includes a metal substrate. The current collector 5 includes a first face 17 and a second face 18. The current collector 5 may be coated on the first and second faces 17, 18 with a mixture including an electrochemically active material, a conductive additive, and a binder. The current collector 5 of the positive electrode 20 may be a metal foil.

[0095] In an embodiment, the positive electrode 20 may be formed using a slurry casting or rolling of a paste or dough containing active material 4 onto a metal foil substrate (current collector 5).

[0096] The aqueous electrolyte ionically couples the negative electrode 10 to the positive electrode 20. The pH of the electrolyte may be between about 1 and 7. The pH of the electrolyte may be between about 4 and 6.

[0097] The electrolyte includes a zinc salt dissolved in water. The zinc salt may be dissolved so that zinc ions are present in the electrolyte in a range from about 0.001 molar to 10 molar. The zinc salt may be dissolved so that zinc ions are present in the electrolyte in a range from about 0.1 molar to about 4 molar. The zinc salt may be selected from a group of zinc salts including zinc sulfate, zinc acetate, zinc citrate, zinc iodide, zinc chloride, zinc perchlorate, zinc bis(trifluoromethanesulfonyl)imide, zinc nitrate, zinc phosphate, zinc triflate, zinc tetrafluoroborate, and zinc bromide.

[0098] The separator 3 is wetted by the electrolyte. The separator 3 is positioned in the cell 100 such that the separator 3 prevents the negative electrode 10 and positive electrode 20 from making physical contact with each other. The separator may be disposed between the negative electrode 10 and the positive electrode 20. The separator 3 may be porous.

[0099] In an embodiment, the cell 100 includes a thin film electrode stack configuration where the negative electrode 10 includes a current collector 1 which is coated on both sides by a layer of zinc metal 2, the separator 3 which is soaked in electrolyte and prevents the negative electrode 10 and positive electrode 20 from contacting each other, and the positive electrode 20 which includes an active layer 4 which is coated on both sides of the current collector 5.

[0100] Referring now to FIG. 2, shown therein is a diagrammatic representation 200 of solvation of a zinc cation, according to an embodiment.

[0101] A zinc cation 204 is solvated with a shell of six water molecules 208 in an octahedral configuration to produce a solvated zinc cation 212. The total solvated zinc cation 212 is the predominant form under which zinc is present in a mildly acidic electrolyte. One requirement for zinc-ion batteries (e.g. cell 100 of FIG. 1) that differs from previous intercalation batteries (e.g. lithium-ion) is a need for interlayer water molecules or another solvent shell surrounding the zinc cation. This is because zinc ions are divalent (i.e. have a 2+ charge). The high charge density causes the zinc ion to tightly bind water or other solvent molecules from the electrolyte such that it is surrounded by a solvent shell, as shown in FIG. 2. For the zinc ion to travel through the electrode material it needs to be able to carry the solvent shell with the zinc ion to the reaction site.

[0102] Referring now to FIG. 3A, shown therein is a layered electrode material 300 for use in a rechargeable zinc battery, according to an embodiment. The layered material 300 may form part of a positive electrode of the zinc battery (e.g. active layer 4 of positive electrode 20 of battery 100 of FIG. 1). The layered material 300 may improve one or more properties of the battery, such as voltage, capacity, the rate at which the battery can be charged/discharged, and energy efficiency.

[0103] The layered electrode material 300 includes a plurality of closely-packed redox active metal slab layers 320. The active metal slab layers 320 each include a plurality of redox active metal centers 360, M, in a close-packed anionic sublattice.

[0104] The active metal slab layer 320 includes a closely-packed anionic sublattice. The anionic sublattice may comprise a single layer or a plurality of layers. The anionic sublattice may comprise a anionic species. The anionic species may include one or more of an oxide, a sulfide, a fluoride, a hydroxide, a borate, a phosphate, a sulfate, a silicate, an aluminate, or the like. The anionic species may include a combination of two or more anionic species. For example, the combination of two or more anionic species may include an oxyhydroxide, an oxyfluoride, a hydroxysulfate, or the like.

[0105] Adjacent slab layers 320 are separated by an interlamellar space 350. The interlamellar space 350 is occupied by one or more pillar species 340. The pillar species 340 impact a distance between the active metal slabs 320, typically referred to as basal plane spacing or d-space 330. The d-spacing 330 is defined as the sum of the height of the interlamellar space 350 and the height of one slab layer 320.

[0106] The layered material 300 may have a d-spacing ranging from 7 angstroms to 20 angstroms. The layered electrode material 300 accepts solvated zinc cations via intercalation into the interlamellar space 350 upon reduction.

[0107] The pillar species 340 may include one or more of water molecules, hydroxide ions, an anionic species (anionic pillar species), a cationic species (cationic pillar species), or ions of one or multiple distinct species.

[0108] The anionic pillar species may include one or more of a nitrate, a sulfate, a carbonate, a phosphate, a borate, a hydroxide, a chloride, an iodide, a perchlorate, a fluoride, or the like.

[0109] The cationic pillar species may include one or more cationic species or other ions which include an element taken from a group including hydrogen, ammonium, tetraalkylammonium, alkali metals, alkaline earth metals, d-block metals, and f-block metals.

[0110] The pillar species 340 may be covalently bonded to atoms in the active metal slab layer 320.

[0111] In particular, the layered material 300 may be a hydrated layered material (i.e. with water molecules in between the slab layers 320). The hydrated layered material (water molecules in between slab layers 320) may be an effective host for reversible zinc intercalation.

[0112] Hydrated layered materials 300 may have a d-space 330 ranging from 7 angstroms to 20 angstroms. A layered material 300 including a monolayer of water may have a d-space 330 of approximately 7 angstroms. The presence of water and/or ions between the active slab layers 320 may create enough space for reversible zinc intercalation to occur. The d-spaces 330 for hydrated layered materials may range from 7 to 20 .

[0113] The layered material 300 may be used as an active material of a positive electrode (e.g. active material 4 of FIG. 1). The layered material 300 may include a transition metal or a transition metal oxide. The layered material 300 may include various design features such as slab layer composition, interlamellar space composition, and d-spacing that improve performance of the zinc battery over conventional zinc batteries. The layered material 300 may improve voltage, capacity, charge/discharge rate, and energy efficiency of the zinc battery.

[0114] The layered material 300 may include one or more transition metals. The layered material 300 may include manganese. The layered material may be a hydrated, layered manganese oxide. The hydrated, layered manganese oxide may be chalcophanite (ZnMn.sub.3O.sub.7.3H.sub.2O) or from the birnessite group. The hydrated, layered manganese oxide may accommodate solvated zinc cations via a reversible intercalation/deintercalation mechanism while maintaining the original layered structure. The layered material 100 may be selected, composed, or designed such that the layered material 100 (and thus the positive electrode) is not converted to a different phase during cycling of the battery. The transition metal of the layered material 100 may be nickel, iron, cobalt, or chromium.

[0115] The transition metal may provide increased voltages in zinc metal batteries. The transition metal includes a basal-plane spacing sufficient to fit or accommodate solvated Zn.sup.2+ cations. Transition metals which may provide increased voltages in zinc metal batteries include nickel, iron, cobalt, and chromium.

[0116] Referring now to FIG. 3B, shown therein is the layered material 300 of FIG. 3A after intercalation of solvated Zn.sup.2+ 310 in the interlamellar space 350, according to an embodiment. In addition to the pillar species 340, the interlamellar space 350 includes intercalated zinc ions.

[0117] The intercalation of solvated Zn.sup.2+ 310 occurs in concomitance with a reduction of the redox active metal centers 360 in the active metal slab layers 320. The reduction of the redox active metal centers 360 may include a reduction from M.sup.5+ to M.sup.4+, M.sup.4+ to M.sup.3+, or M.sup.3+ to M.sup.2+ (where M is the active metal center 360).

[0118] The intercalation/deintercalation of the solvated Zn.sup.2+ into/from the layered material 100 may have very fast kinetics. The very fast kinetics may be attributed to a large d-spacing 330 of the layered material 300. U.S. Pat. No. 9,780,412 to Adams et. al. suggests very fast kinetics for the intercalation/deintercalation of solvated Zn.sup.2+ into/from the layered compound is attributed to the large d-spacing of 10.8 angstroms for Zn.sub.0.25V.sub.2O.sub.5.nH.sub.2O in a zinc battery incorporating vanadium.

[0119] Intercalation in the layered material 300 requires zinc ions 310 to diffuse through the electrode material (e.g. active material 4 of FIG. 1, layered material 300) to reach a redox active metal center 360. Compared to crystal structures characterized by a three-dimensional interstitial network for guest ions (e.g, EMD as shown in FIG. 4), the layered material 300 may provide a simpler, unimpeded path for zinc ions 310 to travel along and through the electrode material to reach the active metal center 360.

[0120] Example MnO.sub.2 structures are illustrated in FIGS. 4 to 6. Various MnO.sub.2 compounds may be suitable for use in layered material 300. MnO.sub.2 compounds may be capable of intercalating zinc ions.

[0121] Referring now to FIG. 4, shown therein is a structural representation of electrolytic manganese dioxide (EMD) 400. EMD 400 is an example of a crystal structure characterized by a three-dimensional interstitial network for guest ions. EMD 400 is a mixture of -MnO.sub.2 and -MnO.sub.2. EMD 400 includes 11 and 12 intercalation tunnels. Zn.sup.2+ diffusion is difficult in the 12 or even 11 intercalation tunnels of EMD 400. The difficulty of Zn.sup.2+ diffusion suggests tunneled EMD (and similarly structured compounds) may be less suitable for use in a rechargeable zinc battery than layered material 300.

[0122] Referring now to FIGS. 5 and 6, shown therein are structural representations of birnessite-type manganese oxides -MnO.sub.2. In an embodiment, the layered intercalation material 300 includes a birnessite-type manganese oxide -MnO.sub.2 such as birnessite (shown in FIG. 5) or buserite (shown in FIG. 6). The interlamellar space (e.g. interlamellar space 350 of FIG. 3) of the birnessite-type manganese oxide may include one or more layers of water. The one or more layers of water may contribute to the ability of the birnessite-type manganese oxide to accommodate zinc ions 310 through intercalation.

[0123] Referring specifically to FIG. 5, shown therein is a structural representation of birnessite 500. Zn.sup.2+ diffusion is facile in the 1 intercalation planes of birnessite 500. Birnessite 500 includes a monolayer of water 504 in the interlamellar space 350, called a monolayer hydrate (MLH) material. Birnessite 500 may have a d-spacing 330 of approximately 7 .

[0124] Referring now to FIG. 6, shown therein is a structural representation of buserite 600. Zn.sup.2+ diffusion is facile in the 2 intercalation planes of buserite 600 (even more so than in birnessite 500). Buserite 600 includes a bilayer of water 604 in the interlamellar space, called a bilayer hydrate (BLH) material. Buserite 600 may have a d-spacing (e.g. d-spacing 330 of FIG. 3) of approximately 10 .

[0125] The difference in d-spacing between birnessite 500 and buserite 600 can be attributed to the monolayer of water 504 and bilayer of water 604, respectively. A wider interlamellar space may provide a lower energy barrier for Zn.sup.2+ to diffuse in the solid. Accordingly, layered materials such as birnessite 500 and buserite 600 that are swollen by water may be particularly suitable material types for use in zinc-ion batteries (due to an ability to accommodate solvated zinc intercalation).

[0126] In another embodiment, the layered material is a nickel oxyhydroxide. In a particular embodiment, the nickel oxyhydroxide may be an -NiOOH.

[0127] -Ni(OH).sub.2/-NiOOH can be used as the positive electrode active material in nickel-metal-hydride, nickel-cadmium, and nickel-zinc batteries. The layered structure of the -Ni.sup.2+ and -Ni.sup.3+ phases comprises of brucite-type slabs well-ordered along a c-axis. In rechargeable batteries using alkaline electrolytes, this phase reversibly cycles by intercalation/deintercalation of H.sup.+.

[0128] -Ni(OH).sub.2/-NiOOH structures have similar stacking of brucite slabs (i.e. acting as active slab layers 320) as in -Ni(OH).sub.2/-NiOOH, but with water molecules and anionic species occupying the interlamellar space 350. Upon standing in alkaline media, -Ni(OH).sub.2/-NiOOH reverts to -phase, which is the thermodynamically stable phase.

[0129] -Ni(OH).sub.2/-NiOOH can be stabilized by substituting trivalent cations into the slab layers 320 and anions in the interlamellar space 350 which compensate for an excess positive charge in the slabs 320. The -Ni.sup.3+ oxyhydroxide may accommodate solvated Zn.sup.2+ due to an increased d-spacing 330 compared to the -Ni.sup.3+ oxyhydroxide.

[0130] Referring now to FIG. 7, shown therein is a graph 700 illustrating X-ray diffraction (XRD) patterns for -NiOOH and stabilized -NiOOH, having the formula: Ni.sub.0.8Al0.2(CO.sub.3).sub.0.1OOH.0.66H.sub.2O. The Ni.sub.0.8Al0.2(CO.sub.3).sub.0.1OOH.0.66H.sub.2O is an aluminum-stabilized, hydrated layered -phase of NiOOH. The d-spacing 330 is increased from 4.6 for -NiOOH to 8.0 for -Ni.sub.0.8Al0.2(CO.sub.3).sub.0.1OOH.0.66H.sub.2O.

[0131] In an embodiment, the layered intercalation material 300 is a birnessite-type manganese oxide having a general formula A.sub.xMn.sup.3-4+O.sub.2.nH.sub.2O. The interlamellar space 350 of the birnessite-type manganese oxide may comprise one or more monovalent or divalent cationic species, A.

[0132] A may be selected specifically to increase the height of the interlamellar space 350. For example, small alkali and alkaline earth cations such as Na.sup.+, K.sup.+, or Ca.sup.2+ present in natural birnessite minerals may be substituted by bulkier tetraalkylammonium cations, such as tetramethylammonium (TMA.sup.+) or tetrabutylammonium (TBA.sup.+).

[0133] Referring now to FIG. 8, shown therein is a graph 800 illustrating X-ray diffraction (XRD) patterns for synthetic layered hydrate -phases of MnO.sub.2, of general formula A.sub.0.2MnO.sub.21.2H.sub.2O wherein the cationic pillar species A.sub.+ is either potassium, tetramethylammonium or tetrabutylammonium, according to an embodiment. The birnessite-type manganese oxide may include substituted bulkier tetraalkylammonium cations.

[0134] As illustrated in graph 600, the substitution of K.sup.+ by TMA.sup.+ and TBA.sup.+ results in a d-spacing 330 increase from 7.0 to 9.5 for TMA.sup.+, and from 7.0 to 16.9 for TBA.sup.+, while maintaining the integrity of the redox active slabs 320 and the mean oxidation state of manganese (about +3.8).

[0135] The electrode is for use in an electrochemical device (e.g. cell 100 of FIG. 1). The electrode made from the layered materials disclosed herein may be a positive electrode. The electrochemical device includes a positive electrode, a negative electrode, and an aqueous electrolyte. The aqueous electrolyte may be any mildly acidic (pH 4 to 7). The aqueous electrolyte may be an otherwise suitable electrolyte known in the art. The electrochemical device is a zinc rechargeable battery. The positive electrode includes a hydrated layered material as described herein (for example, layered material 300 of FIG. 3). The negative electrode may be zinc, a zinc alloy, or a mixture of any two or more such materials. The electrochemical device may include a separator for separating the negative and positive electrodes. The separator may be a porous separator.

[0136] Referring now to FIG. 9, shown therein is a zinc metal battery 900, according to an embodiment. The zinc battery 900 is shown during discharge under an electrical load 902.

[0137] The battery 900 includes a negative electrode 904, a positive electrode 908, an electrolyte 912, and an external circuit 916. During discharge, the external circuit 916 delivers power to an electrical load 902. Electrons are supplied from the oxidation of zinc metal from the negative electrode 904 into zinc cations 920. These zinc cations 920 solvate and migrate through the electrolyte 912 to intercalate in the interlamellar space of the positive electrode active material of the positive electrode 908.

[0138] The negative electrode 904 includes zinc. The negative electrode 904 may be formed substantially of zinc metal. The negative electrode 904 may be formed substantially of a zinc alloy. The negative electrode 904 may be a mixture of zinc metal and zinc alloy.

[0139] The positive electrode 908 includes a layered material (e.g. layered material 300 of FIG. 3). The layered material comprises an active material (e.g. active material 4 of FIG. 1). The layered material comprises a plurality of active metal slab layers (e.g. active metal slab layer 320 of FIG. 3).

[0140] The electrolyte 912 ionically couples the negative electrode 904 to the positive electrode 908. The electrolyte 912 includes a zinc salt dissolved in water. The salt may be dissolved so that zinc ions are present in the electrolyte 912 in a range from about 0.001 molar to 10 molar. The zinc salt may be dissolved so that zinc ions are present in the electrolyte 912 in a range from about 0.1 molar to 4 molar. The zinc salt may be selected from a group including zinc sulfate, zinc acetate, zinc citrate, zinc iodide, zinc chloride, zinc perchlorate, zinc bis(trifluoromethanesulfonyl)imide, zinc nitrate, zinc phosphate, zinc triflate, zinc tetrafluoroborate, and zinc bromide. The pH of the electrolyte 912 may be between 1 and 7. The pH of the electrolyte 912 may be between 4 and 6.

[0141] At the negative electrode 904, zinc metal is oxidized into Zn.sup.2+ cations (e.g. zinc cation 204 of FIG. 2). The Zn.sup.2+ cations solvate into the electrolyte 912.

[0142] At the positive electrode 908 redox active metal centers, M, (for example, redox metal centers 360 of FIG. 3) of the active metal slabs are reduced from M.sup.5+ to M.sup.4+, M.sup.4+ to M.sup.3+, or M.sup.3+ to M.sup.2+ by electrons transported through the external circuit 916.

[0143] Solvated zinc cations 210 are intercalated into the interlamellar space 350 between the slab layers 320. In a rechargeable zinc metal battery, the oxidation of zinc metal (also referred to as stripping) and the Zn.sup.2+ intercalation are fully reversible. Upon charge, solvated Zn.sup.2+ ions are deintercalated from the positive electrode material 908, diffuse through the electrolyte 912, and are reduced to zinc metal (also referred to as plating).

[0144] Referring now to FIG. 10, shown therein is a graph 1000 illustrating galvanostatic cycling of a zinc metal battery, according to an embodiment. The zinc metal battery may be zinc battery 400 of FIG. 9. The zinc metal battery comprises a zinc foil negative electrode, 1 M ZnSO.sub.4+0.1 M MnSO.sub.4 in water electrolyte, and a zinc birnessite/buserite (Zn.sub.xMnO.sub.2.nH.sub.2O) compound as the positive electrode active material is shown. The graph 1000 includes a first panel 1000a illustrating a discharge/charge voltage response over time, and a second panel 1000b illustrating an evolution of specific capacity over cycle number.

[0145] The exact composition of the zinc birnessite/buserite material is unknown since buserite (BLH) is a thermodynamically unstable compound which dehydrates to birnessite (MLH). Drying of the electrodes is likely to convert the material to birnessite prior to assembling the cell and re-soaking in the aqueous electrolyte. It is unclear whether the buserite BLH phase re-forms after the cell is assembled and injected with electrolyte. Regardless, the birnessite/buserite cycles well in the zinc cell with an average discharge voltage of 1.4 V and a specific capacity of approximately 140 mAh/g.

[0146] The layered materials of the present disclosure (e.g. layered material 300 of FIG. 3) and methods of manufacture thereof may utilize targeted chemical composition.

[0147] In an embodiment, the targeted chemical composition is K.sub.0.22Ni.sub.1/3Mn.sub.1/3Co.sub.1/3O.sub.2.nH.sub.2O. The mixture of Ni, Mn and Co in the active slab layers (e.g. active slab layers 320 of FIG. 3) follows design considerations for active materials used as positive electrodes in lithium ion rechargeable batteries (LiNi.sub.1/3Mn.sub.1/3Co.sub.1/3O.sub.2, NMC). The composition of the interlamellar space (e.g. interlamellar space 350 of FIG. 3), however, is tailored for use in zinc metal batteries.

[0148] Referring now to FIG. 11A, shown therein is a scanning electron microscope (SEM) image 1100a of a synthesized K.sub.0.22Ni.sub.1/3Mn.sub.1/3Co.sub.1/3O.sub.2.H.sub.2O material. The K.sub.0.22Ni.sub.1/3Mn.sub.1/3Co.sub.1/3O.sub.2.nH.sub.2O material is a hydrated, layered material. The K.sub.0.22Ni.sub.1/3Mn.sub.1/3Co.sub.1/3O.sub.2.nH.sub.2O material can be synthesized from LiNi.sub.1/3Mn.sub.1/3Co.sub.1/3O.sub.2. The powder comprises very small particles agglomerated together.

[0149] Referring now to FIG. 11B, shown therein is an XRD pattern 1100b for the synthesized K.sub.0.22Ni.sub.1/3Mn.sub.1/3Co.sub.1/3O.sub.2.nH.sub.2O of FIG. 11A.

[0150] The sharp peak 1104 with greatest intensity at 7.0 is associated with the basal plane spacing 330 for K.sub.0.22Ni.sub.1/3Mn.sub.1/3Co.sub.1/3O.sub.2.nH.sub.2O. The interlamellar space of K.sub.0.22Ni.sub.1/3Mn.sub.1/3Co.sub.1/3O.sub.2.nH.sub.2O contains K.sup.+ cations and water molecules. The stoichiometry of K.sup.+ between the active slab layers was identified by energy dispersive X-ray spectroscopy (EDX) during the SEM analysis. The introduction of K.sup.+ and H.sub.2O increased the height of the interlamellar space by 2.24 relative to the starting NMC material (d-spacing=4.76 ).

[0151] Referring now to FIG. 12, shown therein is a graph 1200 of a first galvanostatic cycle of a zinc metal battery including a zinc foil negative electrode, 1 M ZnSO.sub.4/H.sub.2O electrolyte, and K.sub.0.22Ni.sub.1/3Mn.sub.1/3Co.sub.1/3O.sub.2.nH.sub.2O as the positive electrode active material (e.g. active material 4 of FIG. 1).

[0152] The cell was discharged first where solvated Zn.sup.2+ is intercalated into the interlamellar space 350. The discharge provided an average voltage of 1.5 V with a sloping profile associated with the reduction of mixed Ni.sup.4+/Ni.sup.3+, Mn.sup.4+/Mn.sup.3+, and Co.sup.4+/Co.sup.3+ redox centers 360 in the active slab layers 320.

[0153] Upon charge, the solvated Zn.sup.2+ was deintercalated from the interlamellar space 350 with near 100% coulombic efficiency.

[0154] Referring now to FIG. 13, shown therein is a graph 1300 of a first galvanostatic cycle of a zinc metal battery including the parent material LiNi.sub.1/3Mn.sub.1/3Co.sub.1/3O.sub.2 as the positive electrode. Graph 1300 provides a comparative example to graph 1200. The fully lithiated material was charged first to deintercalate Li.sup.+ in order to create vacancies in the interlamellar space 350. Upon discharge, however, only residual Li.sup.+ in the electrolyte which was originally in the structure was able to intercalate into the interlamellar space 350 since the d-spacing 330 is too small (4.76 ) to accommodate solvated Zn.sup.2+. This is in contrast with the cell of FIG. 12, where no Li.sup.+ is present in the electrolyte (only Zn.sup.2+).

[0155] In another aspect, methods of preparing hydrated layered electrode materials disclosed herein (e.g. layered material 300 of FIG. 3) are provided. The layered electrode materials maybe be prepared from transition metal precursors and chemical intercalation of alkali metals ions.

[0156] Prepared layered electrode materials may have a similar morphology to that of the transition metal precursors. Metal hydroxide, carbonate or oxide precursors may be used. A targeted chemical composition process may be used. One example of targeted chemical composition is Na.sub.0.3Ni0.sub.2.0.7H.sub.2O. The Na.sub.0.3Ni0.sub.2.0.7H.sub.2O composition may be achieved from Ni(OH).sub.2 or NiCO.sub.3 precursors prepared by a coprecipitation method or from NiO. The sodium may be introduced as NaOH, Na.sub.2CO.sub.3 or Na.sub.2O.sub.2 concurrently to calcining the precursor between 600 C. to 900 C.

[0157] Following the incorporation of sodium into the layered structure, hydration can be realized by mild oxidation in aqueous media.

[0158] Referring now to FIG. 14A, shown therein is a scanning electron microscope image for the hydrated layered Na.sub.0.3Ni0.sub.2.0.7H.sub.2O. As illustrated in FIG. 14A, the resulting hydrated layered Na.sub.0.3Ni0.sub.2.0.7H.sub.2O maintained the morphology of the NiO precursor, with a very narrow particle size distribution.

[0159] Referring now to FIG. 14B, shown therein is a graph 1400b of an XRD pattern for the hydrated layered Na.sub.0.3Ni0.sub.2.0.7H.sub.2O. The graph 1400b illustrates the successful incorporation of water molecules in the interlamellar space 50, with a d-spacing 330 of 7.1 significantly wider than the anhydrous NaNiO.sub.2 intermediate. Accordingly, this kind of synthesis strategy can be widely applied to obtain a variety of hydrated layered electrode materials with controlled morphology (e.g. for use as layered material 300 of FIG. 3).

[0160] Referring now to FIG. 15, shown therein is a first galvanostatic discharge curve 1500 for a zinc metal battery including Na.sub.0.3Ni0.sub.2.0.7H.sub.2O material as a positive active material of a positive electrode (e.g. active material 4 of positive electrode 20 of FIG. 1). Intercalation of solvated Zn.sup.2+ into the interlamellar space 350 between the NiO.sub.2 slabs (e.g. active metal slabs 20 of FIG. 3) of Na.sub.0.3Ni0.sub.2.0.7H.sub.2O provided an average discharge voltage of 1.7 V and a specific capacity of about 180 mAh/g.

[0161] The following paragraphs describe the experimental methods used herein.

[0162] All electrochemical cells were assembled using a homemade plate design comprising a rubber gasket sandwiched between two acrylic plates. The acrylic plates were bolted together and housed the electrode stack (negative/separator/positive). The electrode stack was compressed together between Ti plates by external screws (torque of 2 in.-lb) which also served as electrical connections.

[0163] The zinc-ion cells (e.g. zinc ion cells shown in FIGS. 10, 12, 13, and 15) were assembled using a zinc negative electrode, 5.5 cm5.5 cm), a separator with 3 mL of electrolyte, and a positive electrode (5 cm5 cm) comprising a coating of active material on a current collector. The zinc negative electrode was a piece of zinc foil (30 m thick, Linyi Gelon LIB Co., Ltd.). The separator used was glass fiber filter membrane (300 m thick). The electrolyte was 1 M ZnSO.sub.4 dissolved in water for all cells with the exception of the cell of FIG. 10 where 1 M ZnSO.sub.4+0.1MnSO.sub.4 in water was used.

[0164] The positive electrodes were prepared by casting a slurry of 87.5 wt. % active material, 6 wt. % Vulcan XC72 carbon black (Cabot Corp.), 2 wt. % activated carbon, 0.1 wt. % oxalic acid, and 4 wt. % PTFE binder in a 2-propanol/water mixture (1:1 vol. ratio) as the solvent onto a sheet of carbon paper (P50, Fuel Cell Store) using a doctor blade. PTFE powder (1 m particles, Sigma-Aldrich) was first dispersed into pure 2-propanol (20 wt. % dispersion) before adding to the slurry mixture. After casting, the electrode was dried at room temperature. The electrolyte used in this cell was 1 M ZnSO.sub.4+0.1 M MnSO.sub.4 in water. The separator used was paper filter (160 m thick). The zinc negative electrode was a piece of zinc foil (30 m thick, Linyi Gelon LIB Co., Ltd.). The cells were cycled at 0.2 mA/cm.sup.2 at room temperature (232 C.).

[0165] The active materials were synthesized with the exception of the LiNi.sub.1/3Co.sub.1/3Mn.sub.1/3O.sub.2 (NMC) used in the positive electrode of the cell shown in FIG. 13, which was purchased from MTI Corp.

[0166] The layered nickel oxyhydroxides shown in FIG. 7 were prepared by a room-temperature precipitation/oxidation method. Briefly, -NiOOH was formed by slowly adding a 0.8 M solution of NaOH to a 0.3 M solution of NiSO.sub.4.6H.sub.2O. The light green precipitate was the vacuum filtered and washed with water until the pH of the filtrate was neutral. This product was then placed in a solution containing 3 M NaOH and 5 wt. % NaOCl. The green product quickly turned to black and the mixture was allowed to react for 2.5 hours before filtering and washing again. The final black powder was dried at 60 C. overnight. The Al-stabilized NiOOH (Ni.sub.0.8Al.sub.0.2(CO.sub.3).sub.0.1OOH.0.66H.sub.2O) was synthesized by slowly adding a solution containing 0.4 M NiSO.sub.4.6H.sub.2O and 0.1 M Al.sub.2(SO.sub.4).sub.3.18H.sub.2O to a second solution containing 2 M NaOH and 0.1 M Na.sub.2CO.sub.3. The light green precipitate was the vacuum filtered and washed with water until the pH of the filtrate was neutral. This product was then placed in a solution containing 3 M NaOH and 5 wt. % NaOCl on ice. The green product quickly turned to black and the mixture was allowed to react for 2.5 hours. The mixture temperature was never allowed to rise above 20 C. Finally, the black product was filtered, washed, and dried for 3 days at room temperature.

[0167] The layered materials shown in FIG. 8 were prepared from chemical oxidation of Mn.sup.2+ by hydrogen peroxide in the presence of tetramethylammonium [TMA] hydroxide). Typically, 20 mL of a mixed aqueous solution of 0.6 M TMAOH and 3 wt % H.sub.2O.sub.2 was added rapidly to 10 mL of 0.3 M MnCl.sub.2.4H.sub.2O aqueous solution. The resulting dark brown suspension was stirred overnight at room temperature. This colloidal suspension of birnessite monosheets was used as the precursor for all three materials. K.sub.0.2MnO.sub.2.1.2H.sub.2O was obtained by mixing the colloidal suspension of the monosheets with a KCl aqueous solution. Typically, 50 mL of 1 M KCl aqueous solution was added dropwise to 50 mL of the colloidal suspension of MnO.sub.2 monosheets (0.02 mol/L) at room temperature. After the solution was left to stand at room temperature for 24 hours, the resulting black precipitate was filtered off, washed with deionized water, and dried at 60 C. in a preheated vacuum oven overnight. TMA.sub.0.2MnO.sub.2.1.2H.sub.2O was obtained by simple filtration of the nanosheet suspension followed by washing with deionized water and drying at 60 C. in a preheated vacuum oven overnight. TBA.sub.0.2MnO.sub.2.1.2H.sub.2O was obtained by redispersing TMA.sub.0.2MnO.sub.2.1.2H.sub.2O powder (60 mmol) in a TBAOH solution (1.5 L, 0.1 mol/L). The suspension was left to stir at room temperature for 48 hours and the dried aggregate was separated by filtration followed by washing with deionized water and drying at 60 C. in a preheated vacuum oven overnight.

[0168] The positive electrode active material of the cell shown in FIG. 10 was synthesized by a room temperature solution method. In a typical synthesis, 600 mL of an aqueous solution containing 0.53 mol/L (M) Mn(CH.sub.3CO.sub.2).sub.2.4H.sub.2O and 0.1 M Mg(CH.sub.3CO.sub.2).sub.2.4H.sub.2O was slowly added to 600 mL of 13.3 M NaOH over a period of an hour. A 600 mL aqueous solution of 0.2 M KMnO.sub.4 was prepared and added drop wise to the previous solution over 1 hour. The slurry was aged statically at room temperature for 15 days. The slurry was filtered and rinsed with water until the pH of filtered solution was below 9.5. An aliquot of the slurry was dried to obtain birnessite and the remaining aliquot was dispersed in 1.8 L water and allowed to age for 2 days to form stable buserite. Following that, the solid was collected to perform ion exchange of magnesium with zinc by dispersing solid in 1 L of 1 M ZnSO.sub.4 for 24 hours. Lastly, the product was filtered, rinsed with water, and dried at 60 C. in a preheated vacuum oven overnight.

[0169] The positive electrode active material (K.sub.0.22Ni.sub.0.33Co.sub.0.33Mn.sub.0.33O.sub.2.nH.sub.2O) characterized in FIG. 11 and used in the cell shown in FIG. 12 was synthesized starting with commercial NMC (MTI Corp.). In a typical synthesis, 80 g of commercial LiNi.sub.1/3Mn.sub.1/3Co.sub.1/3O.sub.2 was dispersed in 800 mL 1 M HCl with stirring to protonate and remove Li. The HCl solution was refreshed everyday for 10 days. After 10 days, the solid was filtered, rinsed with water until filtered solution was neutral, and dried at 60 C. in a preheated vacuum oven overnight. 8 g of previously dried protonated product was dispersed in 800 mL of 0.04 M tetramethylammonium hydroxide solution and allowed to stir for 1 day to suspend solid in solution. The suspension was flocculated in 2 L of 1.5 M KCl and allowed to stir for one day. Flocculated solid was filtered, rinse with water, and dried at 60 C. in a preheated vacuum oven overnight.

[0170] The positive electrode active material (Na.sub.0.3NiO.sub.2.0.7H.sub.2O) characterized in FIG. 14 and used in the cell shown in FIG. 15 was synthesized by a solid-state method. In a typical synthesis, NiO was mixed and ground with 20% mol excess of Na.sub.2O.sub.2 using a mortar and pestle. The solid was transferred to an alumina crucible and placed in a tube furnace under O.sub.2 atmosphere. The tube furnace was heated up to 600 C. at a rate of 5 C./min, held for 8 hours at 600 C., and cooled to room temperature at 5 C./min. Once cooled, the product was transferred to a 300 mL solution of 1.6 mol excess Na.sub.2S.sub.2O.sub.8 with pH >10.5 using NH.sub.4OH. The final product was filtered, rinsed with water, and dried at 60 C. in a preheated vacuum oven overnight.

[0171] While the above description provides examples of one or more apparatus, methods, or systems, it will be appreciated that other apparatus, methods, or systems may be within the scope of the claims as interpreted by one of skill in the art.