WO2019027481A1

WO2019027481A1 - Rechargeable copper oxide electrodes for electrochemical applications

Info

Publication number: WO2019027481A1
Application number: PCT/US2017/045629
Authority: WO
Inventors: Timothy N. LAMBERT; Jonathan DUAY
Original assignee: National Technology & Engineering Solutions Of Sandia, Llc
Priority date: 2017-08-04
Filing date: 2017-08-04
Publication date: 2019-02-07

Abstract

A rechargeable electrochemical battery is disclosed. The battery includes a cell container; a positive electrode comprising a positive electrode active material; a negative electrode comprising a negative electrode active material; a separator disposed between the positive and negative electrodes; and an electrolyte comprising an alkaline aqueous solution. One of the positive electrode active material or the negative electrode active material comprises a copper oxide-based material and a bismuth-based additive. The rechargeable electrochemical battery includes bismuth additives and formulations of copper oxide-based electrodes that allow for the copper oxide-based material to be electrochemically cycled in alkaline electrolyte.

Description

RECHARGEABLE COPPER OXIDE ELECTRODES FOR ELECTROCHEMICAL

APPLICATIONS

STATEMENT OF GOVERNMENT INTEREST

This invention was developed under Contract No. DE-NA0003525 awarded by the United States Department of Energy/National Nuclear Security Administration. The Government has certain rights in this invention.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Non-Provisional Patent Application Serial No. 15/669,587, filed August 4, 2017, which is hereby incorporated by reference in its entirety.

FIELD OF THE INVENTION

This application generally relates to electrochemical battery cells. This application relates more specifically to novel copper oxide electrodes in an alkaline aqueous secondary, or rechargeable, battery and use therein.

BACKGROUND OF THE INVENTION

Primary batteries are designed for single time use and discarded upon discharge. In particular, the electrochemical discharge reaction is irreversible, rendering the battery not rechargeable. On the contrary, secondary batteries are designed to be recharged and reused multiple times. In a primary battery during discharge, the negative active material in the anode is oxidized and provides electrons to the external circuit, while the positive active material in the cathode is reduced and consumes electrons from the external circuit.

A secondary battery utilizes a reaction that is reversible when a charging current is applied to the battery, with the current "recharging" the battery. The chemical reactions that occur during discharge must be able to be reversed by introduction of this charging current. When the secondary battery is being recharged, the positive active material in the cathode is now oxidized, producing electrons, and the negative active material in the anode is now reduced, consuming electrons. This charging current thus restores the electrodes to their original chemical composition.

In secondary batteries, traditional electrode materials such as cathode materials suffer several drawbacks. Many traditional cathodes, e.g., manganese oxides, lose charge capacity over several charge cycles, are Coulombically inefficient, or possess elevated impedance or internal resistance that negatively affect battery discharge. As these traditional batteries progress through charging cycles ("cycling"), battery performance deteriorates. Thus, there is a need for electrode materials that have improved properties and can improve battery performance in rechargeable batteries. Copper oxides have been used as active materials in positive electrodes previously in primary (non-rechargeable) batteries, with initial reports of a battery employing copper oxide in aqueous caustic alkali electrolyte in combination with a zinc anode dating to de Lalande and Chaperon in 1881. However, CuO as a cathode material in aqueous alkaline batteries has only occurred in primary systems to date, with the systems losing charge capacity rapidly upon cycling.

In certain rechargeable battery technologies, such as Li-ion batteries, copper oxide has been employed in both a cathode and an anode material. However, copper oxide, e.g. CuO and/or Cu20, and hydrates of copper oxide, e.g. Cu(OH)2, as a cathode material in for rechargeable alkaline batteries has not occurred due to substantial limitations, which have prevented their adoption for rechargeable alkaline batteries. Instead, attempts at creating an economically desirable rechargeable alkaline battery have typically employed manganese oxides such as electrolytic manganese oxides as electrodes, which on their own suffer from poor cycling at high depths of discharge due to irreversible side reactions such as formation of Mn304 or ZnMn204 in cases where paired with Zn anode.

Alternatively, copper oxide has already been shown to be more efficient and have a higher capacity than electrolytic manganese di-oxide (EMD) under high discharge rate (high current) conditions in primary systems. Given this, plus the higher gravimetric capacity of CuO (2 electrons = 674 mAh/g) than EMD (2 electrons = 616 mAh/g), it is desirable to have a system comprising re-chargeable copper oxide electrodes, which could enable secondary batteries that are competitive with, or better than, secondary batteries having manganese dioxide cathodes.

Even further, copper oxide has the advantage of being environmentally benign, of low cost, easy to synthesize and with a high theoretical gravimetric capacity (674 mAh/g). When copper oxide is paired with an appropriate anode (e.g. Zn, 820 mAh/g), batteries of sufficient energy density at a sufficiently low cost to be useful for stationary (grid) applications could be realized. However, it would be environmentally and economically prohibitive to utilize a copper oxide system in an alkaline electrolyte primary battery due to the necessity to replace the battery after each discharge.

Further, alkaline electrolyte battery systems are more suitable than others in applications where high currents are required, because of the high conductivity of the electrolyte. Therefore, it is desired to create a copper oxide electrode in an alkaline electrolyte battery that can function as a secondary (rechargeable) battery for these applications.

In view of the above, an advantage of the present invention is to provide a rechargeable, or secondary, battery with a copper oxide cathode. Another advantage of the present invention is to provide a rechargeable electrochemical battery cell that whose characteristics are competitive with, or better than, manganese dioxide cathodes.

Still another advantage is that copper oxide can also pair with another electrode and serve as the anode to provide a rechargeable (secondary) battery.

In view of the above, an advantage of the present invention is to provide a rechargeable (secondary) battery with a copper oxide cathode and a zinc anode.

Similarly, copper oxide can serve as the anode in a rechargeable electrochemical battery system when paired with appropriate cathodes such as nickel hydroxide, providing a rechargeable electrochemical battery cell comprised of CuO/Ni(OH)2.

None of the above inventions and patents, taken either singularly or in combination, is seen to describe the instant invention as claimed. What is needed is a system and/or method that satisfies one or more of these needs or provides other advantageous features. Other features and advantages will be made apparent from the present specification. The teachings disclosed extend to those embodiments that fall within the scope of the claims, regardless of whether they accomplish one or more of the aforementioned needs.

SUMMARY OF THE INVENTION

The above objectives are met and the above disadvantages of the prior art are overcome by a secondary, or rechargeable, battery of the present invention.

One embodiment relates to a rechargeable electrochemical battery. The battery includes a cell container; a positive electrode comprising a positive electrode active material; a negative electrode comprising a negative electrode active material; a separator disposed between the positive and negative electrodes; and an alkaline electrolyte. One of the positive electrode active material or the negative electrode active material comprises a copper oxide (CuO) -based material and a bismuth (Bi)-based additive.

Another embodiment relates to a rechargeable battery cell. The battery cell includes a cell container; a cathode comprising a cathode active material, wherein the cathode material comprises copper oxide-based material comprising a bismuth-based additive; an anode comprising an anode active material; and an electrolyte. Yet another embodiment relates to a rechargeable battery cell. The battery cell includes a cell container; a cathode comprising a cathode active material, wherein the cathode material comprises copper oxide-based material comprising a bismuth-based additive; an anode comprising an anode active material; and an electrolyte. The bismuth-based additive is selected from the group consisting of a Bi-salt, Bi-metal, Bi-complex including Bi-alkoxide, Bi-amido and Bi-organo species. The copper oxide-based material is selected from the group consisting of Ag2Cu203, Cu(OH)2, a mixed metal oxide, a mixed metal oxide comprising both copper and bismuth, a binary mixed metal oxide, and a single physical entity comprised of two discrete mixed phases.

In certain embodiments, at least one of the positive electrode active material or the negative electrode active material further includes graphite and polytetrafluoroethylene.

Another embodiment relates to a secondary (rechargeable) electrochemical battery that includes a positive electrode (cathode) comprising a positive electrode active material, a negative electrode (anode) comprising a negative electrode active material, a separator disposed between the positive and negative electrodes, and an alkaline electrolyte, wherein at least one of either the positive electrode active material or the negative electrode active material includes copper oxide and a bismuth-based additive. Alternately, CuO, Cu20, Cu(OH)2 as well as others described below, may be substituted for the copper oxide in the negative electrode active material.

In certain embodiments, the bismuth-based additive is a second independent species

(such as Bi-salt, Bi-metal, Bi-complex including Bi-alkoxide, Bi-amido Bi-organo species), or a Bismuth chalcogenide (e.g. Bi2S3, Bi2Se3, Bi2Te3 and other stoichiometries) or Bismuth pnictide, physically mixed with active copper-based species (e.g. CuO).

Alternative exemplary embodiments relate to other features and combinations of features as may be generally recited in the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The application will become more fully understood from the following detailed description, taken in conjunction with the accompanying figures, wherein like reference numerals refer to like elements, in which:

FIG. 1 is a schematic layout for an exemplary secondary battery containing a CuO electrode. FIG. 2 is a graph demonstrating discharge profiles of a Zn/CuO alkaline cell formed without a Bismuth (Bi) additive.

FIG. 3 is a graph demonstrating discharge profiles of a Zn/CuO alkaline cell comprising a Bi additive

FIG. 4 is a graph showing CuO gravimetric capacity versus cycle number for the Zn/CuO cells observed in FIGS. 2 and 3.

FIG. 5 is a graph displaying the gravimetric discharge capacity of CuO electrode with and without bismuth additive cycling in the absence of Zn.

FIG. 6 is a graph displaying the Obtained Energy Density (based on the area and thickness of the electrodes and separators only) versus cycle number for the Zn/CuO cells with and without additive.

FIG. 7 is a graph showing CuO electrode without a Bi additive cycling in the absence of Zn versus an Hg/HgO reference electrode.

FIG 8 is a graph showing CuO electrode with a Bi additive cycling in the absence of Zn versus an Hg/HgO reference electrode.

FIG. 9 is a graph showing the effect of particle size on the discharge capacity of CuO electrode cycling with additive.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Before turning to the figures which illustrate the exemplary embodiments in detail, it should be understood that the application is not limited to the details or methodology set forth in the following description or illustrated in the figures. It should also be understood that the phraseology and terminology employed herein is for the purpose of description only and should not be regarded as limiting. Unless otherwise indicated herein, reference to copper oxide (CuO) includes copper oxide-based materials as further described below.

Disclosed herein are embodiments of a rechargeable battery having copper oxide- based electrodes comprising a bismuth additive that allow the copper oxide-based material to be electrochemically cycled in alkaline electrolyte. This technical advance involves the discovery of additives and specific formulations of copper oxide-based electrodes that allow for the copper oxide-based material to be electrochemically cycled in alkaline electrolyte. The copper oxide can serve as the cathode, e.g. when cycled versus a Zn anode, or as the anode, e.g., when cycled versus a Ni(OH)2 cathode.

As such, it represents for the first time the demonstration of copper oxide as a viable electrode in an alkaline rechargeable battery. This demonstration of a copper oxide-based electrode with excellent stability and energy capacity in an alkaline electrolyte is a significant and unexpected advancement. Prior patent and academic literature describes such electrodes in batteries as being limited to primary battery applications. Exemplary embodiments of this application for a secondary Zn/CuO battery and a CuO/Ni(OH)2 electrochemical cell is provided. Also within the scope of the disclosed invention are

Referring next to FIG. 1, a schematic layout of an exemplary rechargeable CuO/Zn battery cell 100 is shown. A plastic shim 1 is positioned adjacent a copper mesh current collector 2 in order to provide compression, zinc composite electrode 3 is coupled with a separator 4, separating the zinc composite electrode 3 from the copper oxide composite electrode 5, which is coupled with a nickel mesh 6. The battery cell 100 is encased in plastic casing 7, which acts as a cell container. The copper mesh 2 and nickel mesh 6 are both coupled in electrical communication with nickel tabs 8, which act as electrical leads to the battery cell 100.

Referring next to FIGS. 2 and 3, discharge profiles of two independent Zn/CuO alkaline cells are demonstrated. The first example (FIG. 2) does not include a Bi-additive and the second example (FIG. 3) includes a Bi-additive. The battery without our additive (FIG. 2) demonstrates a typical cycle failure for a CuO electrode with failure observed after only a few cycles. In contrast, the cell containing a Bi additive continues to cycle (FIG. 3). In FIG. 3, the graph represents a typical cycle for a battery formed by including a Bi additive to the cell. This graph demonstrates that the electrode can now be considered a secondary electrode due to its re-chargeability and that the additive has stabilized both the higher and lower voltage plateaus during discharge. Up to 50 cycles of charge and discharge have been demonstrated experimentally, and indications are the cycling would continue past this number as well.

Referring to FIG. 4, the observed capacity (mAh/g) obtained from CuO material 50 cycles for the two cells observed for FIGS. 2 and 3 is shown. As in FIG. 2, the graph shows that without the Bi additive the battery dies quickly, within 10 cycles. With the Bi additive (FIG. 3), the cell cycles well with only a slow capacity loss observed over time. The Bi additive stabilizes copper oxide phases that are formed upon oxidation of Cu (i.e., a copper oxide, e.g. CuO, CU2O, and CU2O3). Bi additive is also useful in other copper oxide-based cathodes such as AgCu02, whereby the Cu(III)-based electrode may discharge at higher voltages, as well as Ag2Cu203 electrodes and even copper hydroxides Cu(OH)2. Copper oxide-based materials as used herein may include by way of example and not limitation, CuO, CU2O and copper hydroxides, and hydrated oxides of copper generally. The Bi additive can be incorporated in numerous ways, such as: using Bi-oxides (e.g. B12O3) in the electrode formulation, Bi-chalcogenides, Bi-pnictides or Bi-halides adding soluble Bi-salts and Bi- complexes to the electrode or electrolyte directly, or preparing mixed Bi_xCui_-xO materials used similarly. In another embodiment, other additive formulations, e.g., M_xCu(i-_X)0 (where M = any metal cation) may be prepared, whereby the added metal cation is used to increase the overall cell voltage. In an embodiment, M is silver Referring to FIG. 5, this graph shows the discharge capacity of CuO electrode cycling in the absence of Zn. That is the CuO is acting as the anode and cycling versus Ni(OH)2. In the absence of zinc, the electrode without the bismuth additive cycles beyond 10 cycles indicating that the addition of bismuth not only improves the stability of the CuO electrode, but also plays a role in preventing zinc transfer from the anode to the cathode in the case where zinc is the anode and copper oxide is the cathode.

Referring to FIG. 6, this graph shows the obtained energy density (Wh/L), based on the area and thickness of the electrodes and separators, versus the cycle number for Zn/CuO cells with and without the Bi additive.

FIG. 7 is a graph showing CuO electrode without a Bi additive cycling in the absence of Zn versus an Hg/HgO reference electrode. That is the CuO is acting as the anode and cycling versus Ni(OH)2. The data shows loss of capacity upon cycling as well as instability in the voltage during discharge.

FIG. 8 is a graph showing CuO electrode with a Bi additive cycling in the absence of Zn versus an Hg/HgO reference electrode. That is the CuO is acting as the anode and cycling versus Ni(OH)2. The Bi additive increases the cycle life and stabilizes the first and second voltage discharge plateaus. FIG. 9 is a graph showing the effect of electrode size on the discharge capacity of CuO electrode cycling. In particular, the graph shows a comparison of an electrode formed from nanosized (< 50 nm diameter) CuO particles and one formed from microsized (< 10 μιη) CuO particles. Based on the experimental data shown, and without being bound by theory, it is believed that the particle size of the active copper oxide has a limited role in the capacity performance of CuO electrodes with the bismuth additive.

The electrodes used to develop the data for the above figures were CuO composite electrodes were prepared by combining X wt% CuO, Y wt% Additive, 30 wt% graphite, and 5 wt% Polytetrafluoroethylene (PTFE) solids with a mortar and pestle (where X + Y = 65). CuO, additive, and graphite powders were mixed thoroughly, and then a PTFE dispersion was added and mixed until uniform. Isopropyl alcohol was then added to produce a malleable putty. The cathode material was rolled out to a thickness of - 0.40 mm, baked at 60 °C for 1 hour, and cut to desired dimensions. One rectangle of cathode material was pressed onto a Ni current collector (Ni gauze spot welded to a Ni tab) at 662 MPa. For the electrodes containing a bismuth additive, the bismuth was added as B12O3 directly into the CuO electrode

In one or more embodiments, the alkaline electrolyte may be an aqueous potassium hydroxide with concentrations ranging from 0.01 to 20 molar (M), or an aqueous sodium hydroxide with concentrations ranging from 0.01 to 20 M, or an aqueous lithium hydroxide with concentrations ranging from 0.01 to 12 M. Alternately, solid or gelled electrolytes may be used.

In an embodiment, the alkaline aqueous solution may be selected from one or more of the group consisting of an aqueous potassium hydroxide with concentrations at 5.9 M, or an aqueous sodium hydroxide with concentrations at 4.4 M, or an aqueous lithium hydroxide with concentrations ranging from 7.5 M. These ranges represent the highest conductivity properties.

The alkaline aqueous solution may be selected from one or more of the group consisting of an aqueous potassium hydroxide, aqueous sodium hydroxide or an aqueous lithium hydroxide with concentrations ranging from 0.01 to 20 M. In an embodiment, the aqueous potassium hydroxide concentration is 0.01 M to 3 M, in another it is 0.01 M to 6 M and in another it is 0.01 M to 20 M. In an embodiment, the aqueous sodium hydroxide concentration is 0.01 M to 3 M, in another it is 0.01 M to 6 M and in another it is 0.01 M to 20 M. In an embodiment, the aqueous lithium hydroxide concentration is 0.01 M to 3 M, in another it is 0.01 M to 8 M (or saturated solution).

In an embodiment, the positive electrode active material or said negative electrode active material may include X% CuO by weight and Y% bismuth-based additive by weight, wherein X + Y is less than or equal to 98%, wherein X and Y do not equal zero. The remainder includes materials including, but not limited to binders and conductive additives. In at least one preferred embodiment X > 85. In other embodiments X > 50, and in still other embodiments, X > 25. The positive electrode active material or said negative electrode active material may include conductive carbon and a binder. In an embodiment, the conductive carbon may be graphite and the binder polytetrafluoroethylene.

In an embodiment, the bismuth-based additive may be independent species physically mixed with copper oxide. The bismuth additive may be a Bi-salt, Bi-metal, Bi-complex including Bi-alkoxide, Bi-amido, Bi-organo species, or a Bismuth chalcogenide, e.g. B12S3, Bi2Se3, Bi2Te3, bismuth pnictide and other stoichiometries thereof or a Bismuth pnictide. The bismuth additive may be added to the electrolyte.

In another embodiment, the cathode copper oxide may be AgCuC , Cu(OH)2, or a mixed metal oxide, e.g., M_xCui-_xO, where M = any metal cation, and 0.1 < x < 0.5. The copper oxide may also be a mixed metal oxide comprising both copper and bismuth, e.g. single phase Bi_xCui_-xO where 0.1 < x < 0.5.

The copper oxide may also be a ternary mixed metal oxide, e.g., Ml_xM2_yCui-_x-_yO, where Ml = any metal cation and M2 = any metal cation where Ml≠ M2

Further, the copper oxide may be a single physical entity comprised of two discrete mixed phases e.g. B12O3-CUO hybrid structure. The Bi-additive may be a Bismuth chalcogenide, e.g. B12S3, Bi2Se3, Bi2Te3 and other stoichiometries.

While the embodiments described herein refer to copper oxide-based materials, the battery electrodes may also be formed by copper sulfide-based materials, and which may be stabilized by the bismuth additive as well as other copper materials, e.g., borides, phosphides and the like.

While the exemplary embodiments illustrated in the figures and described herein are presently preferred, it should be understood that these embodiments are offered by way of example only. Accordingly, the present application is not limited to a particular embodiment, but extends to various modifications that nevertheless fall within the scope of the appended claims. The order or sequence of any processes or method steps may be varied or re- sequenced according to alternative embodiments.

It is important to note that the construction and arrangement of the rechargeable copper oxide electrodes for electrochemical applications as shown in the various exemplary embodiments is illustrative only. Although only a few embodiments have been described in detail in this disclosure, those skilled in the art who review this disclosure will readily appreciate that many modifications are possible (e.g., variations in sizes, dimensions, structures, shapes and proportions of the various elements, values of parameters, mounting arrangements, use of materials, colors, orientations, etc.) without materially departing from the novel teachings and advantages of the subject matter recited in the claims. For example, elements shown as integrally formed may be constructed of multiple parts or elements, the position of elements may be reversed or otherwise varied, and the nature or number of discrete elements or positions may be altered or varied. Accordingly, all such modifications are intended to be included within the scope of the present application. The order or sequence of any process or method steps may be varied or re-sequenced according to alternative embodiments. In the claims, any means-plus-function clause is intended to cover the structures described herein as performing the recited function and not only structural equivalents but also equivalent structures. Other substitutions, modifications, changes and omissions may be made in the design, operating conditions and arrangement of the exemplary embodiments without departing from the scope of the present application.

It should be noted that although the figures herein may show a specific order of method steps, it is understood that the order of these steps may differ from what is depicted.

Claims

1. A rechargeable electrochemical battery comprising:

a cell container;

a positive electrode comprising a positive electrode active material;

a negative electrode comprising a negative electrode active material;

a separator disposed between the positive and negative electrodes; and an alkaline electrolyte;

wherein at least one of the positive electrode active material or the negative electrode active material comprises a copper oxide-based material and a bismuth- based additive.

2. The rechargeable electrochemical battery of claim 1, wherein the alkaline

electrolyte is selected from one or more of the group consisting of an aqueous potassium hydroxide with concentrations ranging from 0.01 to 20 M; an aqueous sodium hydroxide with concentrations ranging from 0.01 to 20 M; and an aqueous lithium hydroxide with concentrations ranging from 0.01 to 12 M.

3. The rechargeable electrochemical battery of claim 1, wherein the at least one of the positive electrode active material or the negative electrode active material further comprises X% copper oxide-based material by weight and Y% bismuth-based additive by weight, wherein X + Y is less than or equal to 98% and wherein X and Y do not equal zero.

4. The rechargeable electrochemical battery of claim 3, wherein the at least one of the positive electrode active material or the negative electrode active material further comprises a conductive carbon and a binder.

5. The rechargeable electrochemical battery of claim 1, wherein the bismuth-based additive is an independent species physically mixed with the copper oxide-based material.

6. The rechargeable electrochemical battery of claim 1, wherein the bismuth-based additive is a Bi-salt, Bi-metal, Bi-compound, Bi-complex, including Bi-alkoxide, Bi-amido or Bi-organo species.

7. The rechargeable electrochemical battery of claim 1, wherein the bismuth-based additive is added to the electrolyte.

8. The rechargeable electrochemical battery of claim 1, wherein the positive electrode comprises AgCu02.

9. The rechargeable electrochemical battery of claim 1, wherein the positive

electrode comprises a copper oxide selected from the group consisting of Ag2Cu203, Cu(OH)2, a mixed metal oxide, a mixed metal oxide comprising both copper and bismuth, a binary mixed metal oxide, and a single physical entity comprised of two discrete mixed phases.

10. The rechargeable electrochemical battery of claim 1, wherein the copper oxide- based material comprises a hydrated oxide of copper.

11. The rechargeable electrochemical battery of claim 1, where the bismuth-based additive is a bismuth chalcogenide and/or bismuth pnictide.

12. A rechargeable battery cell comprising:

a cell container;

a cathode comprising a cathode active material, wherein the cathode material comprises copper oxide-based material comprising a bismuth-based additive; an anode comprising an anode active material;

a separator disposed between the cathode and the anode; and

an electrolyte.

13. The rechargeable electrochemical battery of claim 12, wherein the bismuth-based additive is a bismuth-salt, bismuth-metal, bismuth-complex including bismuth- alkoxide, bismuth-amido or bismuth-organo species.

14. The rechargeable electrochemical battery of claim 12, wherein the cathode

comprises AgCu02.

15. The rechargeable electrochemical battery of claim 12, wherein the cathode

comprises a copper oxide-based material selected from the group consisting of Ag2Cu203, Cu(OH)2, a mixed metal oxide, a mixed metal oxide comprising both copper and bismuth, a binary mixed metal oxide, and a single physical entity comprised of two discrete mixed phases.

16. The rechargeable electrochemical battery of claim 1, wherein the copper oxide- based material comprises a hydrated oxide of copper.

17. The rechargeable electrochemical battery of claim 1, where the Bi-additive is a bismuth chalcogenide or bismuth pnictide.

18. The cell of claim 16, wherein the anode active material comprises zinc.

19. A rechargeable electrochemical battery comprising:

a cell container;

a positive electrode comprising a positive electrode active material;

a negative electrode comprising a negative electrode active material;

wherein at least one of the positive electrode active material or the negative electrode active material comprises a copper sulfide-based material and a bismuth- based additive.