Safe ingestible battery that deactivates rapidly in a biological environment and method of making same
A passivating metal layer in the battery case forms an oxide layer to prevent electrolytic reactions, addressing the risk of tissue damage from ingested batteries and ensuring rapid deactivation, compatible with existing manufacturing processes.
Patent Information
- Application Number
- JP2025212641
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2020-08-26
- Filing Date
- 2025-12-01
- Publication Date
- 2026-02-24
AI Technical Summary
Existing batteries pose a significant risk of causing tissue damage when ingested due to electrolytic reactions in biological environments, and current safety measures fail to provide rapid deactivation and are not compatible with existing manufacturing processes.
Incorporating a passivating metal layer in the cathode or anode case of a battery that forms a metal oxide layer within 2 hours of exposure to biological fluids, inhibiting electrolytic reactions and reducing tissue damage.
The passivating metal layer effectively prevents significant tissue damage by forming a protective oxide layer, reducing electrolytic reactions and ensuring rapid deactivation of the battery in biological environments.
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Abstract
Description
[Technical Field]
[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Application No. 63 / 070,623, filed August 26, 2020, which is incorporated herein by reference in its entirety.
[0002] The present disclosure is directed generally to batteries, and more particularly to batteries that present a reduced or minimal risk of esophageal and / or gastrointestinal damage in a biologically conductive aqueous environment, such as if accidentally swallowed. [Background technology]
[0003] For example, billions of batteries are sold each year to power electronic devices including remote controls, flashlights, cameras, car key fobs, calculators, scales, musical greeting cards, glucometers, clocks, thermometers, virtual pet devices, hearing aids, laser pointers, games, toys, Internet of Things devices, etc. Unfortunately, children, pets, and the elderly are at risk of ingesting batteries due to their widespread presence in homes and throughout society.
[0004] Ingestion of batteries can cause devastating injuries. Gastrointestinal (GI) obstruction is a risk from the ingestion of any foreign body. However, battery ingestion is much more serious than the ingestion of a comparable-sized object, such as a coin, due to the tissue damage caused when the battery discharges in the GI tract. Electric current in conductive GI fluids can cause electrolysis, generating hydroxide ions, thereby creating long-term tissue damage in the gastrointestinal tract. Injuries from ingested batteries have resulted in acute injuries, including esophageal and other GI perforations, tracheolaryngeal fistulas, atrial esophageal fistulas, esophageal strictures, chemical burns, and vocal cord paralysis. These injuries can cause permanent, life-altering damage and even death. Case studies have shown that GI perforations in humans can occur as soon as 5 hours after battery ingestion. In pets, severe GI damage occurs even more rapidly, with transmural esophageal necrosis reported within 1 hour of ingestion in dogs and within 2 to 4 hours in cats.
[0005] Potentially less common, but no less problematic, are injuries to the ears, ear canals, and nasal passages that occur when batteries become lodged in these areas of the body.
[0006] Battery ingestion and injuries are on the rise as manufacturers create more powerful, more energy-dense batteries in smaller casings. This increase in battery power leads to a corresponding increase in the severity of injuries and fatalities from battery ingestion. While safety standards currently regulate locked battery compartments in toys, little has been done to design batteries themselves to increase their safety. In fact, as shown in Figure 1, the incidence of battery ingestion-related injuries continues to rise, even after the introduction of tamper-evident packaging for batteries and locked battery compartments.
[0007] Many attempts have been made to mitigate the problems caused by battery ingestion, however, no safely ingestible batteries currently exist that rapidly deactivate in biological environments.
[0008] Some early studies, reflected in U.S. Patent No. 5,069,989, were premised on the theory that acidic gastric fluids corroded the battery casing to the point that the alkaline electrolyte actually leaked from the cell and caused tissue damage. The proposed solution was a chromium-based alloy of stainless steel, which was thought to be resistant to acid corrosion. However, subsequent experience suggests that this theory and / or solution itself was invalid (as shown in Figure 1, with a steady increase in major or fatal outcomes per person, and confirmed by the inventors' own observations). Ingested batteries that remain in the esophagus are also known to cause injury before exposure to gastric fluids.
[0009] More recent studies have established hydrolysis as the cause of injury. Specifically, when a coin cell is lodged in the esophagus, the aqueous biological fluid surrounding the cell completes a closed circuit, discharging the cell and conducting an electrolytic current. The resulting reaction on and near the surface of the cell casing leads to the formation of hydroxide ions through hydrolysis, which causes alkali burns and potentially tissue perforation in the esophagus.
[0010] Exposure to electrolytic currents can be extremely damaging to tissues, as the pH rises to unsafe levels. In some instances, ingested batteries have caused debilitating injuries and even led to fatal events. One proposed solution involves constructing battery cells with a polymer fuse-type mechanism. U.S. Patent No. 9,130,200 discloses coating the anode with a polymer fuse that decomposes upon contact with bodily fluids. U.S. Patent No. 10,763,486 discloses the use of a "spacer" containing an electronically insulating material that dissolves, softens, or swells upon exposure to aqueous solutions, with the spacer configured to electronically isolate the cell when such a change occurs. Unfortunately, these proposed solutions are not commercially viable because they do not address the need for rapid battery deactivation and introduce inactive materials into batteries of a given size, thereby reducing the battery's volumetric capacity.
[0011] Similar efficacy issues arise in connection with the invention contemplated by U.S. Patent No. 10,700,362. Here, soluble acid is coated onto the cell in an amount intended to be sufficient to neutralize the amount of hydroxide produced by the hydrolysis reaction. However, given the cell capacity and the fact that unabated oxidation of the cathode results in a large, sustained increase in pH, the soluble acid volume is likely insufficient to prevent the loaded battery from causing significant damage over time. Such coatings are also susceptible to degradation at temperatures above ambient and relative humidity levels.
[0012] Each of the aforementioned battery designs and / or battery materials is generally incompatible with existing battery manufacturing processes. None of these proposals provides one or more components that can be utilized in established battery manufacturing lines, which in some circumstances can pose a significant obstacle to the large-scale adoption needed to address the harm caused by battery ingestion.
[0013] Additional proposals focused on the selection of specialized alloys believed to be resistant to reactions that form hydrogen gas during exposure to saliva-containing solutions. Patent Cooperation Treaty Publication No. 2013 / 106821 recommends the selection of materials with high hydrogen gas evolution overvoltages, including materials such as nickel, certain grades of stainless steel, titanium, gold, niobium, and tantalum. In particular, the disclosure is limited to reactive materials that produce an open-circuit voltage of at least 2.0 volts in non-aqueous electrolytes (the applicant claims a device with an open-circuit voltage of at least 2.8 volts, noting that the alkaline cell's lower output voltage of 1.5 V made it less likely to produce harmful electrolytic reactions). If the material's hydrogen gas evolution overvoltage were the only consideration for creating a safe battery, deactivation of the electrolytic reaction upon exposure to a conductive aqueous medium would be instantaneous and would not occur significantly. If material overvoltage were the only consideration, any one of the proposed metals would perform equally well, but as shown in Example i) and Figure 30, they would not perform.
[0014] More specifically, WO 2013 / 106821 fails to consider the current output when the electrodes come into contact with an aqueous medium when the cell circuit is fabricated using the proposed materials. For example, if an electrochemical cell using gold as the cathode electrode and stainless steel 430 as the anode electrode in a neutral salt solution is then subjected to a potential of 3 V, the resulting cell circuit will generate an electrolytic reaction that results in an increase in pH at the cathode and in the environment near the cathode. In other words, the proposed solution of using gold to cover the battery casing does not prevent electrochemical burns when the battery comes into contact with biological tissue. This effect is even more pronounced in the presence of simulated gastric fluid, as seen in Example i) and Figure 30, and occurs at 1.5 V, in contrast to WO 2013 / 106821, which teaches that 1.5 V alkaline batteries are unlikely to produce harmful electrolytic reactions. Therefore, the proposed mechanism of using any metal with a sufficiently high hydrogen gas overpotential, such as gold, will not provide the desired safety improvement.
[0015] Notably, the disclosure of WO 2013 / 106821 lacks design and manufacturing details to provide a battery that functions as a battery when used within a device and rapidly deactivates upon ingestion or exposure to a conductive aqueous medium. While many materials have been proposed, few have been tested, and none have successfully undergone the traditional manufacturing process of stamping or hem folding. At least some of the test devices, including titanium and stainless steel, were stamped into a cathode can shape, but the stamping process is known to form cracks in the outer layer that expose the underlying stainless steel, resulting in an unsafe battery if ingested. Additionally, some of the stamped stainless steel cans are sputter coated or plated with gold.
[0016] In WO 2013 / 106821, when gold, titanium, or S32750(+) / 55 Cu-32 Sn-12 Zn alloy-plated steel(-) pairs were tested, the S32750(+) / 55 Cu-32 Sn-12 Zn alloy-plated steel(-) pair in the anode was identified as the best embodiment. It should be noted that in other tests using stainless steel battery cases plated with nickel or gold, the gold lot performed poorly. This embodiment is inoperable, in part, because the gold coating, as noted in this disclosure, is incomplete, allowing exposure of the stainless steel, and in part, because gold does not form oxides. Figure 30 shows that no oxide grows on gold under potential in an aqueous conductive medium. Additionally, this reference discloses that duplex stainless steel has proven to be a strong candidate, even when coupled to a nickel anode.
[0017] U.S. Patent No. 10,103,361 proposes a three-layer coated material in which the surface of the coin cell casing is made of nickel with an intermediate layer of titanium underneath (all coated onto a conventional battery container). Under ingestion conditions, the nickel layer dissolves, exposing the titanium layer of the ingestion battery. While the outer nickel layer dissolves, hydrolysis reactions continue, causing tissue damage. Additionally, titanium coated materials are generally known not to function as described in this reference. Therefore, there remains a need to provide a battery that does not cause significant tissue damage when accidentally ingested. There is a need to provide one or more components of a battery that can be easily incorporated into existing battery manufacturing processes, enabling the production of batteries that do not cause significant tissue damage when ingested. More specifically, there is a need to provide a battery that does not generate significant amounts of hydroxide over an extended period of time at a potential difference above the electrolysis threshold of about 1.23 V when immersed in a conductive aqueous environment, such as the GI tract. Even more specifically, there is a need to provide a battery that includes a material that can grow a metal oxide layer within 2 hours, 1 hour, or 30 minutes after immersion in a conductive aqueous environment, such as the GI tract. Even more specifically, there is a need to provide a battery that includes a material that can reduce or eliminate electrolysis current within 2 hours, 1 hour, or 30 minutes after immersion in a conductive aqueous environment, such as the GI tract. [Prior art documents] [Patent documents]
[0018] [Patent Document 1] U.S. Patent No. 5,069,989 [Patent Document 2] U.S. Patent No. 9,130,200 [Patent Document 3] U.S. Patent No. 10,763,486 [Patent Document 4] U.S. Patent No. 10,700,362 [Patent Document 5] International Publication No. 2013 / 106821 [Patent Document 6] U.S. Patent No. 10,103,361 Summary of the Invention [Means for solving the problem]
[0019] The present disclosure is based in part on the discovery that the use of an oxide-forming passivating metal in the cathode or anode case of a battery inhibits or reduces the injury caused by that battery if ingested. Accordingly, one aspect described herein provides a battery including a cathode or anode case that includes a passivating metal.
[0020] The following embodiments are provided:
[0021] Embodiment 1 is a battery, a) an anode case; b) a cathode case containing a passivated metal; c) an electrochemical cell comprising an anode, a cathode, and a separator positioned between the anode and the cathode; d) a gasket between the anode case and the cathode case; The cell is one in which the passivating metal is present in a layer having a uniform or variable thickness between 100 nm and 400 μm.
[0022] Embodiment 2 is the battery of embodiment 1, wherein the passivating metal comprises Nb, Ta, an alloy thereof, or any combination thereof.
[0023] In a third embodiment, the passivated metal is 100 nm to 1 μm, 100 nm to 3 μm, 100 nm to 5 μm, 100 nm to 10 μm, 1 μm to 400 μm, 3 μm to 100 μm, 3 μm to 50 μm, 15 μm to 300 μm, 14 μm to 200 μm, 25 μm to 50 μm, 50 μm to 400 μm, 50 μm to 300 μm, 50 μm to 200 3. The battery of embodiment 1 or 2, wherein the conductive layer is present in a layer having a uniform or varying thickness of 50 μm to 175 μm, 55 μm to 400 μm, 55 μm to 300 μm, 55 μm to 200 μm, 60 μm to 400 μm, 60 μm to 300 μm, 60 μm to 200 μm, 200 μm to 300 μm, or 300 μm to 400 μm.
[0024] Embodiment 4 is the battery of any one of embodiments 1-3, wherein the cathode case consists essentially of a layer including a passivating metal, the layer having a uniform or variable thickness of 15 μm to 300 μm, 14 μm to 200 μm, or greater than 50 μm to 300 μm.
[0025] Embodiment 5 is the battery of any one of embodiments 1-4, wherein the cathode case comprises a layer including a passivating metal, the layer having a uniform or variable thickness of 15 μm to 300 μm, 14 μm to 200 μm, or greater than 50 μm to 300 μm.
[0026] Embodiment 6 is the battery of any one of embodiments 1-5, wherein the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof.
[0027] Embodiment 7 is the battery of any one of embodiments 1-6, wherein the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both; the exterior coating comprises Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof; and the exterior coating has a uniform or varying thickness of 100 nm to 7 μm, 100 nm to 5 μm, or 100 nm to 200 nm.
[0028] In an eighth embodiment, the cathode case is a cathode inner conductive layer; and a cathode passivation layer comprising a passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact.
[0029] In a ninth embodiment, the cathode case is Cathode internal conductive layer and a cathode passivation layer comprising a passivating metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact; and the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof, and wherein the exterior coating and the cathode passivation layer are in electrical contact.
[0030] In a tenth embodiment, the cathode case is a cathode inner conductive layer; and a cathode passivation layer comprising a passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact.
[0031] In an eleventh embodiment, the cathode case is a cathode inner conductive layer; and a cathode passivation layer comprising a passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact.
[0032] Embodiment 12 is the battery of any one of embodiments 8 to 11, wherein the cathode passivation layer has a uniform or variable thickness of from 1 μm to 400 μm, from 15 μm to 300 μm, from 14 μm to 200 μm, or from greater than 50 μm to 400 μm, or from greater than 50 μm to 300 μm, or from greater than 50 μm to 200 μm, or from greater than 50 μm to 175 μm.
[0033] Embodiment 13 is the battery of any one of embodiments 8 to 12, wherein the cathode passivation layer has a uniform or varying thickness from 1 μm to 400 μm, from 15 μm to 300 μm, from 14 μm to 200 μm, or from greater than 50 μm to 400 μm, or from greater than 50 μm to 175 μm; and the cathode inner conductive layer has a uniform or varying thickness from 75 μm to 350 μm, or from 125 μm to 350 μm, or from 200 μm to 300 μm, or from 25 μm to 100 μm.
[0034] Embodiment 14 is an embodiment in which the ratio of the thickness of the cathode passivation layer to the thickness of the internal conductive layer is, for example, 8:1 to 1:5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:5, or 6:1 to 1:3, or 6:1 to 1:2, or 6:1 to 1:1.1, or 6:1 to 1:1, 3:1 to 1:5, or 3:1 to 1:3, at least at some point in the bottom portion of the cathode case. , or 3:1 to 1:2, or 3:1 to 1:1.1, or 3:1 to 1:1, or 2:1 to 1:5, or 2:1 to 1:3, or 2:1 to 1:2, or 2:1 to 1:1.1, or 2:1 to 1:1, or 8:1 to 1:2.5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:2, or 3:1 to 1:2.
[0035] Embodiment 15 is the battery of any one of embodiments 8 to 14, wherein the outer coating has a uniform or variable thickness of 100 nm to 200 nm.
[0036] Embodiment 16 is the battery of any one of embodiments 9-15, wherein the outer coating comprises Ni.
[0037] Embodiment 17 is the battery of any one of embodiments 8-16, wherein the surface of the cathode internal conductive layer in electrical contact with the cathode passivation layer is not exposed to the ambient environment after fabrication.
[0038] Embodiment 18 is directed to a method for manufacturing a cathode interior conductive layer that is in electrical contact with a cathode passivation layer within 0.01 mm of the surface of the cathode interior conductive layer. 2 Less than or equal to 0.05 mm 2 Less than or 0.1 mm 2 Less than or 0.5 mm 2 Less than or 1.0 mm 2 Less than or 1.5 mm 2 18. The battery of embodiment 17, wherein less than one battery cell is exposed to the ambient environment after manufacture.
[0039] Embodiment 19 is a cathode case prepared from a coating laminate comprising a passivation layer having a uniform or variable thickness of 60 μm to 200 μm and a conductive layer having a uniform or variable thickness of 50 μm to 190 μm; the cathode case has a uniform or varying thickness of 200 μm to 250 μm, the cathode case including a hemfold with a passivation layer on each side of the hemfold having a uniform or varying thickness of 14 μm to 75 μm and a total internal conductive layer thickness of 222 μm to 50 μm; 19. The battery of any one of embodiments 1-18, wherein the cathode case comprises an annular sidewall comprising a passivation layer having a uniform or varying thickness of 60 pm to 200 pm and an inner conductive layer thickness of 190 μm to 50 μm.
[0040] Embodiment 19a is the battery of any one of embodiments 1 to 18, wherein the cathode case is prepared from a coated laminate including a passivation layer having a uniform or variable thickness of 60 pm to 200 pm and a conductive layer having a uniform or variable thickness of 50 μm to 190 μm. The cathode case has a uniform or variable thickness of 200 μm to 250 μm, the cathode case includes a hemfold, the hemfold includes a first side and a second side, each of the first and second sides further includes a passivation layer having a uniform or variable thickness of 14 μm to 75 μm, the hemfold has a total thickness of 200 μm to 250 μm, and the first side of the hemfold contacts the second side of the hemfold.
[0041] Embodiment 20 is the battery of any one of embodiments 1 to 19, wherein the cathode case includes a hemfold structure.
[0042] Embodiment 21 is the battery of any one of embodiments 8-20, wherein the cathode passivation layer comprises a first layer comprising a first passivation metal and a second layer comprising a second passivation metal.
[0043] Embodiment 22 is the battery of any one of embodiments 8-21, wherein the cathode passivation layer comprises a first layer comprising Ta or an alloy thereof.
[0044] Embodiment 23 is the battery of any one of embodiments 8 to 22, wherein the cathode passivation layer comprises a first layer comprising Ta or an alloy thereof, the first layer having a uniform or variable thickness from 1 μm to 3 μm.
[0045] Embodiment 24 is the battery of any one of embodiments 8-23, wherein the cathode passivation layer comprises a second layer comprising Nb or an alloy thereof.
[0046] Embodiment 25 is the battery of any one of embodiments 8 to 24, wherein the cathode passivation layer comprises a second layer comprising Nb or an alloy thereof, and the second layer has a uniform or variable thickness from 10 μm to 250 μm.
[0047] Embodiment 26 is the battery of any one of embodiments 8 to 25, wherein the cathode inner conductive layer has a uniform or variable thickness from 100 μm to 350 μm.
[0048] Embodiment 27 is the battery of any one of embodiments 1 to 26, wherein the anode case comprises a passivation metal, the passivation metal being present in a layer having a uniform or variable thickness from 100 nm to 400 μm.
[0049] Embodiment 28 is the battery of any one of embodiments 1 to 27, wherein the anode case comprises a passivating metal comprising Nb, Ta, an alloy thereof, or any combination thereof.
[0050] Embodiment 29 is an anode case, an anode inner conductive layer; and an anode passivation layer comprising a passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact.
[0051] Embodiment 30 is an anode case, an anode inner conductive layer; and an anode passivation layer comprising a passivation metal, wherein the anode passivation layer is in electrical contact with the anode inner conductive layer and the anode passivation layer; and the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof, and wherein the exterior coating and the anode passivation layer are in electrical contact.
[0052] In embodiment 31, the anode case is an anode inner conductive layer; and an anode passivation layer comprising a passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact.
[0053] Embodiment 32 is an anode case, an anode inner conductive layer; and an anode passivation layer comprising a passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact.
[0054] Embodiment 33 is a cross-sectional view of an anode passivation layer having a thickness of 100 nm to 1 μm, 100 nm to 3 μm, 100 nm to 5 μm, 100 nm to 10 μm, 1 μm to 400 μm, 3 μm to 100 μm, 3 μm to 50 μm, 15 μm to 300 μm, 14 μm to 200 μm, 25 μm to 50 μm, 50 μm to 400 μm, 50 μm to 300 μm, 50 μm to 2 μm. 33. The battery of any one of embodiments 29 to 32, wherein the thickness of the conductive film is uniform or variable, from 00 μm, 50 μm to 175 μm, 55 μm to 400 μm, 55 μm to 300 μm, 55 μm to 200 μm, 60 μm to 400 μm, 60 μm to 300 μm, 60 μm to 200 μm, 200 μm to 300 μm, or 300 μm to 400 μm.
[0055] Embodiment 34 is the battery of any one of embodiments 29-33, wherein the anode passivation layer has a uniform or varying thickness from 15 μm to 300 μm, from 14 μm to 200 μm, or from greater than 50 μm to 300 μm, and the anode inner conductive layer has a uniform or varying thickness from 75 μm to 350 μm, or from 125 μm to 350 μm, or from 200 μm to 300 μm, or from 25 μm to 100 μm.
[0056] Embodiment 35 is the battery of any one of embodiments 29-34, wherein the anode passivation layer comprises a first layer comprising a first passivation metal and a second layer comprising a second passivation metal.
[0057] Embodiment 36 is an embodiment wherein the anode passivation layer comprises: 36. The battery of any one of embodiments 29 to 35, comprising a first layer comprising Ta or an alloy thereof.
[0058] Embodiment 37 is an embodiment wherein the anode passivation layer comprises: 37. The battery of any one of embodiments 29-36, comprising a first layer comprising Ta or an alloy thereof, the first layer having a uniform or variable thickness of 1 pm to 3 μm.
[0059] Embodiment 38 is an embodiment wherein the anode passivation layer comprises: 38. The battery of any one of embodiments 29 to 37, comprising a second layer comprising Nb or an alloy thereof.
[0060] Embodiment 39 is the battery of any one of embodiments 35 to 38, wherein the second layer has a uniform or variable thickness from 10 μm to 250 μm.
[0061] Embodiment 40 is the battery of any one of embodiments 22 to 32, wherein the anode inner conductive layer has a uniform or variable thickness from 100 μm to 350 μm.
[0062] Embodiment 41 is the battery of embodiment 1, wherein the passivating metal comprises Re, W, or an alloy thereof.
[0063] In embodiment 42, the passivated metal is 100 nm to 1 μm, 100 nm to 3 μm, 100 nm to 5 μm, 100 nm to 10 μm, 3 μm to 100 μm, 1 μm to 400 μm, 3 μm to 50 μm, 15 μm to 300 μm, 14 μm to 200 μm, 25 μm to 50 μm, 50 μm to 400 μm, 50 μm to 300 μm, 50 μm to 2 42. The battery of embodiment 41, wherein the surface active agent is present in a layer having a uniform or varying thickness of 00 μm, 50 μm to 175 μm, 55 μm to 400 μm, 55 μm to 300 μm, 55 μm to 200 μm, 60 μm to 400 μm, 60 μm to 300 μm, 60 μm to 200 μm, 200 μm to 300 μm, or 300 μm to 400 μm.
[0064] Embodiment 43 is the battery of embodiment 41 or 42, wherein the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof.
[0065] Embodiment 44 is the battery of any one of embodiments 41-43, wherein the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof, and further wherein the exterior coating has a uniform or varying thickness from 100 nm to 7 μm, from 100 nm to 5 μm, or from 100 nm to 200 nm.
[0066] Embodiment 45 is a cathode case having: a cathode inner conductive layer; and a cathode passivation layer comprising a passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact.
[0067] Embodiment 46 is a cathode case, a cathode inner conductive layer; and a cathode passivation layer comprising a passivating metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact; and the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof, and wherein the exterior coating and the cathode passivation layer are in electrical contact.
[0068] Embodiment 47 is a cathode case, a cathode inner conductive layer; and a cathode passivation layer comprising a passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact.
[0069] Embodiment 48 is a cathode case having: a cathode inner conductive layer; and a cathode passivation layer comprising a passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact.
[0070] Embodiment 49 is the battery of any one of embodiments 45 to 48, wherein the cathode passivation layer has a uniform or variable thickness of from 15 μm to 300 μm, from 14 μm to 200 μm, or from greater than 50 μm to 400 μm, or from greater than 50 μm to 300 μm, or from greater than 50 μm to 200 μm, or from greater than 50 μm to 175 μm.
[0071] Embodiment 50 is the battery of any one of embodiments 45-49, wherein the cathode passivation layer has a uniform or varying thickness from 15 μm to 300 μm, or from 14 μm to 200 μm, or from greater than 50 μm to 400 μm, or from greater than 50 μm to 175 μm; and the cathode inner conductive layer has a uniform or varying thickness from 75 μm to 350 μm, or from 125 μm to 350 μm, or from 200 μm to 300 μm, or from 25 μm to 100 μm.
[0072] Embodiment 51 is an embodiment of the present invention, wherein the ratio of the thickness of the cathode passivation layer to the thickness of the internal conductive layer is, for example, 8:1 to 1:5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:5, or 6:1 to 1:3, or 6:1 to 1:2, or 6:1 to 1:1.1, or 6:1 to 1:1, 3:1 to 1:5, or 3:1 to 1:3, at least at some point in the bottom portion of the cathode case. or 3:1 to 1:2, or 3:1 to 1:1.1, or 3:1 to 1:1, or 2:1 to 1:5, or 2:1 to 1:3, or 2:1 to 1:2, or 2:1 to 1:1.1, or 2:1 to 1:1, or 8:1 to 1:2.5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:2, or 3:1 to 1:2.
[0073] Embodiment 52 is the battery of any one of embodiments 45 to 51, wherein the outer coating has a uniform or variable thickness from 100 nm to 200 nm.
[0074] Embodiment 53 is the battery of any one of embodiments 45-52, wherein the outer coating comprises Ni.
[0075] Embodiment 54 is the battery of any one of embodiments 45-53, wherein the surface of the cathode internal conductive layer that is in electrical contact with the cathode passivation layer is not exposed to the ambient environment after fabrication.
[0076] Embodiment 55 is directed to a method for removing 0.01 mm of the surface of the cathode interior conductive layer that is in electrical contact with the cathode passivation layer. 2 Less than or equal to 0.05 mm 2 Less than or 0.1 mm 2 Less than or 0.5 mm 2 Less than or 1.0 mm 2 Less than or 1.5 mm 2 55. The battery of any one of embodiments 45-54, wherein less than one of the batteries is exposed to the ambient environment after fabrication.
[0077] Embodiment 56 is a cathode case prepared from a coating laminate including a passivation layer having a uniform or variable thickness of 60 μm to 200 μm and a conductive layer having a uniform or variable thickness of 50 μm to 190 μm; 56. The battery of any one of embodiments 45-55, wherein the cathode case has a uniform or variable thickness of 200 μm to 250 μm, the cathode case comprises a hemfold, the hemfold comprises a first side and a second side, each of the first and second sides further comprising a passivation layer having a uniform or variable thickness of 14 μm to 75 μm, the hemfold has a total thickness of 200 μm to 250 μm, and the first side of the hemfold contacts the second side of the hemfold.
[0078] Embodiment 57 is the battery of any one of embodiments 45-56, wherein the cathode case comprises a hemfold structure.
[0079] Embodiment 58 is the battery of any one of embodiments 45-57, wherein the cathode passivation layer comprises a first layer comprising a first passivation metal and a second layer comprising a second passivation metal.
[0080] Embodiment 59 is an embodiment of the present invention, wherein the cathode passivation layer comprises: 59. The battery of any one of embodiments 45 to 58, comprising a first layer comprising Re, W, or an alloy thereof.
[0081] Embodiment 60 is directed to an embodiment wherein the cathode passivation layer comprises: 60. The battery of any one of embodiments 45-59, comprising a first layer comprising Re, W, or an alloy thereof, the first layer having a uniform or variable thickness from 1 μm to 25 μm.
[0082] Embodiment 61 is an embodiment wherein the cathode passivation layer comprises: 61. The battery of any one of embodiments 45 to 60, comprising a second layer comprising Nb or an alloy thereof.
[0083] Embodiment 62 is an embodiment wherein the cathode passivation layer comprises: 62. The battery of any one of embodiments 45-61, comprising a second layer comprising Nb or an alloy thereof, the second layer having a uniform or varying thickness of 5 μm to 250 μm.
[0084] Embodiment 63 is the battery of any one of embodiments 45 to 62, wherein the cathode inner conductive layer has a uniform or variable thickness from 100 gm to 350 gm.
[0085] Embodiment 64 is the battery of any one of embodiments 41 to 63, wherein the anode case comprises a passivation metal, the passivation metal being present in a layer having a uniform or variable thickness from 100 nm to 400 μm.
[0086] Embodiment 65 is the battery of any one of embodiments 41-64, wherein the anode case comprises a passivating metal comprising Re, W, or an alloy thereof.
[0087] Embodiment 66 is an embodiment of the present invention, wherein the anode case is an anode inner conductive layer; and an anode passivation layer comprising a passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact.
[0088] Embodiment 67 is an embodiment of the present invention, wherein the anode case is an anode inner conductive layer; and an anode passivation layer comprising a passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact; and the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof, and wherein the exterior coating and the anode passivation layer are in electrical contact.
[0089] Embodiment 68 is an embodiment of the present invention, wherein the anode case is an anode inner conductive layer; and an anode passivation layer comprising a passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact.
[0090] Embodiment 69 is an embodiment of the present invention, wherein the anode case is an anode inner conductive layer; and an anode passivation layer comprising a passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact.
[0091] Embodiment 70 is a method for manufacturing an anode passivation layer having a thickness of 100 nm to 1 μm, 100 nm to 3 μm, 100 nm to 5 μm, 100 nm to 10 μm, 3 μm to 100 μm, 1 μm to 400 μm, 3 μm to 50 μm, 15 μm to 300 μm, 14 μm to 200 μm, 25 μm to 50 μm, 50 μm to 400 μm, 50 μm to 300 μm, 50 μm to 2 μm. 69. The battery of any one of embodiments 66-69, wherein the thickness is uniform or variable between 00 μm, 50 μm and 175 μm, 55 μm and 400 μm, 55 μm and 300 μm, 55 μm and 200 μm, 60 μm and 400 μm, 60 μm and 300 μm, 60 μm and 200 μm, 200 μm and 300 μm, or 300 μm and 400 μm.
[0092] Embodiment 71 is the battery of any one of embodiments 66 to 70, wherein the anode passivation layer has a uniform or varying thickness from 15 μm to 300 μm, from 14 μm to 200 μm, or from greater than 50 μm to 300 μm, and the anode inner conductive layer has a uniform or varying thickness from 75 μm to 350 μm, or from 125 μm to 350 μm, or from 200 μm to 300 μm, or from 25 μm to 100 μm.
[0093] Embodiment 72 is the battery of any one of embodiments 66-71, wherein the anode passivation layer further comprises a first layer comprising a first passivation metal and a second layer comprising a second passivation metal.
[0094] Embodiment 73 is the battery of any one of embodiments 66-72, wherein the anode passivation layer further comprises a first layer comprising Re, W, or an alloy thereof.
[0095] Embodiment 74 is the battery of any one of embodiments 66 to 72, wherein the anode passivation layer further comprises a first layer comprising Re, W, or an alloy thereof, the first layer having a uniform or variable thickness from 1 μm to 3 μm.
[0096] Embodiment 75 is the battery of any one of embodiments 66-72, wherein the anode passivation layer further comprises a second layer comprising Nb or an alloy thereof.
[0097] Embodiment 76 is the battery of any one of embodiments 66 to 72, wherein the anode passivation layer further comprises a second layer comprising Nb or an alloy thereof, the second layer having a uniform or variable thickness from 10 μm to 250 μm.
[0098] Embodiment 77 is the battery of any one of embodiments 66 to 72, wherein the anode inner conductive layer has a uniform or variable thickness from 100 μm to 350 μm.
[0099] Embodiment 78 is the battery of embodiment 1, wherein the passivating metal comprises Ti or an alloy thereof; and the battery optionally comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Al, Cu, Cr, or Zn, an alloy thereof, or any combination of two or more thereof.
[0100] Embodiment 79 is the battery of embodiment 78, wherein the passivation metal is present in a layer having a uniform or variable thickness of greater than 50 μm to 300 μm, or greater than 50 μm to 200 μm, 200 μm to 300 μm, or 300 μm to 400 μm.
[0101] Embodiment 80 is the battery of embodiment 78 or 80, wherein the cathode case consists essentially of a layer comprising a passivating metal, the layer having a uniform or variable thickness of greater than 50 μm to 300 μm.
[0102] Embodiment 81 is the battery of embodiment 78 or 80, wherein the cathode case comprises a layer comprising a passivating metal, the layer having a uniform or variable thickness greater than 50 μm to 300 μm.
[0103] Embodiment 82 is the battery of any one of embodiments 78-81, wherein the exterior coating is present on both the exterior surface of the anode case and the exterior surface of the cathode case.
[0104] Embodiment 83 is the battery of any one of embodiments 78-81, wherein the exterior coating is on the exterior surface of the anode case.
[0105] Embodiment 84 is the battery of any one of embodiments 78-83, wherein an exterior coating is present on the exterior surface of the cathode case.
[0106] Embodiment 85 is the battery of any one of embodiments 78 to 84, wherein the outer coating has a uniform or variable thickness of 100 nm to 7 μm, 100 nm to 5 μm, or 100 nm to 200 nm.
[0107] Embodiment 86 is a cathode case comprising: a cathode inner conductive layer; and a cathode passivation layer comprising a passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact.
[0108] Embodiment 87 is a cathode case comprising: a cathode inner conductive layer; and a cathode passivation layer comprising a passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact; and the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof, and wherein the exterior coating and the cathode passivation layer are in electrical contact.
[0109] Embodiment 88 is a cathode case comprising: a cathode inner conductive layer; and a cathode passivation layer comprising a passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact.
[0110] Embodiment 89 is a cathode case comprising: a cathode inner conductive layer; and a cathode passivation layer comprising a passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact.
[0111] Embodiment 90 is the battery of any one of embodiments 86-89, wherein the cathode passivation layer has a uniform or variable thickness of greater than 50 μm to 400 μm, or greater than 50 μm to 300 μm, or greater than 50 μm to 200 μm, or greater than 50 μm to 175 μm.
[0112] Embodiment 91 is the battery of any one of embodiments 86-90, wherein the cathode inner conductive layer has a uniform or variable thickness of 75 μm to 350 μm, or 125 μm to 350 μm, or 200 μm to 300 μm, or 25 μm to 100 μm.
[0113] Embodiment 92 is an embodiment of the present invention, wherein the ratio of the thickness of the cathode passivation layer to the thickness of the internal conductive layer is, for example, 8:1 to 1:5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:5, or 6:1 to 1:3, or 6:1 to 1:2, or 6:1 to 1:1.1, or 6:1 to 1:1, or 3:1 to 1:5, or 3:1 to 1:3, at least at some point in the bottom portion of the cathode case. or 3:1 to 1:2, or 3:1 to 1:1.1, or 3:1 to 1:1, or 2:1 to 1:5, or 2:1 to 1:3, or 2:1 to 1:2, or 2:1 to 1:1.1, or 2:1 to 1:1, or 8:1 to 1:2.5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:2, or 3:1 to 1:2.
[0114] Embodiment 93 is the battery of any one of embodiments 86 to 92, wherein the outer coating has a uniform or variable thickness of 100 nm to 200 nm.
[0115] Embodiment 94 is the battery of any one of embodiments 86-93, wherein the exterior coating comprises Ni.
[0116] Embodiment 95 is the battery of any one of embodiments 86-94, wherein the surface of the cathode internal conductive layer in electrical contact with the cathode passivation layer is not exposed to the ambient environment after fabrication.
[0117] Embodiment 96 is directed to removing 0.01 mm of the surface of the cathode interior conductive layer that is in electrical contact with the cathode passivation layer. 2 Less than or equal to 0.05 mm 2 Less than or 0.1 mm 2 Less than or 0.5 mm 2 Less than or 1.0 mm 2 Less than or 1.5 mm 2 96. The battery of any one of embodiments 86-95, wherein less than one of the batteries is exposed to the ambient environment after fabrication.
[0118] Embodiment 97 is a cathode case prepared from a coating laminate comprising a passivation layer having a uniform or variable thickness of 60 μm to 200 μm and a conductive layer having a uniform or variable thickness of 50 μm to 190 μm; the cathode case has a uniform or varying thickness of 200 μm to 250 μm, the cathode case comprising a hemfold having a passivation layer on each side of the hemfold having a uniform or varying thickness of 14 μm to 75 μm and a total internal conductive layer thickness of 222 μm to 50 μm; 97. The battery of any one of embodiments 86-96, wherein the cathode case comprises an annular sidewall comprising a passivation layer having a uniform or varying thickness of 60 μm to 200 μm and an inner conductive layer thickness of 190 μm to 50 μm.
[0119] Embodiment 98 is the battery of any one of embodiments 86-97, wherein the cathode case comprises a hemfold structure.
[0120] Embodiment 99 is the battery of any one of embodiments 86 to 98, wherein the anode case comprises a passivation metal, the passivation metal being present in a layer having a uniform or variable thickness of greater than 50 μm to 400 μm.
[0121] Embodiment 100 is the battery of any one of embodiments 86-99, wherein the anode case comprises a passivating metal comprising Ti or an alloy thereof, and the battery optionally comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Al, Cu, Cr, or Zn, an alloy thereof, or any combination of two or more thereof.
[0122] Embodiment 101 is an embodiment of the present invention, wherein the anode case is an anode inner conductive layer; and an anode passivation layer comprising a passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact.
[0123] Embodiment 102 is an embodiment of the present invention, wherein the anode case is an anode inner conductive layer; and an anode passivation layer comprising a passivation metal, wherein the anode passivation layer is in electrical contact with the anode inner conductive layer and the anode passivation layer; and the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Al, Cu, Cr, Zn, alloys thereof, or combinations of two or more thereof, and wherein the exterior coating and the anode passivation layer are in electrical contact.
[0124] Embodiment 103 is an embodiment of the present invention, wherein the anode case is an anode inner conductive layer; and an anode passivation layer comprising a passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact.
[0125] Embodiment 104 is an embodiment of the present invention, wherein the anode case is an anode inner conductive layer; and an anode passivation layer comprising a passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact.
[0126] Embodiment 105 is the battery of any one of embodiments 101 to 104, wherein the anode passivation layer has a uniform or variable thickness from 50 μm to 100 μm.
[0127] Embodiment 106 is the battery of any one of embodiments 101 to 105, wherein the anode inner conductive layer has a uniform or variable thickness from 100 μm to 350 μm.
[0128] Embodiment 107 is the battery of any one of embodiments 1-106, further comprising at least one tie layer disposed between the cathode inner conductive layer and the cathode passivation layer, the anode inner conductive layer and the anode passivation layer, or both, wherein the inner conductive layer and the passivation layer remain in electrical contact.
[0129] Embodiment 108 is the battery of any one of embodiments 1-107, further comprising at least one tie layer disposed between the cathode inner conductive layer and the cathode passivation layer, the anode inner conductive layer and the anode passivation layer, or both, wherein the inner conductive layer and the passivation layer remain in electrical contact, and the at least one tie layer comprises a conductive material.
[0130] Embodiment 109 is the battery of any one of embodiments 1-108, further comprising at least one tie layer disposed between the cathode internal conductive layer and the cathode passivation layer, between the anode internal conductive layer and the anode passivation layer, or both, wherein the internal conductive layer and the passivation layer remain in electrical contact, and wherein the at least one tie layer comprises a metal.
[0131] Embodiment 110 is the battery of any one of embodiments 1-109, further comprising at least one tie layer disposed between the cathode internal conductive layer and the cathode passivation layer, between the anode internal conductive layer and the anode passivation layer, or both, wherein the internal conductive layer and the passivation layer remain in electrical contact, and wherein the at least one tie layer comprises an adhesive.
[0132] Embodiment 111 is the battery of any one of embodiments 1-110, further comprising at least one tie layer disposed between the cathode internal conductive layer and the cathode passivation layer, between the anode internal conductive layer and the anode passivation layer, or both, wherein the internal conductive layer and the passivation layer remain in electrical contact, and wherein the at least one tie layer comprises an adhesive, wherein the adhesive comprises a pressure-sensitive adhesive, a rubber adhesive, an epoxy, a polyurethane, a silicone adhesive, a phenolic resin, a UV-curable adhesive, an acrylate adhesive, a laminating adhesive, a fluoropolymer, or any combination of two or more thereof.
[0133] Embodiment 112 is the battery of embodiment 111, wherein the lamination adhesive comprises low or high density polyethylene, polyolefin, polyolefin derivative, acid-containing adhesive, ionomer, terpolymer of ethylene, acrylate, or ethylene vinyl acetate.
[0134] Embodiment 113 is the battery of embodiment 112, wherein the acid-containing adhesive comprises EAA, EMAA, an ionomer, a terpolymer of ethylene, an acid, or an acrylate.
[0135] Embodiment 114 is the battery of any one of embodiments 107 to 113, wherein at least one tie layer has a uniform or variable thickness of 100 nm to 400 μm, 100 nm to 350 μm, 1 μm to 350 μm, 200 μm to 350 μm, 1 μm to 50 μm, 5 μm to 50 μm, 50 μm to 250 μm, or 5 μm to 200 μm.
[0136] Embodiment 115 is the battery of any one of embodiments 1-114, wherein the anode inner conductive layer and / or the cathode inner conductive layer comprises aluminum, stainless steel, chromium, gold, vanadium, nickel, silver, copper, magnesium, zinc, alloys thereof, or a combination of any two or more thereof.
[0137] Embodiment 116 is the battery of any one of embodiments 1-115, wherein the anode inner conductive layer and / or the cathode inner conductive layer comprises stainless steel.
[0138] Embodiment 117 is the battery of any one of embodiments 1 to 116, wherein the stainless steel comprises SS304, SS316, SS430, duplex 2205, duplex 2304, duplex 2507, or one or more other steels having a chromium content of 10 wt. % or more and / or a nickel content of 0.1 wt. % or more.
[0139] Embodiment 118 is the battery of any of embodiments 1-117, comprising a passivation metal in the passivation layer.
[0140] Embodiment 119 is the battery of any of embodiments 1-118, comprising a passivation metal in the passivation layer, the passivation layer comprising a first layer comprising a first passivation metal and a second layer comprising a second passivation metal.
[0141] Embodiment 120 is the battery of any of embodiments 1-119, wherein the passivated metal is a substantially pure metal.
[0142] Embodiment 121 is the battery of any of embodiments 1-120, wherein the passivating metal is an alloy.
[0143] Embodiment 122 is the battery of any of embodiments 1-121, wherein the passivating metal comprises an alloy of at least two passivating metals.
[0144] Embodiment 123 is the battery of any one of embodiments 1 to 122, wherein the anode case has a uniform or variable thickness of 50 μm to 400 μm.
[0145] Embodiment 124 is the battery of any one of embodiments 1 to 123, wherein the cathode case has a uniform or variable thickness of 50 μm to 400 μm, or 200 μm to 250 μm.
[0146] Embodiment 125 is the battery of any one of embodiments 1 to 124, further comprising a water-impermeable coating disposed on and covering the rim of the cathode case, and optionally disposed on a portion of the exterior surface of the anode case and / or a portion of the exterior surface of the cathode case.
[0147] Embodiment 126 is the battery of any one of embodiments 1 to 125, further comprising a water-impermeable coating disposed on a portion of the exterior surface of the anode case and / or a portion of the exterior surface of the cathode case and covering the rim of the cathode case, wherein the water-impermeable coating is selected from natural rubber, TFE, Exxon Butyl, chloroprene, epichlorohydrin, ethylene-propylene, fluorosilicone, hydrogenated nitrile, liquid silicone rubber, medical-grade ethylene propylene, silicone, nitrile, perfluoroelastomer, polyacrylate, polyurethane, styrene butadiene, Teflon®, Vamac, PTFE, and Viton.
[0148] Embodiment 127 is the battery of any one of embodiments 1 to 126, further comprising a water-impermeable coating disposed on and covering the rim of the cathode case, and optionally disposed on a portion of the outer surface of the anode case and / or a portion of the outer surface of the cathode case, wherein the water-impermeable coating is the same material as the gasket.
[0149] Embodiment 128 includes a cathode inner conductive layer including an outer bottom surface, an outer annular surface, and a rim surface; the outer bottom surface is covered by a cathode passivation layer; 128. The battery of any one of embodiments 1-127, wherein the outer annular surface and the rim surface are encased by a cathode passivation layer, a gasket, a water-impermeable coating, or any combination of any two or more thereof.
[0150] Embodiment 129 is the battery of any one of embodiments 1 to 128, wherein the gasket comprises an elastomeric material or plastic, such as nylon, polytetrafluoroethylene, fluorinated ethylene-propylene, chlorotrifluoroethylene, perfluoroalkoxy polymer, polyvinyl, polyethylene, polyethylene terephthalate, polypropylene, polystyrene, polysulfone, polyacrylicate, polyurethane, silicone rubber, and any combination of any two or more thereof.
[0151] Embodiment 130 is a battery described in any one of embodiments 125 to 129, wherein the water-impermeable coating comprises rubber, Buna, silicone, silicone rubber, PTFE, Viton, or an elastomeric material, or a plastic such as nylon, polytetrafluoroethylene, fluorinated ethylene-propylene, chlorotrifluoroethylene, perfluoroalkoxy polymer, polyvinyl, polyethylene, polyethylene terephthalate, polypropylene, polystyrene, polysulfone, polyacrylicate, polyurethane, and any combination of any two or more thereof.
[0152] Embodiment 131 is a coin cell or cylindrical battery in which the battery case comprises a sealing cup, a bottom can, and a gasket, wherein the outer diameter of the sealing cup is smaller than the inner diameter of the bottom can, at least a portion of the sealing cup is positioned inside the bottom can with the gasket between the sealing cup and the bottom can, and the annular wall of the bottom can is crimped against the annular wall of the sealing cup, and further wherein the battery case comprises a passivated metal.
[0153] Embodiment 132 is the battery of embodiment 131, wherein the sealing cup is the anode case and the bottom can is the cathode case, and further wherein the bottom can comprises a passivated metal.
[0154] Embodiment 133 is the battery of embodiment 131, wherein the sealing cup is the cathode case and the bottom can is the anode case, and further wherein both the bottom can and the sealing cup comprise a passivated metal.
[0155] Embodiment 134 is the battery of any one of embodiments 1 to 130, wherein the battery is a button or coin cell battery.
[0156] Embodiment 135 is the battery of any one of embodiments 1 to 134, wherein the electrochemical cell has a voltage of 10 V or less, 5 V or less, 3 V or less, or 1 V or less.
[0157] Embodiment 136 is the battery of any one of embodiments 1 to 135, wherein the battery is a 3 volt or 1.5 volt button cell or coin cell.
[0158] Embodiment 137 is an embodiment of the present invention in which the battery is a CR927, CR1025, CR1130, CR1216, CR1220, CR1225, CR1616, CR1620, CR1625, CR1632, CR2012, CR2016, CR2025, CR2032, CR2320, CR2335, CR2354, CR2412, CR2430, CR2450, CR2477, CR2507, CR3032, or CR11108 lithium coin cell, or a S 137. The battery of any one of embodiments 1-136, wherein the battery is an R41, SR43, SR44, SR45, SR48, SR54, SR55, SR57, SR58, SR59, SR60, SR63, SR64, SR65, SR66, SR67, SR68, SR69, S516, SR416, SR731, SR512, SR714, SR712 silver oxide coin cell, or an LR41, LR44, LR54, or LR66 alkaline coin cell battery.
[0159] Embodiment 138 is the battery of any one of embodiments 1 to 137, wherein the battery is a CR2032, CR2016, or CR2025 lithium coin cell battery.
[0160] Embodiment 139 is the battery of any one of embodiments 1 to 138, wherein the battery is an AAAA, AAA, AA, A, B, C, D, E 90 / N, 4001, 810, 910A, AM5, LR1, MN9100, or UM-5 cylindrical battery.
[0161] Embodiment 140 is the battery of any one of embodiments 1-139, wherein a conductive path is formed between the anode and the cathode when at least a portion of the anode case and a portion of the cathode case are in electrical contact via a conductive aqueous medium.
[0162] Embodiment 141 is the battery of any one of embodiments 1-140, wherein a conductive pathway is formed between the anode and cathode through the conductive aqueous medium when at least a portion of the anode case and a portion of the cathode case contact the conductive aqueous medium, and further, the conductive pathway is reduced or inhibited upon continued contact with the conductive aqueous medium.
[0163] Embodiment 142 is the battery of any one of embodiments 1-141, wherein a conductive pathway is formed between the anode and cathode through the conductive aqueous medium when at least a portion of the anode case and a portion of the cathode case contact the conductive aqueous medium, and further wherein the conductive pathway is reduced or inhibited in less than 2 hours, or less than 1 hour, or less than 30 minutes after initial contact with the conductive aqueous medium.
[0164] Embodiment 143 is the battery of any one of embodiments 1-142, wherein the anode passivation layer and / or cathode passivation layer oxidizes when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium.
[0165] Embodiment 144 is the battery of any one of embodiments 1 to 143, wherein the anode passivation layer and / or the cathode passivation layer oxidize to form an oxide layer when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium, and the battery provides a current of less than 1.5 mA, or less than 1 mA, or less than 0.5 mA, or less than 0.3 mA after the oxide layer is formed.
[0166] Embodiment 145 is the battery of any one of embodiments 1 to 144, wherein the anode passivation layer and / or the cathode passivation layer oxidize to form an oxide layer when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium, and wherein the battery provides a current of less than 1.5 mA, or less than 1 mA, or less than 0.5 mA, or less than 0.3 mA after the oxide layer is formed, and further wherein the oxide layer is formed in less than 2 hours, or less than 1 hour, or less than 30 minutes after initial contact with the conductive aqueous medium.
[0167] Embodiment 146 is the battery of any one of embodiments 1-145, wherein an electrolytic reaction occurs when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium, and the electrolytic reaction is inhibited or reduced in less than 2 hours, or less than 1 hour, or less than 30 minutes after initial contact with the conductive aqueous medium.
[0168] Embodiment 147 is a battery described in any one of embodiments 140 to 146, wherein contact with a conductive aqueous medium includes placing the battery on a hydrated tissue such that the hydrated tissue contacts both at least a portion of the anode case and a portion of the cathode case to form a conductive pathway.
[0169] Embodiment 148 is the battery of embodiment 147, wherein the hydrated tissue is hydrated porcine esophageal tissue.
[0170] Embodiment 149 is the battery of any one of embodiments 140-146, wherein contacting with a conductive aqueous medium comprises immersion in 25% Ringer's solution.
[0171] Embodiment 150 is the battery of embodiment 149, wherein the pH of the 25% Ringer's solution is less than 9, or less than 8, or less than 7 after immersion in the 25% Ringer's solution for 120 minutes, or 60 minutes, or 20 minutes, or 10 minutes.
[0172] Embodiment 151 is the battery of embodiment 149 or 150, wherein the 25% Ringer's solution has a starting pH of 5 to 7.5, and the average pH of the 25% Ringer's solution sampled at 5-minute intervals over 60 minutes after immersion of the battery in the 25% Ringer's solution does not exceed an average pH of 10, 9.5, 9, 8.5, or 8.
[0173] Embodiment 152 is an embodiment of the present invention, wherein the cathode case comprises: a cathode inner conductive layer; a cathode passivation layer comprising a passivation metal comprising Ta, Nb, W, Ti, an alloy thereof, or any combination thereof; The cathode passivation layer is a cathode case having a uniform or variable thickness between 1 μm and 400 μm.
[0174] Embodiment 153 is the cathode case of embodiment 152, further comprising an exterior coating on the exterior surface of the cathode case, the exterior coating comprising Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof.
[0175] Embodiment 154 is the cathode case of embodiment 153, wherein the outer coating has a uniform or variable thickness of 100 nm to 7 μm or 100 nm to 5 μm.
[0176] Embodiment 155 is the cathode case of embodiment 153 or 154, wherein the outer coating has a uniform or variable thickness of 100 nm to 200 nm.
[0177] Embodiment 156 is the cathode case of any one of embodiments 153-155, wherein the outer coating comprises Ni.
[0178] Embodiment 157 is the cathode case of any one of embodiments 152 to 156, wherein the cathode passivation layer has a uniform or variable thickness between 14 μm and 200 μm.
[0179] Embodiment 158 is the cathode case of any one of embodiments 152 to 157, wherein the passivating metal comprises Nb or an alloy thereof.
[0180] Embodiment 159 is the cathode case of any one of embodiments 152 to 157, wherein the passivating metal comprises Ta or an alloy thereof.
[0181] Embodiment 160 is the cathode case of any one of embodiments 152-157, wherein the passivating metal comprises W or an alloy thereof.
[0182] Embodiment 161 is the cathode case of any one of embodiments 152 to 157, wherein the passivating metal comprises Ti or an alloy thereof.
[0183] Embodiment 162 is the cathode case of any one of embodiments 152 to 157, wherein the passivating metal comprises Re or an alloy thereof.
[0184] Embodiment 163 is the cathode case of any one of embodiments 152 to 1162, wherein the cathode inner conductive layer has a uniform or variable thickness between 100 μm and 350 μm.
[0185] Embodiment 164 is a cathode case according to any one of embodiments 152-163, wherein the cathode inner conductive layer comprises aluminum, stainless steel, chromium, gold, vanadium, nickel, silver, copper, magnesium, zinc, alloys thereof, or a combination of any two or more thereof.
[0186] Embodiment 165 is the cathode case of any one of embodiments 152-164, wherein the cathode interior conductive layer comprises stainless steel.
[0187] Embodiment 166 is an embodiment in which the ratio of the thickness of the cathode passivation layer to the thickness of the internal conductive layer is, for example, 8:1 to 1:5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:5, or 6:1 to 1:3, or 6:1 to 1:2, or 6:1 to 1:1.1, or 6:1 to 1:1, 3:1 to 1:5, or 3:1 to 1:3, or 3:1 to 1:5. 166. The cathode case of any one of embodiments 152 to 165, wherein the ratio of SiO2 to SiO2 is 8:1 to 1:2, or 3:1 to 1:1.1, or 3:1 to 1:1, or 2:1 to 1:5, or 2:1 to 1:3, or 2:1 to 1:2, or 2:1 to 1:1.1, or 2:1 to 1:1, or 8:1 to 1:2.5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:2, or 3:1 to 1:2.
[0188] Embodiment 167 is the cathode case of any one of embodiments 152 to 166, wherein the cathode passivation layer oxidizes to form an oxide layer when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium, and the battery provides a current of less than 1.5 mA, or less than 1 mA, or less than 0.5 mA, or less than 0.3 mA after the oxide layer is formed, and further wherein the oxide layer is formed in less than 2 hours, or less than 1 hour, or less than 30 minutes after initial contact with the conductive aqueous medium.
[0189] Embodiment 168 is directed to a method for manufacturing a cathode interior conductive layer in which (i) the surface of the cathode interior conductive layer in electrical contact with the cathode passivation layer is not exposed to the ambient environment after fabrication, or (ii) within 0.01 mm of the surface of the cathode interior conductive layer in electrical contact with the cathode passivation layer is 2 Less than or equal to 0.05 mm 2 Less than or 0.1 mm 2 Less than or 0.5 mm 2 Less than or 1.0 mm 2 Less than or 1.5 mm 2 168. The cathode case of any one of embodiments 152-167, wherein less than one of the cathode cases is exposed to the ambient environment after fabrication.
[0190] Embodiment 169 is the cathode case of any one of embodiments 1 to 168, wherein the cathode case includes a hemfold structure.
[0191] Embodiment 170 is the cathode case of any one of embodiments 152-169, wherein the cathode inner conductive layer and the cathode passivation layer both comprise a coating laminate.
[0192] Embodiment 171 is a cathode case prepared from a coating laminate comprising a passivation layer having a uniform or variable thickness of 60 μm to 200 μm and a conductive layer having a uniform or variable thickness of 50 μm to 190 μm; 170. A cathode case according to any one of embodiments 152 to 170, wherein the cathode case has a uniform or variable thickness of 200 μm to 250 μm, the cathode case comprises a hemfold, the hemfold comprises a first side and a second side, each of the first and second sides further comprising a passivation layer having a uniform or variable thickness of 14 μm to 75 μm, the hemfold has a total thickness of 200 μm to 250 μm, and the first side of the hemfold is in contact with the second side of the hemfold.
[0193] Embodiment 172 is the cathode case of any one of embodiments 152 to 170, wherein the cathode case is interchangeable with a cathode case of a commercially manufactured button cell or coin cell battery.
[0194] Embodiment 173 is a laminate comprising: a conductive layer having a uniform or variable thickness between 10 μm and 400 μm; a passivation layer comprising a passivation metal selected from Ta, Nb, W, Ti, alloys thereof, and combinations thereof, the passivation layer having a uniform or varying thickness between 10 μm and 400 μm; The stack is a stack that is for use in an anode case or a cathode case.
[0195] Embodiment 174 is the laminate of embodiment 173, further comprising an outer coating.
[0196] Embodiment 175 is the laminate of embodiment 173 or 174, wherein the conductive layer has a uniform or variable thickness between 175 μm and 300 μm.
[0197] Embodiment 176 is the laminate of any one of embodiments 173 to 175, wherein the passivation layer has a uniform or variable thickness from 1 μm to 100 μm.
[0198] Embodiment 177 is the laminate of any one of embodiments 174 to 176, wherein the outer coating has a uniform or variable thickness of 100 nm to 7 μm, 100 nm to 5 μm, or 100 nm to 200 nm.
[0199]
[0199] Embodiment 178 is the laminate of any one of embodiments 173 to 177, wherein the laminate has a uniform or variable thickness from 50 μm to 330 μm.
[0200] Embodiment 179 is a method of manufacturing a laminate for use in an anode case or a cathode case, comprising: a conductive layer; a passivation layer comprising a passivation metal selected from Ta, Nb, W, Ti, alloys thereof, and combinations thereof; The method is The method includes depositing a conductive layer and a passivation layer.
[0201] Embodiment 180 is a method of manufacturing a laminate for use in an anode case or a cathode case, the laminate comprising: a conductive layer having a uniform or variable thickness between 10 μm and 400 μm; a passivation layer comprising a passivation metal selected from Ta, Nb, W, Ti, alloys thereof, and combinations thereof, the passivation layer having a uniform or varying thickness between 10 μm and 400 μm; The method is The method includes coating a conductive layer and a passivation layer.
[0202] Embodiment 181 is the method of embodiment 179 or 180, wherein the conductive layer has a uniform or variable thickness of 50 μm to 100 μm, or 75 μm to 200 μm, or 175 μm to 300 μm.
[0203] Embodiment 182 is the method of any one of embodiments 179 to 181, wherein the passivation layer has a uniform or variable thickness of 1 μm to 75 μm, or 50 μm to 100 μm, or 75 μm to 200 μm, or 175 μm to 300 μm.
[0204] Embodiment 183 is the method of any one of embodiments 179 to 182, wherein the laminate has a uniform or variable thickness between 75 μm and 400 μm.
[0205] Embodiment 184 is the method of any one of embodiments 179-183, further comprising laminating an outer coating to the passivation layer of the laminate.
[0206] Embodiment 185 is the method of any one of embodiments 179-183, further comprising applying an outer coating to the passivation layer of the laminate.
[0207] Embodiment 186 is the method of any one of embodiments 179-183, further comprising depositing an outer coating on the passivation layer of the laminate.
[0208] Embodiment 187 is a method of making a laminate for use in the anode case or cathode case of the battery of any one of embodiments 1 to 171, comprising: a conductive layer; a passivation layer; The method is depositing a conductive layer and a passivation layer; The method optionally includes laminating an outer coating to a passivation layer, the passivation layer being disposed between the conductive layer and the outer coating.
[0209] Embodiment 188 is a method of making a laminate for use in the anode case or cathode case of the battery of any one of embodiments 1 to 171, comprising: a conductive layer; a passivation layer; The method is coating a conductive layer and a passivation layer; The method optionally includes coating an outer coating onto a passivation layer, the passivation layer being disposed between the conductive layer and the outer coating.
[0210] Embodiment 189 is a laminate produced by the method of any one of embodiments 179-188.
[0211] Embodiment 190 is the laminate of any one of embodiments 173-178 or 189, wherein the conductive layer comprises stainless steel.
[0212] Embodiment 191 is a method of manufacturing a cathode case, comprising stamping the laminate of any one of embodiments 173-178 or 189 to form a cathode case including a bottom, an annular side, and a rim; a conductive layer forming an inner surface of the cathode case; and A passivation layer forms the exterior surface of the cathode case.
[0213] Embodiment 192 is a method of manufacturing a cathode case, comprising stamping the laminate of any one of embodiments 173-178 or 189 to form a cathode case including a bottom, an annular side, and a rim; a conductive layer forming an inner surface of the cathode case; and The outer coating forms the exterior surface of the cathode case, and the passivation layer is between the conductive layer and the outer coating, the passivation layer being in electrical contact with both the conductive layer and the outer coating.
[0214] Embodiment 193 is extending the annular side portion of the cathode case to form an extended annular side portion of the cathode case and a lower annular side portion of the cathode case, the extended annular side portion having a thickness less than that of the lower annular side portion; 193. The method of embodiment 191 or 192, further comprising folding the extended annular side portion toward the center of the cathode case to form a hemfold.
[0215] Embodiment 194 is a method of manufacturing a cathode case, comprising providing an internal support member including a bottom, an annular side, a rim, an inner surface, and an outer surface; The method includes depositing a passivation layer on an outer surface of an internal support member, and depositing a first conductive material on an inner surface and optionally on a rim of the internal support member to form an internal conductive layer.
[0216] Embodiment 195 is a method of manufacturing a cathode case, comprising providing an internal support member including a bottom, an annular side, a rim, an inner surface, and an outer surface; depositing a passivation layer on an exterior surface of the internal support member; depositing a first conductive material onto the interior surface and optionally the rim of the interior support member to form an interior conductive layer; and depositing a second conductive material over the passivation layer and optionally the rim to form an outer coating.
[0217] Embodiment 196 is a method of making a cathode case, comprising: a) forming a passivated metal into a passivated cup having a bottom, an annular side, and a rim, each of the bottom, annular side, and rim having an inner surface and an outer surface; b) forming an inner conductive metal having a bottom, an annular side, and a rim, each of the bottom, annular side, and rim having an inner surface and an outer surface; c) placing an inner conductive cup within the passivation cup, the outer surface of the inner conductive cup being in electrical contact with the inner surface of the passivation cup, thereby forming a cathode case.
[0218] Embodiment 197 is a method described in embodiment 196, wherein the annular side of the inactivation cup extends beyond the annular side of the inner conductive cup, and further includes a step of folding the rim of the inactivation cup over the rim of the inner conductive cup to form a hem fold.
[0219] Embodiment 198 is the method of embodiment 196, wherein the rim of the passivation cup partially covers the rim of the inner conductive cup, or the rim of the passivation cup covers the rim of the inner conductive cup.
[0220] Embodiment 199 is a method according to any one of embodiments 196 to 198, wherein forming the passivation cup and / or the inner conductive cup comprises a process selected from stamping, wire forming, metal casting, or metal injection molding.
[0221] Embodiment 200 is a cathode case manufactured by the method of any one of embodiments 191-199.
[0222] Embodiment 201 is a battery comprising the cathode case of embodiment 200.
[0223] Embodiment 202 is a battery including the cathode case and / or anode case of any one of FIGS.
[0224] Embodiment 203 is a) an anode case; b) a cathode case i) a cathode inner conductive layer comprising aluminum (Al), stainless steel, chromium (Cr), gold (Au), vanadium (V), nickel (Ni), silver (Ag), copper (Cu), magnesium (Mg), zinc (Zn), alloys thereof, or a combination of any two or more thereof; ii) a cathode passivation layer comprising a passivation metal comprising niobium (Nb), tantalum (Ta), an alloy thereof, or any combination thereof, the cathode passivation layer having a uniform or variable thickness between 1 μm and 400 μm; iii) the ratio of the thickness of the cathode passivation layer to the thickness of the internal conductive layer is between 8:1 and 1:2.5, at least at some point in the bottom portion of the cathode case; iv) the cathode case has a uniform or variable thickness of 50 μm to 400 μm; v) the cathode case includes a hemfold; vi) Further, the cathode inner conductive layer and the cathode a cathode case to which the passivation layer is in electrical contact; c) an electrochemical cell comprising an anode, a cathode, and a separator positioned between the anode and the cathode; e) a gasket between the anode case and the cathode case.
[0225] Embodiment 204 is the battery of embodiment 203, wherein the passivation metal is present in a layer having a uniform or variable thickness from 14 μm to 200 μm.
[0226] Embodiment 205 is the battery of embodiment 203, wherein the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof, and wherein the exterior coating has a uniform or varying thickness from 100 nm to 7 μm or from 100 nm to 5 μm.
[0227] Embodiment 206 is the battery of embodiment 203, wherein the ratio of the thickness of the cathode passivation layer to the thickness of the internal conductive layer is, for example, 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:2, or 3:1 to 1:2, or 2:1 to 1:2, at least at some point in the bottom portion of the cathode casing.
[0228] Embodiment 207 is the battery of embodiment 203, wherein the outer coating comprises Ni and has a uniform or variable thickness between 100 nm and 200 nm.
[0229] Embodiment 208 is the battery of embodiment 203, wherein the surface of the cathode interior conductive layer in electrical contact with the cathode passivation layer is not exposed to the ambient environment after fabrication.
[0230] Embodiment 209 is directed to removing 0.01 mm of the surface of the inner conductive layer that is in electrical contact with the passivation layer. 2 Less than or equal to 0.05 mm 2 Less than or 0.1 mm 2 Less than or 0.5 mm 2 Less than or 1.0 mm 2 Less than or 1.5 mm 2 204. The battery of embodiment 203, wherein less than one battery cell is exposed to the ambient environment after manufacture.
[0231] Embodiment 210 is a cathode case prepared from a coating laminate including a passivation layer having a uniform or varying thickness between 60 μm and 200 μm and a conductive layer having a uniform or varying thickness between 50 μm and 190 μm; the cathode case has a uniform or varying thickness of 200 pm to 250 pm, the cathode case comprising a hemfold having a passivation layer on each side of the hemfold having a uniform or varying thickness of 14 μm to 75 μm and a total internal conductive layer thickness of 222 μm to 50 μm; 204. The battery of embodiment 203, wherein the cathode case comprises an annular sidewall comprising a passivation layer having a uniform or varying thickness of 60 μm to 200 μm and an inner conductive layer thickness of 190 μm to 50 μm.
[0232] Embodiment 210a is an embodiment in which the cathode case is prepared from a coating laminate including a passivation layer having a uniform or variable thickness between 60 μm and 200 μm and a conductive layer having a uniform or variable thickness between 50 μm and 190 μm; 204. The battery of embodiment 203, wherein the cathode case has a uniform or varying thickness of 200 μm to 250 μm, the cathode case comprises a hemfold, the hemfold comprises a first side and a second side, each of the first and second sides further comprising a passivation layer having a uniform or varying thickness of 14 μm to 75 μm, the hemfold has a total thickness of 200 μm to 250 μm, and the first side of the hemfold contacts the second side of the hemfold.
[0233] Embodiment 211 is the battery of embodiment 203, wherein the cathode inner conductive layer has a uniform or variable thickness from 100 μm to 350 μm.
[0234] Embodiment 212 is the battery of embodiment 203, wherein the cathode inner conductive layer comprises stainless steel.
[0235] Embodiment 213 is the battery of embodiment 203, wherein the cathode case has a uniform or variable thickness of 50 μm to 400 μm, or 200 μm to 250 μm.
[0236] Embodiment 214 is the battery of embodiment 203, wherein the battery is a button or coin cell battery.
[0237] Embodiment 215 is the battery of embodiment 203, wherein a conductive pathway is formed between the anode and the cathode through the conductive aqueous medium when at least a portion of the anode case and a portion of the cathode case contact the conductive aqueous medium, and further wherein the conductive pathway is reduced or inhibited in less than 2 hours, or less than 1 hour, or less than 30 minutes after initial contact with the conductive aqueous medium.
[0238] Embodiment 216 is the battery of embodiment 203, wherein when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium, the cathode passivation layer oxidizes to form an oxide layer, and the battery provides a current of less than 1.5 mA, or less than 1 mA, or less than 0.5 mA, or less than 0.3 mA after the oxide layer is formed.
[0239] Embodiment 217 is the battery of embodiment 203, wherein the cathode passivation layer oxidizes to form an oxide layer when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium, and wherein the battery provides a current of less than 1.5 mA, or less than 1 mA, or less than 0.5 mA, or less than 0.3 mA after the oxide layer is formed, and further wherein the oxide layer is formed in less than 2 hours, or less than 1 hour, or less than 30 minutes after initial contact with the conductive aqueous medium.
[0240] Embodiment 218 is the battery of embodiment 203, wherein an electrolytic reaction occurs when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium, and the electrolytic reaction is inhibited or reduced in less than 2 hours, or less than 1 hour, or less than 30 minutes after initial contact with the conductive aqueous medium.
[0241] Embodiment 219 is the battery of embodiment 215, wherein contact with the conductive aqueous medium includes placing the battery on a hydrated tissue such that the hydrated tissue contacts both at least a portion of the anode case and a portion of the cathode case to form a conductive path, and the hydrated tissue is hydrated porcine esophageal tissue.
[0242] Embodiment 220 is directed to the method of claim 220, wherein contacting with a conductive aqueous medium comprises immersion in 25% Ringer's solution; i) after immersion in 25% Ringer's solution for 120 minutes, 60 minutes, 20 minutes, or 10 minutes, the pH of the 25% Ringer's solution is less than 9, or less than 8, or less than 7; and / or ii) The battery of embodiment 215, wherein the 25% Ringer's solution has an initial pH of 5 to 7.5, and the average pH of the 25% Ringer's solution sampled at 5-minute intervals over a 60-minute period after immersion of the battery in the 25% Ringer's solution does not exceed an average pH of 9.5, 9, 8.5, or 8.
[0243] Embodiment 221 is a) a cathode inner conductive layer comprising aluminum (Al), stainless steel, chromium (Cr), gold (Au), vanadium (V), nickel (Ni), silver (Ag), copper (Cu), magnesium (Mg), zinc (Zn), alloys thereof, or a combination of any two or more thereof; b) a cathode passivation layer comprising a passivation metal comprising Ta, Nb, W, Ti, alloys thereof, or any combination thereof, the cathode passivation layer having a uniform or varying thickness between 1 μm and 400 μm; c) the ratio of the thickness of the cathode passivation layer to the thickness of the internal conductive layer is between 8:1 and 1:2.5 at least at some point in the bottom portion of the cathode case; d) the cathode case has a uniform or variable thickness of 50 μm to 400 μm; e) Further, the cathode case is a cathode case including a hemfold.
[0244] Embodiment 222 is the cathode case of embodiment 221, further comprising an exterior coating on an exterior surface of the cathode case, the exterior coating comprising Ni, Al, Cu, Cr, Zn, alloys thereof, or any combination of two or more thereof, and the exterior coating having a uniform or variable thickness of 100 nm to 7 pm or 100 nm to 5 μm.
[0245] Embodiment 223 is the cathode case of embodiment 222, wherein the outer coating comprises Ni and has a uniform or variable thickness between 100 nm and 200 nm.
[0246] Embodiment 224 is the cathode case of embodiment 221, wherein the cathode passivation layer has a uniform or variable thickness between 14 μm and 200 μm.
[0247] Embodiment 225 is the cathode case of embodiment 221, wherein the passivating metal comprises Nb or an alloy thereof.
[0248] Embodiment 226 is the cathode case of embodiment 221, wherein the passivating metal comprises Ta or an alloy thereof.
[0249] Embodiment 227 is the cathode case of embodiment 221, wherein the cathode inner conductive layer has a uniform or variable thickness between 100 μm and 350 μm.
[0250] Embodiment 228 is the cathode case of embodiment 221, wherein the cathode interior conductive layer comprises stainless steel.
[0251] Embodiment 229 is the cathode case of embodiment 221, wherein the ratio of the thickness of the cathode passivation layer to the thickness of the internal conductive layer, at least at some point in the bottom portion of the cathode case, is 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:2, or 3:1 to 1:2, or 2:1 to 1:2.
[0252] Embodiment 230 is (i) the surface of the cathode interior conductive layer that is in electrical contact with the cathode passivation layer is not exposed to the ambient environment after fabrication; or (ii) 0.01 mm of the surface of the cathode internal conductive layer that is in electrical contact with the cathode passivation layer. 2 Less than or equal to 0.05 mm 2 Less than or 0.1 mm 2 Less than or 0.5 mm 2 Less than or 1.0 mm 2 Less than or 1.5 mm 2 222. The cathode case of embodiment 221, wherein less than the cathode case is exposed to the ambient environment after fabrication.
[0253] Embodiment 231 is a cathode case prepared from a coating laminate comprising a passivation layer having a uniform or variable thickness of 60 μm to 200 μm and a conductive layer having a uniform or variable thickness of 50 μm to 190 μm; the cathode case has a uniform or variable thickness of 200 μm to 250 μm, the cathode case including a hemfold having a passivation layer on each side of the hemfold having a uniform or variable thickness of 14 μm to 75 μm and a total internal conductive layer thickness of 222 μm to 50 μm; 222. The cathode case of embodiment 221, wherein the cathode case comprises an annular sidewall comprising a passivation layer having a uniform or varying thickness of 60 pm to 200 pm and an inner conductive layer thickness of 190 μm to 50 μm.
[0254] Embodiment 23 la is a cathode case prepared from a coating laminate comprising a passivation layer having a uniform or variable thickness of 60 μm to 200 μm and a conductive layer having a uniform or variable thickness of 50 μm to 190 μm; A cathode case as described in embodiment 221, wherein the cathode case includes a hemfold, the hemfold includes a first side and a second side, each of the first and second sides further having a passivation layer having a uniform or varying thickness of 14 μm to 75 μm, the hemfold has a total thickness of 200 μm to 250 μm, and the first side of the hemfold contacts the second side of the hemfold.
[0255] Embodiment 232 is the cathode case of embodiment 221, wherein the cathode case is interchangeable with the cathode case of a commercially manufactured button cell or coin cell battery. [Brief explanation of the drawings]
[0256] [Figure 1] Figure 1 shows a chart from the National Poison Data System (NPDS) showing the frequency and severity (primary and fatal outcomes) of battery ingestion. [Figure 2] FIG. 1 shows a cross-sectional schematic view of an exemplary coin or button cell battery according to one embodiment of the present disclosure. [Figure 3] FIG. 1 shows a cross-sectional schematic view of an exemplary coin or button cell battery according to one embodiment of the present disclosure. [Figure 4]FIG. 1 illustrates a cross-sectional schematic view of an exemplary cathode case according to an embodiment of the present disclosure. [Figure 5A] FIG. 2 shows a cross-sectional schematic view of an exemplary cathode case according to an embodiment of the present disclosure. [Figure 5B] FIG. 2 illustrates a cross-sectional schematic view of an exemplary cathode case according to an embodiment of the present disclosure. [Figure 5C] FIG. 2 shows a cross-sectional schematic view of an exemplary cathode case according to an embodiment of the present disclosure. [Figure 5D] FIG. 2 illustrates a cross-sectional schematic view of an exemplary cathode case according to an embodiment of the present disclosure. [Figure 5E] FIG. 2 shows a cross-sectional schematic view of an exemplary cathode case according to an embodiment of the present disclosure. [Figure 5F] FIG. 2 shows a cross-sectional schematic view of an exemplary cathode case according to an embodiment of the present disclosure. [Figure 5G] FIG. 2 shows a cross-sectional schematic view of an exemplary cathode case according to an embodiment of the present disclosure. [Figure 5H] FIG. 2 shows a cross-sectional schematic view of an exemplary cathode case according to an embodiment of the present disclosure. [Figure 5I] FIG. 2 shows a cross-sectional schematic view of an exemplary cathode case according to an embodiment of the present disclosure. [Figure 5J] FIG. 2 shows a cross-sectional schematic view of an exemplary cathode case according to an embodiment of the present disclosure. [Figure 5K] FIG. 2 shows a cross-sectional schematic view of an exemplary cathode case according to an embodiment of the present disclosure. [Figure 5L] FIG. 2 shows a cross-sectional schematic view of an exemplary cathode case according to an embodiment of the present disclosure. [Figure 5M] FIG. 2 shows a cross-sectional schematic view of an exemplary cathode case according to an embodiment of the present disclosure. [Figure 5N] FIG. 2 shows a cross-sectional schematic view of an exemplary cathode case according to an embodiment of the present disclosure. [Figure 6A] 1 shows a cross-sectional schematic view of an exemplary cathode case illustrating placement of a passivation layer after crimping, according to an embodiment of the present disclosure. [Figure 6B] 1 shows a cross-sectional schematic view of an exemplary cathode case illustrating placement of a passivation layer after crimping, according to an embodiment of the present disclosure. [Figure 6C] 1 shows a cross-sectional schematic view of an exemplary cathode case illustrating placement of a passivation layer after crimping, according to an embodiment of the present disclosure. [Figure 6D] 10 is an SEM image of a cathode case according to an embodiment of the present disclosure illustrating the placement of the passivation layer after crimping. [Figure 7A] 1 shows a cross-sectional schematic view of an exemplary cathode case, illustrating placement of a sealant layer or extension gasket after crimping, according to an embodiment of the present disclosure. [Figure 7B] 1 shows a cross-sectional schematic view of an exemplary cathode case, illustrating placement of a sealant layer or extension gasket after crimping, according to an embodiment of the present disclosure. [Figure 8] 1 shows a cross-sectional schematic view of an exemplary cathode case illustrating the placement of the rim after crimping, according to one embodiment of the present disclosure. [Figure 9] FIG. 1 shows a cross-sectional schematic view of an exemplary coin or button cell battery according to one embodiment of the present disclosure. [Figure 10] FIG. 2 shows a cross-sectional schematic view of an exemplary anode case according to one embodiment of the present disclosure. [Figure 11] 1 shows a cross-sectional schematic view of an exemplary multi-layer stack. [Figure 12] 1 shows a cross-sectional schematic view of an exemplary multi-layer stack. [Figure 13] 1 shows a schematic diagram illustrating an exemplary method for manufacturing a cathode case. [Figure 14A] 1 shows a schematic diagram illustrating a more exemplary method for manufacturing a cathode case. [Figure 14B] 1 shows a schematic diagram illustrating a more exemplary method for manufacturing a cathode case. [Figure 14C] 1 shows a schematic diagram illustrating a more exemplary method for manufacturing a cathode case. [Figure 14D] 1 shows a schematic diagram illustrating a more exemplary method for manufacturing a cathode case. [Figure 15A] 10 shows a schematic diagram illustrating yet another exemplary method for manufacturing a cathode case. [Figure 15B]1 shows an SEM image of a portion of a cathode case with cracks in the passivation layer after hem folding. [Figure 15C] 10 shows an SEM image of a portion of a cathode case showing no cracks in the passivation layer after hem folding. [Figure 16A] 1 shows a schematic diagram illustrating a more exemplary method for manufacturing a cathode case. [Figure 16B] 1 shows a schematic diagram illustrating a more exemplary method for manufacturing a cathode case. [Figure 17] 10 shows a schematic diagram illustrating yet another exemplary method for manufacturing a cathode case. [Figure 18A] 1 shows a photograph of a four-probe milliohmmeter (Extech Model #380580) useful for measuring the resistance of the cathode case of the present disclosure. [Figure 18B] 1 shows a photograph of a four-probe milliohmmeter (Extech Model #380580) useful for measuring the resistance of the cathode case of the present disclosure. [Figure 18C] FIG. 1 shows a schematic diagram illustrating the measurement of the cathode case resistance of the present disclosure. [Figure 19] 1 shows a graph of circuit current across different types of refractory metals when immersed in 25% Ringer's solution and subjected to constant 1.5V and 3.3V DC voltages. [Figure 20] 1 shows a graph of the circuit current across different types of refractory metals when immersed in a simulated gastric fluid solution when subjected to constant 1.5V and 3.3V DC voltages. [Figure 21] Graphs comparing the DC circuit current in the same cathode can made from a tantalum cathode case before (left) and after (right) scratching using an external voltage source of 3.3 V with a 10 kOhm parallel resistive load when partially immersed in 25% Ringer's solution. [Figure 22] 1 shows a graph comparing the DC circuit current of cells made from stainless steel 304 and refractory metal cathode cans using an external voltage source of 3.3 V at different resistive loads. [Figure 23]1 shows a graph comparing the DC circuit current of batteries made from stainless steel 304 and refractory metal cans using an external voltage source of 3.3 V at different resistive loads when partially immersed in 25% Ringer's solution. [Figure 24A] 12 shows photographs of the ham after 120 minutes and after 30 minutes for a tantalum shim exposed to hydrated ham powered by an external power source. [Figure 24B] 12 shows photographs of the ham after 120 minutes and after 30 minutes for a tantalum shim exposed to hydrated ham powered by an external power source. [Figure 24C] 1 shows a graph of current versus time for a tantalum shim exposed to hydrated ham using an external power supply. [Figure 25] 1 shows a graph of voltage versus time for tantalum, titanium, gold, and SS430 shims exposed to hydrated hum using a CR2032 battery as the power source. [Figure 26] 1 shows a photographic comparison of deli ham after 24 hours of exposure in contact with batteries made with stainless steel, titanium, and tantalum cases. The top row shows the ham that was in contact with the cathode side, and the bottom row shows the anode side of the coin cell battery and the portion of the ham that was in contact with the anode side of the battery. [Figure 27] 1 shows a photographic comparison of delamination in contact cells made with stainless steel, titanium, and tantalum cathode cases after 24 hours of exposure. [Figure 28] 1 shows a graph of battery aging performance reflected as mass change over 21 days exposed to 60° C. and 90% RH, measured at 0, 8, 15 and 21 days. [Figure 29] 1 shows a graph of battery aging performance reflected as voltage change over 21 days exposed to 60° C. and 90% RH, measured at 0, 8, 15 and 21 days. [Figure 30] 1 shows the change in metal oxidation resistance in 25% non-lactating Ringer's solution for nickel, gold, niobium, and stainless steel. DETAILED DESCRIPTION OF THE INVENTION
[0257] Description of Specific Embodiments As used herein, the term "about" refers to numerical values, including, for example, integers, fractions, and percentages, whether explicitly stated or not. Unless otherwise stated or apparent from the context in which the value is used, all numerical values, whether preceded by the term "about" or not, are approximations and generally refer to a range of numerical values (e.g., + / - 5 to 10% of the recited range) that one of ordinary skill in the art would consider equivalent to the recited value (e.g., having the same function or result). When terms such as at least and about precede a list of numerical values or ranges, the term modifies all of the values or ranges provided in that list. In some instances, the term about may include numerical values that are rounded to the nearest significant figure.
[0258] As used herein, "a" or "an" means "at least one" or "one or more," unless specified otherwise. As used herein, the term "or" means "and / or," unless specified otherwise. In the context of multiple dependent claims, the use of "or" when referring back to other claims refers to those claims in the alternative only.
[0259] Unless expressly stated otherwise herein or indicated to the contrary by the context of use, when an aspect or embodiment of the subject matter herein is described or described as comprising, including, containing, having, consisting of, or consisting of certain features or elements, one or more features or elements in addition to those explicitly described or described may be present in the embodiment. However, any alternative aspect or embodiment of the subject matter herein may be described or described as consisting essentially of certain features or elements, where the aspect or embodiment is free of features or elements that would materially alter the operating principle or distinguishing characteristics of that aspect or embodiment. Furthermore, any aspect or embodiment of the subject matter herein may be described or described as consisting of certain features or elements, where only those features or elements specifically described or described as associated with that aspect or embodiment are present, for that aspect or embodiment, or for only minor variations thereof. Additionally, the term "comprising" is encompassed by the terms "consisting essentially of" and "consisting of." Similarly, the term "consisting essentially of" is intended to include aspects, embodiments, features, or elements encompassed by the term "consisting of."
[0260] As used herein, "passivating metal" refers to a metal that, when present on the exterior surface of the cathode case or both the anode and cathode cases of a battery, reduces or inhibits water electrolysis when the battery is immersed in a conductive aqueous medium. When the passivating metal is present on the exterior surface of the cathode case or both the anode and cathode cases of a battery and the battery is not in contact with an aqueous conductive medium, the metal retains electrical conductivity. The passivating metal can be, for example, Ta, Nb, W, Re, or Ti.
[0261] In some embodiments, the passivation metal is a substantially pure metal. In some embodiments, there may be more than one passivation metal. In other embodiments, the passivation metal is an alloy. In other embodiments, the passivation metal comprises an alloy of at least two passivation metals.
[0262] As used herein, "passivation layer" refers to at least one layer of the cathode case or at least one layer of both the anode case and the cathode case that includes a passivation metal.
[0263] As used herein, "deactivated" includes, but is not limited to, the inability of the battery to cause significant damage in a biological environment. A reduction in water electrolysis is one indicator that the battery has been deactivated. One indicator of reduced water electrolysis may be a reduction in bubbles from the anode when the battery is in contact with a conductive aqueous medium. Alternatively, a stable pH below 8 near the anode terminal may indicate reduced electrolysis. Another indicator of deactivation is a reduction in the electrolytic current draw of the battery immersed in a conductive aqueous medium to less than 1 mA, less than 100 μA, less than 10 μA, or less than 1 μA.
[0264] As used herein, "rapid inactivation" or "rapidly inactivate" means, without limitation, that inactivation occurs in less than 2 hours, less than 30 minutes, less than 15 minutes, less than 10 minutes, less than 5 minutes, less than 1 minute, or less than 15 seconds while immersed in a conductive aqueous medium.
[0265] As used herein, "electrical contact" refers to contact between two or more components that allows an electric current with a specific resistance to flow between the two or more components. Current can flow between two or more components when an electric potential is applied. Current can, but need not, flow continuously through materials in electrical contact. Current flow through an electrical contact can be determined by measuring electrical resistance, current, and / or voltage. The terms current, resistance, and / or voltage can be used interchangeably with the terms current, electrical resistance, and / or voltage.
[0266] In one embodiment, electrical contact can be measured by determining the electrical resistance between the inner conductive layer and the passivation layer. In one embodiment, the electrical resistance between the two materials (e.g., between the two layers) is less than 1 ohm, between 0.01 ohm and 1 ohm, between 1 ohm and 10 ohms, or between 10 ohms and 100 ohms.
[0267] In some embodiments, the electrical contact comprises at least two conductive surfaces (e.g., an internal conductive layer and a passivation layer) that are in physical contact by coating, pressing, covering, crimping, stamping, pinching, soldering, welding, and / or the use of adhesives. In other embodiments, the electrical contact comprises at least two conductive surfaces in close proximity, allowing quantum tunneling between the surfaces. In another embodiment, a quantum tunneling composite material is used to make the electrical contact.
[0268] As used herein, a "conductive path" includes, but is not limited to, a path through which charge can flow to complete a circuit between the anode (negative terminal) and cathode (positive terminal) of a battery. The anode case 201 and cathode case 202 of a battery can form a conductive path when both are in contact with a conductive aqueous medium, as shown in FIG. 2, for example. Water electrolysis is one indicator of the presence of a conductive path. One indicator of water electrolysis can be the presence of bubbles from the anode when the battery is in contact with a conductive aqueous medium. Alternatively, an increase in pH near the anode terminal can indicate the presence of a conductive path.
[0269] In tests performed on dry batteries as described herein, the battery is considered "dry" when it is not in contact with an aqueous medium, or, if in contact with an aqueous medium, it is removed from the medium and allowed to dry for at least about 24 hours, for example, by placing it in a desiccator.
[0270] "Increased" refers to an increase relative to a reference. In some embodiments, "increased" refers to an increase of 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 100% or more, 200% or more, 1000% or more, 10,000%, and / or 100,000% relative to a reference value. In some embodiments, "increase" refers to an increase of 5% to 100%, 100% to 10,000%, or 10,000% to 1,000,000%.
[0271] In some embodiments, the increase can be related to the resistance between the internal conductive layer and the passivation layer before, during, or after contact with a conductive aqueous medium, hi some embodiments, the increase can be related to the resistance of a similar cell without the passivation metal that is subjected to the same conditions as the cell with the passivation metal.
[0272] "Reduced" refers to a reduction relative to a reference. In some embodiments, "reduced" refers to a reduction of 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 99% or more, or 100% relative to a reference value. In some embodiments, "reduced" refers to a reduction of 5% to 50%, 10% to 20%, or 50% to 100%.
[0273] In some embodiments, the reduction may relate to the electrical contact, current, or voltage of the cell prior to contact with the conductive aqueous medium, hi some embodiments, the reduction may relate to the electrical contact, electrochemical reaction rate, current, or voltage of a similar cell without the passivating metal.
[0274] "Inhibited" means preventing an effect from occurring relative to a reference. In some embodiments, inhibition may relate to the electrochemical reaction or electrolytic current of the cell prior to contact with the conductive aqueous medium.
[0275] As used herein, "conductive aqueous media" includes, but is not limited to, saline and buffered aqueous solutions; bodily fluids such as digestive fluids, saliva, mucus, chyme, bile, moist tissue, and blood; and conductive water-containing solutions such as aqueous gels. The resistivity of the conductive aqueous media is 1 MOhm-cm or less. The pH of the conductive aqueous media can range from 1-9 pH, 1-3 pH, 4-7 pH, and 7-9 pH to model different biological solutions.
[0276] As used herein, "non-conductive aqueous medium" refers to purified or deionized water, or a solution of water containing a non-ionic cleaning detergent, having a resistivity greater than 1 Mohm-cm.
[0277] As used herein, a layer, or material, or component having a "uniform" thickness has a consistent thickness that does not vary by more than, for example, 0-0.5%, or 0-1%, or 0-5%, or 0-10%, or 0-12%, or 0-15% within the layer. When a thickness range or value is specified, the layer does not vary by, for example, more than 0-0.5%, or 0-1%, or 0-5%, or 0-10%, or 0-12%, or 0-15% within the specified range or from the specified value.
[0278] As used herein, a layer, material, or component having a "varying" thickness is one that varies within the layer, for example, by 15% to 500%, or 15% to 300%, or 15% to 200%, or 15% to 100%, or 15% to 50%, or 15% to 25%, or 15% to 20%. When a thickness range or value is specified, the layer can vary, for example, by 15% to 500%, or 15% to 300%, or 15% to 200%, or 15% to 100%, or 15% to 50%, or 15% to 25%, or 15% to 20% within the specified range (or from the specified value), and the range includes the recited endpoints unless otherwise indicated.
[0279] For purposes of this disclosure, a layer having a uniform or varying thickness within a specified range is a layer having at least some portion of that layer within the specified range, the range including the recited endpoints unless otherwise indicated. A layer having a uniform or varying thickness within a specified range or value may also have some portion of the layer outside the specified range. A layer may have up to 30%, or 0.1% to 20%, or 0.1% to 10% of the layer outside the recited thickness range or value. For example, a cathode case including a hemfold structure (see Figures 15B and 15C) may have a region at the bend of the hemfold or at the end where at least a portion of that layer is outside the specified range or value.
[0280] I. Exemplary Batteries The present disclosure provides batteries that are safer than existing batteries and less likely to cause tissue damage when ingested, for example, by a child or pet accidentally swallowing the battery. In some embodiments, the batteries rapidly deactivate in a conductive aqueous environment, such as in contact with biological tissue, in the presence of a potential difference provided by the battery. The present disclosure relates to any battery, and in certain embodiments, the present disclosure provides coin or button cell batteries, such as nominal 3 volt or nominal 1.5 volt button cell batteries.
[0281] In some embodiments disclosed herein, the battery includes Ta. In other embodiments, the battery includes Nb. In some embodiments, the battery includes Ti. In some embodiments, the battery includes W. In some embodiments, the battery includes Re. In some embodiments, the battery includes an alloy of Re, Ta, Nb, W, and / or Ti. In some embodiments, the battery includes any combination of Re, Ta, Nb, W, and / or Ti. In some embodiments disclosed herein, the cathode case or the anode case and the cathode case include Re, or Ta, or Nb, or W, or Ti, or any combination of two or more thereof. In some embodiments, the cathode case or the anode case and the cathode case include an alloy of Re, Ta, Nb, W, and / or Ti, or any combination of two or more thereof.
[0282] In some embodiments disclosed herein, the battery includes a passivation metal. In some embodiments disclosed herein, the battery includes a passivation metal in a passivation layer.
[0283] In some embodiments disclosed herein, the battery includes an internal conductive layer. In some embodiments, the internal conductive layer is disposed between the passivation layer and the anode or cathode of the electrochemical cell. In some embodiments, the internal conductive layer is in electrical contact with the passivation layer and in electrical contact with the anode or cathode of the electrochemical cell.
[0284] In some embodiments, the battery includes a passivating metal, wherein the passivating metal is present in a layer having a uniform or variable thickness between 100 nm and 400 μm. In some embodiments, the passivating metal has a thickness between 100 nm and 1 μm, between 100 nm and 3 μm, between 100 nm and 5 μm, between 100 nm and 10 μm, between 1 μm and 400 μm, between 3 μm and 100 μm, between 3 μm and 50 μm, between 15 μm and 300 μm, between 14 μm and 200 μm, between 25 μm and 50 μm, between 50 μm and 400 μm, between 50 μm and 300 μm, The thickness of the polymer may be in a layer having a uniform or varying thickness of 0 μm, 50 μm to 200 μm, 50 μm to 175 μm, 55 μm to 400 μm, 55 μm to 300 μm, 55 μm to 200 μm, 60 μm to 400 μm, 60 μm to 300 μm, 60 μm to 200 μm, 200 μm to 300 μm, or 300 μm to 400 μm. Additional exemplary ranges are disclosed throughout this application.
[0285] Provided herein is a cathode case including a cathode interior conductive layer and a cathode passivation layer including a passivation metal, wherein the cathode interior conductive layer and the cathode passivation layer are in electrical contact. In some embodiments, a battery of the present disclosure comprises a cathode case including a cathode interior conductive layer and a cathode passivation layer including a passivation metal, wherein the cathode interior conductive layer and the cathode passivation layer are in electrical contact.
[0286] In some embodiments, the inner conductive layer has a uniform or varying thickness of from 1 μm to 400 μm, or from 175 μm to 300 μm, or from 75 to 300 μm. Other examples of inner conductive layer thicknesses are provided throughout.
[0287] In some embodiments, the thickness of the passivation layer relative to the internal conductive layer is selected to minimize or prevent exposure of the surface of the internal conductive layer that is in electrical contact with the passivation layer when the battery or cathode case is exposed to or immersed in a conductive aqueous medium. In some embodiments, the thickness of the passivation layer relative to the internal conductive layer is selected to minimize or prevent cracking of the passivation layer during manufacturing, for example, during a crimping, rolling, or folding process (e.g., a process to create a hemfold). A hemfold is a process used to fold the annular sidewall toward the interior surface of the cathode case. This facilitates the presentation of the passivation layer at the cathode case rim. A hemfold is shown at least in FIGS. 14A, 14D, and 15A, 15B, and 15C. The thickness of the passivation layer that minimizes or prevents cracking will vary based on the selection of the passivation layer, the internal conductive layer, and the configuration of the cathode and / or anode case.
[0288] In some embodiments, the thickness of the passivation layer is between 1% and 10,000% of the thickness of the internal conductive layer. In some embodiments, the thickness of the passivation layer is between 10% and 1,000% of the thickness of the internal conductive layer. In some embodiments, the thickness of the passivation layer is between 100% and 10,000% of the thickness of the internal conductive layer. In some embodiments, the thickness of the passivation layer is between 100% and 1,000% of the thickness of the internal conductive layer. In some embodiments, the thickness of the passivation layer is between 100% and 500% of the thickness of the internal conductive layer.
[0289] In some embodiments, the internal conductive layer and passivation layer (of either the anode or cathode) have a uniform or varying thickness in a ratio (passivation layer:internal conductive layer) of 1:1-5, or 1:1.1-4.5, or 1:1.5-4, or 1:2-3, or 1:1, or 1:1.2, or 1:1.5, or 1:2, or 1:2.5, or 1:3, or 1:3.5, or 1:4, or 1:4.5, or 1:5. In some embodiments, the internal conductive layer and passivation layer (of either the anode or cathode) have a uniform or varying thickness in a ratio (passivation layer:internal conductive layer) of 1:1-20, or 1:1-10, or 1:10, or 1:20. In other embodiments, the conductive and passivation layers in the laminate have uniform or varying thicknesses with a ratio (passivation layer:internal conductive layer) of 1 to 20:1, or 1 to 10:1, or 10:1, or 20:1. In other embodiments, the conductive and passivation layers in the laminate have uniform or varying thicknesses with a ratio (passivation layer:internal conductive layer) of 1 to 5:1, or 1.1 to 4.5:1, or 1.5 to 4:1, or 2 to 3:1, or 1:1, or 1.2:1, or 1.5:1, or 2:1, or 2.5:1, or 3:1, or 3.5:1, or 4:1, or 4.5:1, or 5:1. For clarity, a ratio range of 1:1 to X means 1:1 to 1:X, and 1 to X:1 means 1:X to 1:1. In some embodiments, the internal conductive and passivation layers (of either the anode or cathode) have a ratio of 8:1 to 1:5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:5, or 6:1 to 1:3, or 6:1 to 1:2, or 6:1 to 1:1.1, or 6:1 to 1:1, 3:1 to 1:5, or 3:1 to 1:3, or 3:1 to 1:2, or 3:1 to 1:1.1, or 3:1 to 1:1, or has a uniform or varying thickness in a ratio (passivation layer:inner conductive layer) of 2:1 to 1:5, or 2:1 to 1:3, or 2:1 to 1:2, or 2:1 to 1:1.1, or 2:1 to 1:1, or 8:1 to 1:2.5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:2, or 3:1 to 1:2, for example, at least one point on the bottom portion of the cathode case (e.g., 413 in FIG. 4).
[0290] In some embodiments, the passivation metal is present in a layer having a uniform or varying thickness sufficient to prevent exposure of the surface of the inner conductive layer that is in electrical contact with the passivation layer to the ambient environment. In some embodiments, the uniform layer is within 0.01 mm of the inner conductive layer to the ambient environment. 2 Less than or equal to 0.05 mm 2 Less than or 0.5 mm 2 Less than or 1.0 mm 2 Less than or 1.5 mm 2 In some embodiments, the passivation metal is present in a layer having a uniform or varying thickness that reduces or prevents cracking of the layer upon folding. In some embodiments, the uniform layer may be exposed to less than 0.01 mm of the inner conductive layer during folding, crimping, or any other manufacturing process that stretches or makes the metal layer thinner in the final manufactured product compared to the thickness of the metal layer at the start of the manufacturing process. 2 Less than or equal to 0.05 mm 2 Less than or 0.5 mm 2 Less than or 1.0 mm 2 Less than or 1.5 mm 2 The cathode interior conductive layer is prevented from being exposed to the ambient environment for less than 0.01 mm2, or less than 0.05 mm2, or less than 0.1 mm2, or less than 0.5 mm2, or less than 1.0 mm2, or less than 1.5 mm2 of the surface of the cathode interior conductive layer in electrical contact with the cathode passivation layer is exposed to the ambient environment after fabrication. In some embodiments, post-fabrication means after the cathode case is formed into a can or case. In some embodiments, post-fabrication means after the cathode case is assembled into a battery. In some embodiments, post-fabrication means after the cathode is assembled into a battery that is ready for use.
[0291] In some embodiments, the combined thickness of the internal conductive layer and passivation layer is no greater than 50 μm, 100 μm, 200 μm, 300 μm, or 400 μm, hi some embodiments, the combined thickness of the internal conductive layer and passivation layer is 25 μm to 400 μm, or 25 μm to 50 μm, or 50 μm to 100 μm, or 100 μm to 200 μm, or 200 μm to 300 μm, or 300 μm to 400 μm.
[0292] In one embodiment of a coin cell battery with an anode case and a cathode case, the entire cell has a height of 3.2 mm and an outer diameter of 20 mm. The combination of the various layers of the anode case and cathode case described herein is selected to maintain the final overall cell dimensions.
[0293] FIG. 2 illustrates a cross-sectional view of an exemplary coin or button cell battery 200 according to one embodiment of the present disclosure.
[0294] The exemplary battery 200 includes: an anode case 201; a cathode case 202 containing a passivated metal; The electrochemical cell includes an anode 203, a cathode 205, a separator 204 positioned between the anode and cathode, and a gasket 206 between the anode case and the cathode case.
[0295] The separator generally provides physical separation between the anode and cathode and can be made from any material known in the art. Additionally, an electrolyte can be included in the battery, as is well understood in the art.
[0296] A gasket 206 may be advantageously disposed between the anode case and the cathode case to provide a seal between the anode case and the cathode case. The gasket may comprise a non-conductive material, such as an elastomeric material or another polymer. As shown in FIG. 2, the cathode case 202 may include a cathode inner conductive layer 202a and a cathode passivation layer 202b, where the cathode inner conductive layer and the cathode passivation layer are in electrical contact.
[0297] In some embodiments, after at least a portion of the passivation layer contacts the conductive aqueous medium, electrolysis of the conductive aqueous medium is reduced or inhibited (e.g., compared to that observed from a battery without a passivation layer). When the battery is immersed or partially immersed in a conductive aqueous medium, the passivation metal undergoes at least partial electrochemical oxidation upon contact with the conductive aqueous medium. In some embodiments, the oxide formed is an oxide of the passivation metal. In one embodiment, a surface oxide develops or propagates on the portion of the passivation metal exposed to the conductive aqueous medium. In some embodiments, the passivation metal forms a native surface oxide comprising an oxide of the passivation metal that is continuous across the surface exposed to the conductive aqueous medium. In some embodiments, the passivation metal forms, grows, or transforms into a continuous solid outer oxide layer, particularly under an applied potential. In some embodiments, the oxide layer forms in less than two hours when the battery is exposed to the oxidation current generated when immersed in a conductive aqueous medium and the battery electrodes are in electrical contact through the aqueous medium.
[0298] In some embodiments, the batteries and / or cathode cases described herein generate a current of less than 1.5 mA, or less than 1 mA, or less than 0.5 mA, or less than 0.3 mA within 2 hours, or less than 1 hour, or less than 30 minutes, or less than 10 minutes of initial contact with an aqueous conductive medium. In some embodiments, the oxide layer, once formed, maintains an oxidation current of less than 1.5 mA, or less than 1 mA, or less than 0.5 mA, or less than 0.3 mA.
[0299] In some embodiments, the surface oxide may be resistant to further oxidation. Without being bound by theory, it is believed that resistance to further oxidation may inhibit the oxidative half-reaction of electrolysis at the cathode. Reduction or inhibition of the oxidative half-reaction may in turn inhibit the reductive half-reaction of electrolysis at the anode. Under these conditions, the production of hydroxide ions, which create a basic environment that can cause tissue damage, is reduced or inhibited, improving safety in the event of ingestion.
[0300] In some embodiments, a battery including a passivation metal (e.g., in a passivation layer) can inhibit or reduce electrolysis in a conductive aqueous medium (e.g., compared to that observed from a battery without a passivation layer) when immersed in the conductive aqueous medium for an extended period of time, e.g., less than 5 hours, less than 3 hours, less than 2 hours, less than 1 hour, 1-2 hours, 1-3 hours, 1-5 hours, 2-3 hours, 2-5 hours, or 3-5 hours.
[0301] In other embodiments, the passivation layer includes a surface oxide prior to contact with the aqueous conductive medium. This surface oxide can be a native oxide formed upon exposure to air. The surface oxide can also be formed by exposure to an acidic solution, a basic solution, or an oxidizing solution with or without an applied electrical potential across the passivation layer. This surface oxide can also be formed by depositing a metal oxide using a deposition process, exposing the passivation layer to a furnace having an oxygen-rich atmosphere, or exposing the passivation layer to an oxygen plasma. The surface oxide, as discussed above, provides resistance to further oxidation of the passivation metal and can effectively limit the resulting maximum current draw of an exemplary battery while immersed in a conductive aqueous environment.
[0302] Whether the surface oxide is a native oxide, formed prior to assembly of the battery, formed after assembly of the battery but prior to contact with conductive aqueous media, or occurs upon exposure to conductive aqueous media, the resulting maximum electrolytic current draw of the battery may be limited to less than 1 mA, less than 100 μA, less than 10 μA, or less than 1 μA for a relatively short period of time, such as within 2 hours, 1 hour, 30 minutes, 20 minutes, 10 minutes, 5 minutes, or 1 minute.
[0303] In some embodiments, when immersed in an aqueous conductive medium, where the aqueous conductive medium is simulated saliva, gastric fluid, or intestinal fluid, the battery or cathode case described herein generates an oxidation current of 1 mA or less, or 0.5 mA or less, within 120 minutes, or within 30 minutes, or within 10 minutes of initial contact with the aqueous conductive medium, each resulting in minimal damage in the Ham test and / or simulated pig esophagus test described herein. In some embodiments, the exterior surface of the battery or cathode case is abrasion resistant and the surface area of the stainless steel inner conductive layer exposed to the ambient environment is within 0.5 mm 2 Keep it below.
[0304] In some embodiments, the battery is a button or coin cell type battery. In other embodiments, the electrochemical cells of the exemplary battery have a voltage of 10 V or less, 5 V or less, 3 V or less, or 1 V or less. In another embodiment, the exemplary battery is a 3 volt or 1.5 volt button or coin cell.
[0305] In other embodiments, exemplary batteries are CR927, CR1025, CR1130, CR1216, CR1220, CR1225, CR1616, CR1620, CR1625, CR1632, CR2012, CR2016, CR2025, CR2032, CR2320, CR2335, CR2354, CR2412, CR2430, CR2450, CR2477, CR2507, CR3032, or CR11108 lithium coin cell batteries. In some embodiments, the exemplary battery is an SR41, SR43, SR44, SR45, SR48, SR54, SR55, SR57, SR58, SR59, SR60, SR63, SR64, SR65, SR66, SR67, SR68, SR69, S516, SR416, SR731, SR512, SR714, or SR712 silver oxide coin cell battery. In other embodiments, the exemplary battery is an LR41, LR44, LR54, or LR66 alkaline coin cell battery. In further embodiments, the battery is a CR2032, CR2016, or CR2025 lithium coin cell battery. In other embodiments, the battery is an AAAA, AAA, AA, A, B, C, D, E 90 / N, 4001, 810, 910A, AM5, LR1, MN9100, or UM-5 cylindrical battery.
[0306] In other embodiments, the exemplary battery is a secondary battery. In other embodiments, the exemplary battery is a rechargeable battery.
[0307] The batteries of the present disclosure are manufactured within industry standard dimensions. Accordingly, the dimensions of the internal conductive and passivation layers are selected to provide a complete and operational battery that meets these standards. The current IEC standard for portable primary (non-rechargeable) batteries is number 60086. The relevant US standard is the ANSI Cl 8 series, developed by a committee of the US National Electrical Manufacturers Association (NEMA). The batteries disclosed herein can be made to any industry-accepted standard size.
[0308] For example, a CR2032 battery has an outer diameter of 20 mm and a height of 3.2 mm.
[0309] A. Exemplary Batteries with Ta or Nb Passivation Layers 1. Exemplary Cells with Ta or Nb Passivation Layer on Cathode Case In some embodiments, the batteries disclosed herein include a cathode case comprising a passivation metal, wherein the passivation metal comprises Nb, Ta, an alloy thereof, or any combination thereof. In other embodiments, the passivation metal comprising Nb, Ta, an alloy thereof, or any combination thereof is present in a passivation layer having a uniform or variable thickness of 100 nm to 400 μm, 100 nm to 3 μm, 3 μm to 100 μm, 3 μm to 50 μm, 200 μm to 300 μm, or 300 μm to 400 μm.
[0310] In some embodiments, a battery comprising a cathode case comprising a passivating metal comprising Nb, Ta, an alloy thereof, or any combination thereof, further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, or any combination of two or more thereof.
[0311] In some embodiments, the cathode case is an internal support member. In some embodiments, the cathode case does not include an internal conductive layer, and the battery does not include an external coating. In other embodiments, the cathode case consists essentially of a layer including a passivation metal, the layer having a uniform or variable thickness between 200 μm and 300 μm. In yet other embodiments, the cathode case consists essentially of a layer including a passivation metal, the layer having a uniform or variable thickness between 200 μm and 300 μm.
[0312] As used herein, an "external coating" is a metal layer on the outside of the cathode case, anode case, or both, that provides lower contact resistance than passivated metal and / or improves the aesthetics of the battery by providing high brightness or gloss.
[0313] In further embodiments, the battery comprising a passivating metal comprising Nb, Ta, an alloy thereof, or any combination thereof, comprises an exterior coating on the exterior surface of the anode case or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, or any combination of two or more thereof, and further wherein the exterior coating has a uniform or varying thickness of 100 nm to 7 μm, 100 nm to 5 μm, or 100 nm to 200 nm.
[0314] In another embodiment, the cathode case comprises a cathode inner conductive layer and a cathode passivation layer comprising Ta, Nb, an alloy thereof, or any combination thereof, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact, and the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, or any combination of two or more thereof, and wherein the exterior coating and the cathode passivation layer are in electrical contact.
[0315] In some embodiments, a battery including a cathode case including a passivation layer including Nb, Ta, alloys thereof, or any combination thereof does not include an external coating. In other embodiments, the cathode case consists essentially of a cathode inner conductive layer and a cathode passivation layer including a passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact. In other embodiments, the cathode case consists essentially of a cathode inner conductive layer and a cathode passivation layer including a passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact.
[0316] In other embodiments, a cathode passivation layer comprising Nb, Ta, alloys thereof, or any combination thereof has a uniform or variable thickness between 100 nm and 100 μm, between 100 nm and 3 μm, between 3 μm and 25 μm, or between 25 μm and 50 μm. In some embodiments, the passivation layer has a uniform or variable thickness between 15 μm and 300 μm, between 14 μm and 200 μm, or between greater than 50 μm and 300 μm, or between greater than 50 μm and 200 μm. In some embodiments, the cathode internal conductive layer has a uniform or variable thickness between 175 μm and 300 μm.
[0317] In yet another embodiment, the cathode passivation layer comprising Nb, Ta, an alloy thereof, or any combination thereof further comprises a first layer comprising a first passivation metal and a second layer of a second passivation metal. In some embodiments, the cathode passivation layer comprises a first layer comprising Ta or an alloy thereof. In other embodiments, the cathode passivation layer comprises a first layer comprising Ta or an alloy thereof, the first layer having a uniform or variable thickness between 1 μm and 3 μm.
[0318] In another embodiment, the cathode passivation layer includes a second layer comprising Nb or an alloy thereof. In another embodiment, the cathode passivation layer includes a first layer comprising Nb or an alloy thereof, and the second layer has a uniform or variable thickness of 10 μm to 250 μm, or 10 μm to 30 μm. In yet another embodiment, the cathode internal conductive layer has a uniform or variable thickness of 75 μm to 300 μm, or 175 μm to 300 μm.
[0319] 2. Exemplary Cells with Ta and / or Nb Passivation Layers on the Cathode and Anode Cases In one embodiment, an exemplary battery 300, such as that illustrated in FIG. an anode case 301 including an anode inner conductive layer 301a and an anode passivation layer 301b including a passivation metal including Nb, Ta, an alloy thereof, or any combination thereof, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact; a cathode case 302 including a cathode interior conductive layer 302a and a cathode passivation layer 302b including a passivation metal, the cathode interior conductive layer and the cathode passivation layer being in electrical contact; The electrochemical cell includes an anode 303, a cathode 305, a separator 304 positioned between the anode and cathode, and a gasket 306 between the anode case and the cathode case.
[0320] The materials for the inner conductive layer of the anode and the inner conductive layer of the cathode case are selected from any known in the battery art. The anode case provides a protective barrier for the anode and generally comprises an electrically conductive material.
[0321] In one embodiment of the battery disclosed herein, in which the cathode case comprises a passivation metal comprising Nb or Ta, an alloy thereof, or any combination thereof, the battery also includes an anode case comprising an anode inner conductive layer and an anode passivation layer comprising a passivation metal comprising Nb, Ta, an alloy thereof, or any combination thereof, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact, and the battery further includes an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, or any combination of two or more thereof, and wherein the exterior coating and the anode passivation layer are in electrical contact.
[0322] In another embodiment of a battery comprising an anode case including an anode passivation layer comprising an anode internal conductive layer and a passivation metal comprising Nb, Ta, an alloy thereof, or any combination thereof, wherein the anode internal conductive layer and the anode passivation layer are in electrical contact, the battery does not include an external coating on the exterior surface of the anode case or the exterior surface of the cathode case. In yet another embodiment, the anode case consists essentially of the anode internal conductive layer and the anode passivation layer comprising a passivation metal comprising Nb, Ta, an alloy thereof, or any combination thereof, wherein the anode internal conductive layer and the anode passivation layer are in electrical contact. In yet another embodiment, the anode case consists of the anode internal conductive layer and the anode passivation layer comprising a passivation metal comprising Nb, Ta, an alloy thereof, or any combination thereof, wherein the anode internal conductive layer and the anode passivation layer are in electrical contact.
[0323] In one embodiment, the anode passivation layer comprising Nb, Ta, alloys thereof, or any combination thereof has a uniform or variable thickness of 100 nm to 400 μm, 100 nm to 100 μm, 100 nm to 3 μm, 3 μm to 25 μm, or 25 μm to 50 μm. In another embodiment, the anode passivation layer comprising Nb, Ta, alloys thereof, or any combination thereof has a uniform or variable thickness of 100 nm to 100 μm, 100 nm to 3 μm, 3 μm to 25 μm, or 25 μm to 50 μm, and the anode inner conductive layer has a uniform or variable thickness of 175 μm to 300 μm, or 200 μm to 300 μm.
[0324] In a further embodiment, the anode passivation layer comprising Nb, Ta, an alloy thereof, or any combination thereof further comprises a first layer comprising a first passivation metal and a second layer of a second passivation metal.
[0325] In some embodiments, the anode passivation layer includes a first layer comprising Ta or an alloy thereof. In some embodiments, the anode passivation layer includes a first layer comprising Ta or an alloy thereof, the first layer having a uniform or variable thickness between 1 μm and 3 μm. In some embodiments, the anode passivation layer includes a second layer comprising Nb or an alloy thereof. In some embodiments, the anode passivation layer includes a second layer comprising Nb or an alloy thereof, the second layer having a uniform or variable thickness between 10 μm and 250 μm, or between 10 μm and 30 μm. In some embodiments, the anode internal conductive layer has a uniform or variable thickness between 75 μm and 300 μm, or between 200 μm and 300 μm.
[0326] Exemplary Batteries with BW or Re Passivation Layers 1. Exemplary Cells with W or Re Passivation Layer on Cathode Case In other embodiments of the batteries disclosed herein, the cathode case includes a passivation metal including W, Re, or an alloy thereof. In other embodiments, the cathode case includes a passivation layer including W, Re, or an alloy thereof, the passivation layer having a uniform or variable thickness of 100 nm to 400 μm, or 100 nm to 25 μm, or 100 nm to 3 μm, or 3 μm to 25 μm. The thickness of the passivation layer can be selected to support a selected manufacturing process.
[0327] In some embodiments, a battery including a cathode case comprising W, Re, or an alloy thereof further includes an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, where the exterior coating includes Ni, Al, Cu, Cr, Zn, or any combination of two or more thereof.
[0328] In further embodiments, the battery comprising W, Re, or an alloy thereof includes an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, or any combination of two or more thereof, and further wherein the exterior coating has a uniform or varying thickness of 100 nm to 7 μm, 100 nm to 5 μm, or 100 nm to 200 nm.
[0329] In another embodiment, the cathode case comprises a cathode inner conductive layer and a cathode passivation layer comprising W, Re, or an alloy thereof, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact, and the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of any two or more thereof, and wherein the exterior coating and the cathode passivation layer are in electrical contact.
[0330] In other embodiments, the cathode passivation layer comprising W, Re, or an alloy thereof has a uniform or variable thickness between 100 μm and 25 μm, between 3 μm and 25 μm, or between 1 μm and 3 μm. In some embodiments, the cathode interior conductive layer has a uniform or variable thickness between 200 μm and 300 μm.
[0331] In some embodiments, a battery including a cathode case comprising W, Re, or an alloy thereof does not include an external coating on the exterior surface of the anode case or the exterior surface of the cathode case. In some embodiments, the battery includes a cathode case consisting essentially of a cathode internal conductive layer and a cathode passivation layer comprising a passivation metal, the cathode internal conductive layer and the cathode passivation layer being in electrical contact. In some embodiments, the battery includes a cathode case consisting essentially of a cathode internal conductive layer and a cathode passivation layer comprising a passivation metal, the cathode internal conductive layer and the cathode passivation layer being in electrical contact.
[0332] In yet another embodiment, the cathode passivation layer comprising W, Re, or an alloy thereof further comprises a first layer comprising a first passivation metal and a second layer comprising a second passivation metal. In some embodiments, the cathode passivation layer comprises a first layer comprising W, Re, or an alloy thereof. In other embodiments, the cathode passivation layer comprises a first layer comprising W, Re, or an alloy thereof, the first layer having a uniform or variable thickness between 1 μm and 25 μm. In another embodiment, the cathode passivation layer comprises a second layer comprising Nb or an alloy thereof. In some embodiments, the cathode passivation layer comprises a second layer comprising Nb or an alloy thereof, the second layer having a uniform or variable thickness between 5 μm and 30 μm. In yet another embodiment, the cathode internal conductive layer has a uniform or variable thickness between 200 μm and 300 μm.
[0333] 2. Exemplary Cells with W or Re Passivation Layers on the Cathode and Anode Cases In one embodiment, also shown in FIG. 3, an exemplary battery 300 includes: an anode case 301 including an anode inner conductive layer 301a and an anode passivation layer 301b including a passivation metal including W, Re, or an alloy thereof, wherein the anode inner conductive layer and the anode passivation metal layer are in electrical contact; a cathode case 302 including a cathode interior conductive layer 302a and a cathode passivation layer 302b including a passivation metal, the cathode interior conductive layer and the cathode passivation layer being in electrical contact; The electrochemical cell includes an anode 303, a cathode 305, a separator 304 positioned between the anode and cathode, and a gasket 306 between the anode case and the cathode case.
[0334] In one embodiment of the battery disclosed herein, in which the cathode case comprises a passivation metal comprising W, Re, or an alloy thereof, the battery also comprises an anode case comprising an anode inner conductive layer and an anode passivation layer comprising a passivation metal comprising W, Re, or an alloy thereof, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact, and the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, or any combination of two or more thereof, and wherein the exterior coating and the anode passivation layer are in electrical contact.
[0335] In another embodiment, the anode case includes an anode internal conductive layer and an anode passivation layer including a passivation metal including W, Re, or an alloy thereof, the anode internal conductive layer and the anode passivation layer being in electrical contact, and the battery does not include an external coating on the exterior surface of the anode case or the exterior surface of the cathode case. In yet another embodiment, the anode case consists essentially of the anode internal conductive layer and the anode passivation layer including a passivation metal including W or Re, the anode internal conductive layer and the anode passivation layer being in electrical contact. In another embodiment, the anode case consists of the anode internal conductive layer and the anode passivation layer including a passivation metal including W or Re, the anode internal conductive layer and the anode passivation layer being in electrical contact.
[0336] In one embodiment, the anode passivation layer comprising W, Re, or an alloy thereof has a uniform or variable thickness of 100 nm to 25 μm, 3 μm to 25 μm, or 1 μm to 3 μm. In another embodiment, the anode passivation layer comprising W, Re, or an alloy thereof has a uniform or variable thickness of 100 nm to 25 μm, 3 μm to 25 μm, or 1 μm to 3 μm, and the anode inner conductive layer has a uniform or variable thickness of 75 μm to 300 μm or 200 μm to 300 μm.
[0337] In further embodiments, the anode passivation layer comprising W, Re, or an alloy thereof further comprises a first layer comprising a first passivation metal and a second layer comprising a second passivation metal. In some embodiments, the anode passivation layer further comprises a first layer comprising W, Re, or an alloy thereof. In some embodiments, the anode passivation layer further comprises a first layer comprising W, Re, or an alloy thereof, the first layer having a uniform or variable thickness between 1 μm and 3 μm. In some embodiments, the anode passivation layer further comprises a second layer comprising Nb or an alloy thereof. In some embodiments, the anode passivation layer further comprises a second layer comprising Nb or an alloy thereof, the second layer having a uniform or variable thickness between 10 μm and 30 μm. In some embodiments, the anode internal conductive layer has a uniform or variable thickness between 75 μm and 300 μm or between 200 μm and 300 μm.
[0338] C. Exemplary Battery with Ti Passivation Layer 1. Exemplary Battery with Ti Passivation Layer on Cathode Case In other embodiments of the batteries disclosed herein, the cathode case includes a passivation metal including Ti or an alloy thereof, and the battery optionally includes an exterior coating on the exterior surface of the anode case, the exterior surface of the cathode case, or both, where the exterior coating includes Al, Cu, Cr, Zn, or any combination of two or more thereof. In other embodiments, the passivation metal including Ti is present in a layer having a uniform or variable thickness of 1 μm to 400 μm, greater than 50 μm to 400 μm, greater than 50 μm to 300 μm, greater than 50 μm to 200 μm, 200 μm to 300 μm, or 300 μm to 400 μm. The thickness of the passivation layer can be selected to support a selected manufacturing process.
[0339] In one embodiment, the battery does not include an external coating on the exterior surface of the anode case or the exterior surface of the cathode case. In one embodiment, the cathode case consists essentially of a layer including a passivation metal containing Ti, the layer having a uniform or variable thickness between 200 pm and 300 pm. In another embodiment, the cathode case consists essentially of a layer including a passivation metal containing Ti, the layer having a uniform or variable thickness between 200 μm and 300 μm.
[0340] In other embodiments, an exterior coating comprising Al, Cu, Cr, Zn, or any combination of two or more thereof is present on both the exterior surface of the anode case and the exterior surface of the cathode case. In other embodiments of the batteries disclosed herein in which the cathode case comprises a passivation metal comprising Ti or an alloy thereof, the exterior coating, if present, does not comprise Ni. In other embodiments, the exterior coating is present on the exterior surface of the anode case. In other embodiments, the exterior coating is present on the exterior surface of the cathode case. In some embodiments, the exterior coating has a uniform or variable thickness of 100 nm to 7 μm or 100 nm to 5 μm.
[0341] In some embodiments, the cathode case includes a cathode inner conductive layer and a cathode passivation layer including a passivation metal including Ti or an alloy thereof, and the cathode inner conductive layer and the cathode passivation layer are in electrical contact. In other embodiments, the cathode case includes a cathode inner conductive layer and a cathode passivation layer including a passivation metal including Ti or an alloy thereof, and the cathode inner conductive layer and the cathode passivation layer are in electrical contact, and the battery further includes an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, and the exterior coating includes Al, Cu, Cr, Zn, or any combination of two or more thereof, and the exterior coating and the cathode passivation layer are in electrical contact.
[0342] In another embodiment, the cathode case consists essentially of a cathode inner conductive layer and a cathode passivation layer comprising a passivation metal comprising Ti or an alloy thereof, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact.
[0343] In a further embodiment, the cathode case comprises a cathode internal conductive layer and a cathode passivation layer comprising a passivation metal comprising Ti or an alloy thereof, the cathode internal conductive layer and the cathode passivation layer being in electrical contact. In another embodiment, the cathode passivation layer comprising Ti or an alloy thereof has a uniform or variable thickness between 50 μm and 100 μm. In a further embodiment, the cathode passivation layer comprising Ti or an alloy thereof has a uniform or variable thickness between 50 μm and 100 μm, and the cathode internal conductive layer has a uniform or variable thickness between 175 μm and 300 μm.
[0344] 2. Exemplary Battery with Ti Passivation Layers on the Cathode and Anode Cases In one embodiment of the battery disclosed herein, in which the cathode case comprises a passivation metal comprising Ti or an alloy thereof, the battery also comprises an anode case comprising an anode inner conductive layer and an anode passivation layer comprising a passivation metal comprising Ti or an alloy thereof, the anode inner conductive layer and the anode passivation layer being in electrical contact. In some embodiments, the anode case comprises a passivation metal.
[0345] In some embodiments, the anode case comprises a passivating metal comprising Ti or an alloy thereof, and the battery optionally comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Al, Cu, Cr, or Zn, an alloy thereof, or any combination of two or more thereof.
[0346] In a similar embodiment, the anode case includes an anode inner conductive layer and an anode passivation layer including a passivation metal including Ti or an alloy thereof, the anode inner conductive layer and the anode passivation layer being in electrical contact, and the battery further includes an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, the exterior coating including Al, Cu, Cr, Zn, or any combination of two or more thereof, and the exterior coating and the anode passivation layer being in electrical contact.
[0347] In another embodiment, the anode case comprises an anode inner conductive layer and an anode passivation layer comprising a passivation metal comprising Ti or an alloy thereof, the anode inner conductive layer and the anode passivation layer being in electrical contact, and the battery further comprises an exterior coating on the exterior surface of the anode case or the exterior surface of the cathode case.
[0348] In another embodiment, the anode case consists essentially of an anode inner conductive layer and an anode passivation layer comprising a passivation metal comprising Ti or an alloy thereof, the anode inner conductive layer and the anode passivation layer being in electrical contact.
[0349] In yet another embodiment, the anode case comprises an anode inner conductive layer and an anode passivation layer comprising a passivation metal comprising Ti or an alloy thereof, the anode inner conductive layer and the anode passivation layer being in electrical contact.
[0350] In some embodiments, the anode passivation layer comprising Ti or an alloy thereof has a uniform or varying thickness between 50 μm and 100 μm. In other embodiments, the anode passivation layer has a uniform or varying thickness between 50 μm and 100 μm, and the anode interior conductive layer has a uniform or varying thickness between 75 μm and 350 μm, or between 125 μm and 350 μm, or between 25 μm and 100 μm, or between 175 μm and 300 μm, or between 200 μm and 300 μm.
[0351] II. Exemplary Cathode Case A. Exemplary Cathode Case Construction 4 shows an exemplary cathode case useful in the batteries of the present disclosure. Cathode case 400 includes a bottom 413, an annular side 412, and a rim 414. The case includes an inner conductive layer 403 and a passivation layer 404. The passivation layer covers the outer surfaces 415 of the bottom and annular side, and the inner conductive layer covers at least a portion of the inner surface 416 of the cathode case that may be in physical contact with the electrochemical cell.
[0352] The exposed surfaces of the layers are important for the proper functioning of the exemplary battery. Figures 5A-5N show cross-sectional views of several different embodiments of cathode cases including multiple layers in different orientations for use in the exemplary battery.
[0353] B. Exemplary Cathode Case Structure with Multiple Layers In some embodiments, the passivation layer 502 extends over the rim of the cathode case 500a, as shown in Figure 5A. In other embodiments, for example 500b (Figure 5B), the passivation layer 504 extends down the interior wall 501 over the rim of the cathode case covering the inner conductive layer 503 except on the inside bottom surface of the cathode case.
[0354] Embodiment 500f (FIG. 5F) shows that passivation layer 514 comprises more than 50% of the total thickness of the cathode case. Internal conductive layer 513 comprises less than 50% of the total thickness of the cathode case. In some embodiments, internal conductive layer 513 may not be present. In that embodiment, passivation layer 514 is the cathode case.
[0355] In yet another embodiment, shown as cathode case 500c in FIG. 5C, passivation layer 506 is applied across the surface in a continuous coating from case exterior surface 506b to case interior surface 506a. The exterior surface of case 506b and the interior surface of case 506a can be the same or different materials and are in electrical contact. Internal support member 505 is completely encased by the passivation layer. The internal support member can be conductive or non-conductive and can be constructed of any material that can maintain the can shape and is capable of being crimped to seal the battery.
[0356] In some examples, the cathode passivation layer further comprises multiple layers. In one embodiment 500m, the cathode case comprises a first layer comprising a passivation metal 534, a second layer of passivation metal 533, and a cathode interior conductive layer 532 (FIG. 5M).
[0357] In some embodiments, the thickness of the passivation layer relative to the internal conductive layer is selected to minimize or prevent exposure of the internal conductive layer to a conductive aqueous medium when a battery described herein is immersed in the conductive aqueous medium. In some embodiments, the thickness of the passivation layer relative to the internal conductive layer is selected to minimize or prevent cracking of the passivation layer during manufacturing. The passivation layer thickness that minimizes or prevents cracking will vary based on the selection of the passivation metal, the internal conductive layer material, and the configuration of the cathode and / or anode case.
[0358] In some embodiments, the passivation metal is present in a layer having a uniform or varying thickness sufficient to prevent exposure of the inner conductive layer to the ambient environment. In some embodiments, the passivation metal is present in a layer having a thickness of 0.01 mm or less. 2 Less than or equal to 0.05 mm 2 Less than or 0.1 mm 2 Less than or 0.5 mm 2 Less than or 1.0 mm 2 Less than or 1.5 mm 2In some embodiments, the passivation metal is present in a layer having a uniform or varying thickness sufficient to prevent exposure to the ambient environment of a surface area of the internal conductive layer that is less than 0.01 mm thick. In some embodiments, the passivation metal is present in a layer having a uniform or varying thickness that reduces or prevents cracking of the layer upon folding ... 2 Less than or equal to 0.05 mm 2 Less than or 0.1 mm 2 Less than or 0.5 mm 2 Less than or 1.0 mm 2 Less than or 1.5 mm 2 The surface area of the coating is present in a layer having a uniform or varying thickness sufficient to prevent exposure of less than 100 nm to the ambient environment.
[0359] C. Exemplary Cathode Case Structure with Tie Layer In another embodiment 500 e ( FIG. 5E ), the inner conductive layer 510 and the passivation layer 512 are joined by a bonding layer 511 .
[0360] As used herein, a "tie layer" refers to a layer between an internal conductive layer and a passivation layer that keeps these layers attached to one another and that can facilitate, rather than prevent, electrical contact between these two layers.
[0361] In one such embodiment, the exemplary battery includes at least one tie layer disposed between the cathode internal conductive layer and the cathode passivation layer, between the anode internal conductive layer and the anode passivation layer, or both, such that the internal conductive layer and the passivation layer remain in electrical contact.
[0362] In other embodiments, the exemplary battery includes at least one tie layer disposed between the cathode internal conductive layer and the cathode passivation layer, between the anode internal conductive layer and the anode passivation layer, or both, wherein the internal conductive layer and the passivation layer remain in electrical contact, and the at least one tie layer includes an electrically conductive material.
[0363] In some embodiments, the exemplary battery includes at least one tie layer disposed between the cathode internal conductive layer and the cathode passivation layer, between the anode internal conductive layer and the anode passivation layer, or both, such that the internal conductive layer and the passivation layer remain in electrical contact, and the at least one tie layer comprises a metal. For example, metals such as Ni or Al can be used as the tie layer in the coating process. In some embodiments, the tie layer comprises a metal sheet. In one particular embodiment, the tie layer comprises nickel metal in the coating process. In another embodiment, a binder metallurgically bonds the conductive layer and the passivation layer.
[0364] In another embodiment, an exemplary battery includes at least one tie layer disposed between the cathode internal conductive layer and the cathode passivation layer, between the anode internal conductive layer and the anode passivation layer, or both, such that the internal conductive layer and the passivation layer remain in electrical contact, and the at least one tie layer includes an adhesive. In further embodiments, the adhesive includes a pressure-sensitive adhesive, a rubber adhesive, an epoxy, a polyurethane, a silicone adhesive, a phenolic resin, a UV-curable adhesive, an acrylate adhesive, a laminating adhesive, a fluoropolymer, or any combination of two or more thereof.
[0365] In some embodiments, the tie layer comprises multiple layers or multiple components. In one embodiment, the tie layer is a multi-layer structure including one or more lamination adhesives in contact with the internal conductive layer and the passivation layer. In some embodiments, the lamination adhesive is thin, e.g., 0.1-10 μm. In some embodiments, the adhesive may be present in grooves and crevices on the internal conductive layer or the passivation layer, or both, which may be formed by increasing surface roughness using polishing techniques known in the art and described herein for laminates.
[0366] For example, the tie layer may be a multi-component structure comprising an adhesive layer intermixed with conductive particles embedded in contact with a passivation layer, an adhesive layer intermixed with conductive particles embedded in contact with an inner conductive layer, or both. In one embodiment, the tie layer is a multi-component structure comprising a layer (e.g., a 25-40 μm layer) of acrylic pressure-sensitive adhesive intermixed with conductive particles embedded in contact with a passivation layer and an inner conductive layer. More specifically, in some embodiments, the tie layer comprises a laminating adhesive comprising low- or high-density polyethylene, polyolefin, polyolefin derivative, acid-containing adhesive, ionomer, ethylene terpolymer, acrylate, or ethylene-vinyl acetate. In other embodiments, the acid-containing adhesive comprises EAA, EMAA, ionomer, ethylene terpolymer, acid, or acrylate.
[0367] In some embodiments, the tie layer has a uniform or varying thickness of 100 nm to 400 μm, 100 nm to 350 μm, 1 μm to 350 μm, 200 μm to 350 μm, 1 μm to 50 μm, 5 μm to 50 μm, 50 μm to 250 μm, or 5 μm to 200 μm, which can result in some embodiments in which the anode case and / or cathode case each have a uniform or varying overall thickness of 50 μm to 400 μm, or 200 μm to 400 μm.
[0368] D. Exemplary Cathode Case Structure with Exterior Coating The exterior coating of the battery's cathode case, anode case, or both, can be a highly conductive material, such as a metal, to reduce contact resistance during normal operation of the battery or to improve the aesthetics of the battery case. When a battery including a passivation layer and exterior coating is immersed in an aqueous conductive medium, the exterior coating exposed on the exterior surface can oxidize and dissolve as part of the oxidation reaction on the battery's positive electrode. When the exterior coating oxidizes, the passivation layer is exposed to the conductive aqueous medium, reducing or inhibiting the electrolytic reaction. Possible material combinations and thickness ranges are described in the previous section.
[0369] In cathode case embodiment 500d shown in Figure 5D, an inner conductive layer 507 makes up the majority of the inner surface of the cathode case. A passivation layer 508 covers the outer surface of the inner conductive layer and extends over the rim. The outer surface of the passivation layer is coated with an outer coating 509, leaving the inner surface of the cathode case exposed to the inner conductive layer.
[0370] In embodiment 500g shown in FIG. 5G, a passivation layer 516 comprising a passivation metal is applied as a continuous coating over the inner, outer, and rim surfaces of an inner support member 515. The inner support member is completely enveloped by the passivation layer. The inner support member can be composed of any material, conductive or non-conductive, capable of maintaining a can shape and capable of being crimped to seal the battery. The passivation layer is then coated with an outer coating 517, which results in the inner, outer, and rim surfaces of the cathode case being covered with the outer coating.
[0371] In another embodiment 500h shown in Figure 5H, a passivation layer 519 covers the outer surface of the inner conductive layer 518 and extends over the rim. The outer surface and rim surface of the passivation layer and the inner surface of the inner conductive layer are coated with an outer coating 520, such that the inner and outer surfaces of the cathode case are covered with the outer coating.
[0372] In embodiment 500i shown in Figure 5I, passivation layer 522 covers the outer surface of inner conductive layer 521 without extending over the rim. The outer surface of the passivation layer and the inner and rim surfaces of the inner conductive layer are coated with outer coating 523, such that the inner and outer surfaces of the cathode case are covered with the outer coating.
[0373] 5J, a passivation layer 525 covers the outer surface of the inner conductive layer 524 and extends down the inner surface over the rim of the cathode case covering the inner conductive layer except for the inside bottom surface of the cathode case. The surfaces of the passivation layer and the surfaces of the inner conductive layer not covered by the passivation layer are coated with an outer coating 526, and the inner and outer surfaces of the cathode case are covered by the outer coating.
[0374] In embodiment 500k shown in Figure 5K, passivation layer 528 comprises more than 50% of the total thickness of the cathode case. Inner conductive layer 527 comprises less than 50% of the total thickness of the cathode case. The outer surface of the passivation layer is covered with an outer coating 529. The inner surface of the cathode case is composed of the inner conductive layer. The surface of the rim of the cathode case includes the passivation layer.
[0375] In 5001 shown in Figure 5L, the passivation layer 530 comprises more than 90% of the total thickness of the cathode case. All exposed surfaces, including the inner surface, rim, and outer surface of the passivation layer, are covered with an outer coating 531.
[0376] In the embodiment 500n shown in FIG. 5N, the cathode case includes a first layer 537 including a passivation metal, a second layer 536 of a passivation metal, an outer coating 538, and a cathode inner conductive layer 535.
[0377] E. Example cathode case structure during crimping FIG. 6A shows an enlarged cross-sectional schematic view of a section of a cathode case 600a according to one embodiment, having a bottom 613, annular side or outer annular surface 612, and a rim 614. A gasket 606 is also shown. FIGS. 6A, 6B, 6C, 7A, 7B, and 8 represent partial cross-sectional schematic views of a complete battery, but for clarity, do not show the anode case or the battery's internal components. FIG. 6D shows an SEM image of a cross-section of a prototype correlating to the schematic view of FIG. 6C without the gasket. In this embodiment, a portion of the annular side is crimped to form a crimped region 615 that includes a rim or rim surface 614. In some embodiments, for example, as depicted in FIG. 6A, the passivation layer 604 extends over the rim and is partially covered by the gasket 606 during the crimping process. When assembled into a battery, the internal conductive layer 603 has no exposed surface on the battery's exterior. In another embodiment, such as 600b depicted in FIG. 6B, the passivation layer 604 extends down the inner sidewall over the rim and is covered by a gasket 606 during the crimping process. In some embodiments, the passivation layer 604 (a section of cathode case 600c is shown in FIG. 6C) is stretched and thinned from its initial wall thickness in a process such as a stamping process and hemmed onto the inner conductive layer 603. A section of a fabricated cathode case 600d is shown in FIG. 6D, which shows an SEM image of the cross section of one exemplary prototype crimped cell with a hemfold. In this particular example in FIG. 6D, the thickness of the passivation layer 604 starts at about 200 μm and has a varying thickness within the rim 614 due to the stamping method, with the inner conductive layer (also referred to in some embodiments as an inner support member) within the thinned portion of the rim 614 having a thickness that varies from 5 μm to 100 μm.
[0378] 7A and 7B, in some embodiments, the interface between the inner conductive layer 703 and the passivation layer 704 is exposed at the rim 714 of the cathode case. Cathode cases 700a and 700b have a bottom or outer bottom surface 713, an annular side 712, a rim 714, and a crimped region 715. In some embodiments, such as 700a, the exposed interface is covered with a water-impermeable coating 710 to prevent the inner conductive layer 703 from being exposed to the aqueous conductive medium during immersion. In other embodiments, such as 700b, the exposed interface is covered with an extended gasket 706 to prevent the inner conductive layer 703 from being exposed to the aqueous conductive medium during immersion.
[0379] 8 shows an enlarged cross-sectional schematic view of a section of a cathode case 800 according to one embodiment, having a bottom 813, an annular side 812, and a rim 814. A gasket 806 is also shown. In this embodiment, a portion of the annular side is crimped to form a crimped area 815 that includes the rim 814. In these embodiments, the crimped area has a fishhook shape in which the rim is rotated toward the bottom of the cathode case and the rim surface is embedded within the gasket. A portion of the passivation layer 804 is covered by the gasket. The inner conductive layer 803 has no surface exposed to the cell's exterior and is therefore protected during immersion in a conductive aqueous medium.
[0380] F. Exemplary Anode and Cathode Case Materials The anode and cathode case components can comprise a variety of materials known to those skilled in the art. Suitable materials for the internal conductive layers include, but are not limited to, conductive metals. In certain embodiments, the internal conductive layers comprise aluminum, stainless steel, chromium, tungsten, gold, vanadium, nickel, niobium, titanium, tantalum, silver, alloys thereof, or any combination thereof. In certain embodiments, the anode internal conductive layer and / or the cathode internal conductive layer comprise stainless steel. In some embodiments, the internal conductive layers comprise aluminum, stainless steel, chromium, gold, vanadium, nickel, silver, copper, magnesium, zinc, alloys thereof, or combinations of any two or more thereof.
[0381] In certain embodiments, a stainless steel disk of thickness varying from 5 pm to 300 pm can be placed over a portion of the passivation layer. The stainless steel disk is in electrical contact with the passivation layer and can be an inner conductive layer and / or an inner support member.
[0382] Stainless steel is an alloy and is commercially available in various forms. Stainless steels useful for the inner conductive layer include, but are not limited to, SS304, SS316, SS430, duplex 2205, duplex 2304, duplex 2507, or one or more other stainless steels having a chromium content of 10% by weight or more and / or a nickel content of 0.1% by weight or more. The chromium content creates an oxide state that favors electron transfer from the battery contents, similar to current commercially available batteries.
[0383] In some embodiments, a layer comprising vanadium may be disposed between the internal conductive layer and the passivation layer, hi some embodiments, the vanadium-containing layer is 1% to 95%, or 25% to 80%, or greater than 75% vanadium in combination with one or more of the other bond materials, composite materials, internal conductive materials, or passivation metals described herein.
[0384] In addition to conductive metals, the inner conductive layer and / or passivation layer may comprise a conductive composite. In one embodiment, conductive particles are embedded in a non-conductive medium to form an overall conductive film that is coated on the cathode case as the inner conductive layer and / or passivation layer. In another embodiment, silver, nickel, conductive carbon black, carbon nanotubes, graphene, graphite, and / or carbon fiber are used as the conductive particles in the conductive composite film.
[0385] In some embodiments, the cathode case includes an internal support member. In some embodiments, the internal support member is an internal conductive layer. In some embodiments, the internal support member includes an insulating material. In some embodiments, the internal support member includes a thermosetting elastomer. Examples of thermosetting elastomers include, but are not limited to, polydimethylsiloxane, cross-linked polyurethane coatings, cross-linked acrylates, rubberized epoxies, or any combination thereof. The cross-linked acrylates may be cross-linked using an ultraviolet light source in some embodiments. After coating, molding, or thermoforming to form an internal support member including the insulating material, the overall shrinkage of the insulating material is, in some embodiments, less than 30%, less than 15%, or less than 5%. After coating, molding, or thermoforming to form an internal support member including the insulating material, the overall shrinkage of the insulating material is, in some embodiments, 0-30%, 0-15%, or 0-5%.
[0386] In some embodiments, the decomposition temperature of the thermosetting polymer is greater than 85° C., greater than 100° C., greater than 125° C., greater than 150° C., greater than 175° C., or greater than 200° C. In some embodiments, the decomposition temperature of the thermosetting polymer is a temperature between 85° C. and 100° C., or between 100° C. and 125° C., or between 125° C. and 150° C., or between 150° C. and 175° C., or between 175° C. and 200° C., or between 200° C. and 500° C.
[0387] In some embodiments, an exemplary battery includes a water-impermeable coating disposed on and covering the rim surface of the cathode case, and optionally a water-impermeable coating disposed on a portion of the exterior surface of the anode case, or optionally disposed on a portion of the exterior surface of the cathode case, or optionally disposed on both a portion of the exterior surface of the anode case and a portion of the exterior surface of the cathode case. The water-impermeable coating may be selected from natural rubber, TFE, Exxon Butyl, chloroprene, epichlorohydrin, ethylene-propylene, fluorosilicone, hydrogenated nitrile, liquid silicone rubber, medical-grade ethylene propylene, silicone, nitrile, perfluoroelastomer, polyacrylate, polyurethane, styrene butadiene, Teflon®, Vamac, PTFE, viton, or any combination of one or more thereof.
[0388] In other embodiments, the exemplary battery includes a water-impermeable coating disposed on and covering the rim of the cathode case, optionally disposed on a portion of the exterior surface of the anode case, and optionally disposed on a portion of the exterior surface of the cathode case, wherein the water-impermeable coating is the same material as the gasket.
[0389] In further embodiments, the cathode interior conductive layer further includes an outer bottom surface, an outer annular surface, and a rim surface, wherein the outer bottom surface is encased by a cathode passivation layer, and the outer annular surface and the rim surface are encased by a cathode passivation layer, a gasket, a water-impermeable coating, or any combination thereof.
[0390] In some embodiments, the water impermeable coating comprises rubber, Buna, silicone, silicone rubber, PTFE, Viton, or an elastomeric material, or a plastic such as nylon, polytetrafluoroethylene, fluorinated ethylene-propylene, chlorotrifluoroethylene, perfluoroalkoxy polymer, polyvinyl, polyethylene, polyethylene terephthalate, polypropylene, polystyrene, polysulfone, polyacrylicate, polyurethane, and combinations thereof.
[0391] The gasket may be constructed from any material known in the art, hi some embodiments, the gasket comprises an elastomeric material or plastic such as nylon, polytetrafluoroethylene, fluorinated ethylene-propylene, chlorotrifluoroethylene, perfluoroalkoxy polymer, polyvinyl, polyethylene, polyethylene terephthalate, polypropylene, polystyrene, polysulfone, polyacrylicate, polyurethane, silicone rubber, or any combination of two or more thereof.
[0392] G. Exemplary Anode Case Structures 10 shows an exemplary anode case useful in the batteries of the present disclosure. Anode case 1000 includes a top 1007, an annular side 1008, and a hemfold 1009. The anode case includes an inner conductive layer 1001a and a passivation layer 1001b. In another embodiment, when the battery is assembled as shown in FIG. 3, the hemfold is completely embedded within the gasket.
[0393] Each of the exemplary cathode case structures, including layer orientations and material types, described with respect to the embodiment of FIG. 6 are applicable to the anode case.
[0394] In some embodiments, the passivation layer extends over the hemfold 1009 of the anode case.
[0395] In yet another embodiment, the passivation layer is applied over the entire surface of the anode case in a continuous coating from the outer surface to the inner surface of the case. The materials from the outer surface of the anode case to the inner surface of the case can be the same or different. In another embodiment, the outer surface of the anode case is a passivated metal, and the inner surface of the anode case is stainless steel or aluminum. In another embodiment, in which the anode includes an internal support member, the internal support member is completely enveloped by the passivation layer so that the internal support member is not on the outer surface of the anode case. The internal support member can be composed of any material, conductive or non-conductive, that can maintain the anode shape and that has the ability to withstand pressure from the crimp used to seal the cell. In one embodiment, the internal support member is stainless steel.
[0396] In some embodiments, the inner conductive layer and the passivation layer are joined by a bonding layer, hi some embodiments, the bonding is a conductive adhesive.
[0397] H. Cathode case as sealing cup FIG. 2 shows an exemplary coin cell battery. The "anode case" is defined as the battery case in direct contact with the anode of the electrochemical cell, and the "cathode case" is defined as the battery case in direct contact with the cathode of the electrochemical cell. The shape and size of the cathode and anode cases can vary depending on the type of battery. A typical coin cell battery casing includes a sealing cup and a bottom can. FIG. 2 shows an exemplary coin cell battery in which the sealing cup is the anode case 201 and the bottom can is the cathode case 202.
[0398] The present disclosure also contemplates certain embodiments in which the configuration is opposite to that described above. In certain embodiments, the sealing cup is the cathode case and the bottom can is the anode case. In one embodiment, as shown in FIG. 9 , the battery is a coin cell or cylindrical battery including a battery case, the battery case including a sealing cup 901, a bottom can 902, and a gasket 906, the outer diameter of the sealing cup being smaller than the inner diameter of the bottom can, at least a portion of the sealing cup being positioned inside the bottom can with the gasket between the sealing cup and the bottom can, and the annular wall of the bottom can being pressed against the annular wall of the sealing cup. The battery further includes an electrochemical cell including an anode 903, a cathode 905, and a separator 904 positioned between the anode 903 and the cathode 905. In this embodiment, the cathode case is the sealing cup and the anode case is the bottom can. In some embodiments, the rim surface of the sealing cup is advantageously embedded in a gasket after assembly to protect the rim surface of the sealing cup from exposure to the conductive aqueous medium during immersion.
[0399] III. Examples of contact with conductive aqueous media Contacting the battery with the conductive aqueous medium includes immersing or partially immersing the battery in the conductive aqueous medium, or contacting the battery with moist tissue, such as tissue in the mouth, throat, esophagus, or any other part of the GI tract of a mammal. In some embodiments, contacting with the conductive aqueous medium includes placing the battery on hydrated tissue such that at least a portion of the anode case contacts the hydrated tissue. In some embodiments, the hydrated tissue is hydrated ham, and in embodiments, the tissue is hydrated porcine esophageal tissue.
[0400] In another embodiment, contacting with the conductive aqueous medium includes immersing the battery in the conductive aqueous medium with the anode terminal facing up. Both the anode and cathode are in contact with the conductive aqueous medium. A fully immersed battery has the entire anode and the entire cathode in contact with the conductive aqueous medium. Partial immersion includes embodiments in which 1) all of the anode case but only a portion of the cathode case, 2) all of the cathode case but only a portion of the anode case, or 3) portions of both the anode case and the cathode case are in contact with the conductive aqueous medium.
[0401] In one embodiment, the conductive aqueous medium is 20 mL of 25% Ringer's solution or saline solution with an initial pH of 5-7. In some embodiments, the average pH of the solution over the first 60 minutes after the battery is immersed does not exceed an average pH of 10 at 5-minute sampling intervals. The pH should be measured directly in the solution container 3 cm above the center of the anode case using pH paper without mixing. In yet another embodiment, the pH of the solution does not exceed 9.5 for 10-60 minutes after immersion. In another embodiment, the pH of the solution does not exceed 9 for 10-60 minutes after immersion. In yet another embodiment, the pH of the solution does not exceed 8.5 for 10-60 minutes after immersion. In yet another embodiment, the pH of the solution does not exceed 8 for 10-60 minutes after immersion. In yet another embodiment, the pH of the solution does not exceed 7 for 10-60 minutes after immersion.
[0402] IV. Exemplary Laminates Next, the present disclosure provides a multilayer laminate useful for forming either an anode case or a cathode case. A laminate is a layered material made of two or more layers, which are attached in any order using heat, pressure, welding, adhesives, or other techniques known in the art. An exemplary multilayer laminate 1100 is shown in FIG. 11, where 1103 represents a conductive layer, 1104 represents a passivation layer, and 1105 represents a bonding layer. The bonding layer is between the conductive layer and the passivation layer. The conductive layer and the passivation layer can be electrically connected after lamination by exposure to pressure and temperature to secure the conductive layer to the passivation layer.
[0403] The multilayer laminates described herein can be advantageously used to form electrode cases, such as cathode cases, anode cases, or both, for the batteries described herein.
[0404] In some embodiments, the tie layer comprises: a) a plurality of layers; b) an adhesive layer in contact with the passivation layer; c) an adhesive layer in contact with the conductive layer; or d) includes a), b) and / or c).
[0405] In some embodiments, the conductive layer has a uniform or varying thickness of 100 nm to 400 μm, 100 nm to 350 μm, 1 μm to 350 μm, 200 μm to 350 μm, 1 μm to 50 μm, 50 μm to 200 μm, 25 μm to 300 μm, or 175 μm to 300 μm.
[0406] In another embodiment, the conductive layer is stainless steel, and the surface in contact with the bonding layer has a rough surface including peaks and valleys. The surface roughness can be formed by chemical means such as etching, or by physical means such as scoring, stamping, polishing, or sandblasting. The bonding layer is deposited into the valleys during the lamination process, and the peaks make direct electrical contact with the passivation layer, creating metal-to-metal contact. This can reduce the resistance from the conductive layer to the passivation layer. The bonding layer can be insulating, since electrical contact can be made directly between the conductive layer and the passivation layer. In other embodiments, the passivation layer has a rough surface. In other embodiments, both the conductive layer and the passivation layer have rough surfaces.
[0407] In some embodiments, the passivation layer can have a uniform or variable thickness between 100 nm and 400 μm, between 100 nm and 350 μm, between 1 μm and 350 μm, hi some embodiments, the passivation layer has a uniform or variable thickness between 200 μm and 350 μm, between 1 μm and 50 μm, between 1 μm and 100 μm, between 1 μm and 300 μm, between 14 μm and 200 μm, or between 50 μm and 200 μm.
[0408] In some embodiments, the binder has a uniform or varying thickness of 100 nm to 400 μm, 100 nm to 350 μm, 1 μm to 350 μm, 200 μm to 350 μm, 1 μm to 50 μm, or 50 μm to 200 μm.
[0409] Another exemplary multilayer stack 1200 is shown in FIG. 12, where 1203 represents a conductive layer, 1204 represents a passivation layer, and 1206 represents the interface between the conductive and passivation layers. In some embodiments, the conductive and passivation layers are directly bonded and in electrical contact with each other. The conductive and passivation layers can be mechanically and electrically bonded by methods known in the art. For example, physical vapor deposition and chemical vapor deposition are useful for forming layers having thicknesses between 1 nm and 10 μm. Coating, diffusion bonding, welding, pinching, stamping, or otherwise mechanically fastening the layers are useful processes for forming layers having thicknesses between 1 μm and 400 μm, 75 μm and 330 μm, or 200 μm and 330 μm.
[0410] Laminating a conductive layer to a passivation layer is one method of producing a laminate for use in an anode case or a cathode case for a battery of any one of the preceding embodiments, wherein the laminate comprises a conductive layer and a passivation layer. Coating a conductive layer to a passivation layer is another method of producing a laminate for use in an anode case or a cathode case for a battery, wherein the laminate comprises a conductive layer and a passivation layer.
[0411] In one embodiment, the multilayer laminate is a cladding, coated laminate, or heavy cladding material. The conductive layer is stainless steel, and the passivation layer is niobium, tantalum, titanium, tungsten, or alloys thereof. Cladding is a process that metallurgically bonds dissimilar metals. One method of cladding can be achieved by a continuous roll bonding process, combining two or more metal strips. First, the individual strips are chemically or mechanically cleaned. The strips then pass through a rolling mill designed for cladding. As the layers pass through the mill, the rolls apply tremendous pressure, reducing the thickness of the strip and producing a cladding. Typically, the resulting cladding is further heat-treated to facilitate future stamping into the battery casing.
[0412] Additionally, an external coating can be laminated onto the passivation layer of the laminate to produce a laminate including the external coating, the passivation layer, and the conductive layer. For example, a coating can be used to attach the external coating to the passivation layer of the laminate, which can then be attached to the conductive layer. In one laminate manufacturing embodiment, the passivation layer is disposed between the conductive layer and the external coating, and the method includes laminating the conductive layer, the passivation layer, and the external coating. In another manufacturing embodiment, a laminate for use in an anode case or cathode case for a battery of any one of the preceding embodiments is manufactured by coating the conductive layer, the passivation layer, and the external coating. The resulting laminate includes the conductive layer, the passivation layer, and the external coating, and the passivation layer is disposed between the conductive layer and the external coating.
[0413] In one embodiment, a conductive layer; and a passivation layer comprising a passivation metal, wherein the laminate is for use in an anode case or a cathode case of a battery.
[0414] In another embodiment, the stack includes a passivation layer comprising a passivation metal selected from Ta, Nb, W, Re, Ti, alloys thereof, and combinations thereof.
[0415] In another embodiment, the laminate further comprises an outer coating.
[0416] In some embodiments, the laminates described herein are used to prepare material used in preparing wires or punchings (as used herein, a blank, for purposes of this application, is a flat metal sheet that is placed into a stamping press to become a cathode or anode case or can). In some embodiments, the laminate is a punching. In some embodiments, the laminate is a wire. In some embodiments, the punching is stamped or otherwise formed into a case. In some embodiments, the wire is formed into a case or can using known wire forming processes. In some embodiments, the conductive layer and passivation layer in the laminate have uniform or varying thicknesses in a ratio (passivation layer:conductive layer) of 1:1-5, or 1:1.1-4.5, or 1:1.5-4, or 1:2-3, or 1:1, 1:1.1, or 1:1.2, or 1:1.5, or 1:2, or 1:2.5, or 1:3, or 1:3.5, or 1:4, or 1:4.5, or 1:5. In some embodiments, the conductive and passivation layers in the laminate have uniform or varying thicknesses in a ratio (passivation layer:conductive layer) of 1:1-20, or 1:1-10, or 1:10, or 1:20. In other embodiments, the conductive and passivation layers in the laminate have uniform or varying thicknesses in a ratio (passivation layer:conductive layer) of 1-20:1, or 1-10:1, or 10:1, or 20:1. In other embodiments, the conductive and passivation layers in the laminate have uniform or varying thicknesses in a ratio (passivation layer:conductive layer) of 1 to 5:1, or 1.1 to 4.5:1, or 1.5 to 4:1, or 2 to 3:1, or 1:1, or 1.1:1, or 1.2:1, or 1.5:1, or 2:1, or 2.5:1, or 3:1, or 3.5:1, or 4:1, or 4.5:1, or 5:1.In some embodiments, the conductive and passivation layers of the laminate have a ratio of 8:1 to 1:5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:5, or 6:1 to 1:3, or 6:1 to 1:2, or 6:1 to 1:1.1, or 6:1 to 1:1, 3:1 to 1:5, or 3:1 to 1:3, or 3:1 to 1:2, or 3:1 to 1:1. and having a uniform or varying thickness with a ratio (passivation layer:internal conductive layer) of 1, or 3:1 to 1:1, or 2:1 to 1:5, or 2:1 to 1:3, or 2:1 to 1:2, or 2:1 to 1:1.1, or 2:1 to 1:1, or 8:1 to 1:2.5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:2, or 3:1 to 1:2.
[0417]
[0454] In some embodiments, the conductive and passivation layers in the laminate have a uniform or varying thickness of 1 μm to 400 μm, or 10 μm to 400 μm, or 50 μm to 400 μm, or 10 μm to 300 μm, or 50 μm to 300 μm, or 100 μm to 200 μm. The conductive and passivation layers have a uniform or varying thickness as described herein.
[0418] The manufacturing process can vary the thickness of the conductive and passivation layers. Stamping, rolling, pressing, and other manufacturing processes cause thinning of the layers. In some embodiments, thinning occurs in one layer. In some embodiments, thinning occurs in two or more layers. In some embodiments, the thinning process is not uniform across the layers. For example, as seen in FIG. 15A , the annular side of the stamped cathode case can be stretched or elongated (1501) so that the total layer thickness in that region is thinner than the rest of the cathode case and thinner than regions of the cathode case where the layers in that region were not stretched. In some embodiments, a folding process is used to fold the stretched region 1501 to provide region 1502, which has a total thickness that can be uniform or variable and is similar to the thickness of the side 1505 of the cathode case.
[0419] In one example where the total laminate thickness is 200-250 μm, the laminate passivation layer has a uniform or varying thickness of 70 μm-200 μm, and the laminate conductive layer has a uniform or varying thickness of 50 μm-180 μm. Areas of the cathode case that experience bending and / or folding during manufacturing have passivation layers with uniform or varying thicknesses of 14 μm-40 μm, for example. The cathode case annular wall has a passivation layer with a uniform or varying thickness of 70 μm-200 μm and an inner conductive layer with a uniform or varying thickness of 50 μm-180 μm, as shown in FIG. 15A.
[0420] In some embodiments, the cathode cases described herein can be prepared from a coating stack including a passivation layer having a uniform or varying thickness of 60 μm to 200 μm and a conductive layer having a uniform or varying thickness of 50 μm to 190 μm. In some embodiments, the cathode cases described herein have a uniform or varying thickness of 200 μm to 250 μm, the cathode case includes a hemfold having a passivation layer on each side of the hemfold having a uniform or varying thickness of 14 μm to 75 μm and a total internal conductive layer thickness of 222 μm to 50 μm, and the cathode case includes an annular sidewall including a passivation layer having a uniform or varying thickness of 60 μm to 200 μm and an internal conductive layer thickness of 190 μm to 50 μm.
[0421] In some embodiments, the cathode cases described herein can be prepared from a coating stack including a passivation layer having a uniform or variable thickness of 60 μm to 200 μm and a conductive layer having a uniform or variable thickness of 50 μm to 190 μm. In some embodiments, the cathode cases described herein have a uniform or variable thickness of 200 μm to 250 μm, the cathode case includes a hemfold, the hemfold includes a first side and a second side, each of the first and second sides further includes a passivation layer having a uniform or variable thickness of 14 μm to 75 μm, the hemfold has a total thickness of 200 μm to 250 μm, and the first side of the hemfold contacts the second side of the hemfold. An example of a hemfold can be seen in FIG. 15C. In section 1502, a first side of the hemfold has a passivation layer facing the interior of the cathode case, and a second side of the hemfold has a passivation layer facing the exterior of the cathode case. The interior conductive layers on each side of the hemfold come together as a result of the folding process.
[0422] In some embodiments, the thickness of the laminate layers is selected to enable the final cathode or anode case to have a conductive layer with a uniform or variable thickness of 14 μm to 200 μm, or 25 μm to 300 μm, or 175 μm to 300 μm. In some embodiments, the thickness of the laminate layers is selected to enable the final cathode or anode case to have a passivation layer with a uniform or variable thickness of 1 μm to 75 μm, or 1 μm to 300 μm, or 1 μm to 100 μm. In some embodiments, the thickness of the laminate layers is selected to enable the final cathode or anode case to have an outer coating with a uniform or variable thickness of 100 nm to 7 μm, or 100 nm to 5 μm. In some embodiments, the laminate has a uniform or varying thickness of 50 μm to 400 μm, or 175 μm to 400 μm, or 100 μm to 330 μm, or 276 μm to 330 μm.
[0423] In some embodiments, prior to formation of the cathode case, the laminate has a uniform or varying thickness of 1 μm to 400 μm, 50 μm to 400 μm, 100 μm to 400 μm, or 150 μm to 400 μm, or 100 μm to 300 μm, or 100 μm to 200 μm, or 200 μm to 300 μm, or 200 μm to 250 μm.
[0424] In some embodiments, cathode cases made from laminates disclosed herein have a uniform or variable thickness that is the same or substantially the same as the original laminate. In other embodiments, the manufacturing process may alter the thickness of the laminate, as well as the thickness of the laminate's conductive and passivation layers. Stamping, rolling, pressing, and other manufacturing processes cause thinning of the laminate and its layers. In some embodiments, thinning occurs in one layer. In some embodiments, thinning occurs in two or more layers. In some embodiments, the thinning process is not uniform across the layers. For example, as seen in FIG. 15A , the annular side of a pressed cathode can can be stretched or stretched (1501) so that the total layer thickness in that region is thinner than the rest of the can and the layers in that region are thinner than regions of the can that were not stretched. In some embodiments, a folding process is used to fold the stretched region (1501) to provide a region 1502 that has a total thickness similar to the rest of the can.
[0425] In one example where the total laminate thickness is 200-250 μm, the laminate passivation layer has a uniform or varying thickness of 70 μm-200 μm, and the internal conductive layer has a uniform or varying thickness of 50 μm-180 μm. The area of the cathode case that is subjected to bending and / or folding has a final passivation layer with a uniform or varying thickness of 14 μm-40 μm. See, for example, 1502 in FIGS. 15A and 15C.
[0426] V. Exemplary Manufacturing Methods The present disclosure further provides methods for manufacturing the aforementioned exemplary cathode case, anode case, and exemplary battery. Specific examples herein use the cathode case as an example. These manufacturing methods can also be applied to the anode case. Several methods are available, including the following non-limiting examples: In one embodiment shown in FIG. 13, the method for manufacturing the cathode case includes: a) providing a laminate 1330 including a conductive layer 1303 and a passivation layer 1304 with an interface 1305 between the conductive layer and the passivation layer; b) stamping the laminate 1330 to form a cathode case 1300 including a bottom, annular sides, and a rim; c) forming a conductive path through the layer; The conductive layer 1303 forms the inner surface of the cathode case, and the passivation layer 1304 forms the outer surface of the cathode case.
[0427] In one method, an exemplary cathode case is stamped from the exemplary laminate to form a cathode case including a bottom, annular sides, and a rim, with the conductive layer forming the inner surface of the case and the passivation layer forming the outer surface of the case. In another method, an exemplary cathode case is stamped from the exemplary laminate to form a cathode case including a bottom, annular sides, and a rim, with the conductive layer forming the inner surface of the case and the outer coating forming the outer surface of the case. Another method for forming a cathode case includes stamping the exemplary laminate including a conductive layer and a passivation layer, with the passivation layer disposed between the conductive coating and the outer coating, into a cup shape having a bottom, annular sidewall, and a rim.
[0428] In another embodiment, shown in FIG. 14 , a method of manufacturing a cathode case 1400 includes rolling the edge of the case 1401 toward the center of the case 1401 to wrap the passivation layer 1404 over the rim 1414 of the case. In doing so, the exterior surface of the cathode case after crimping does not include the inner conductive layer 1403. In some embodiments, the edge of the case is rolled at least 270° or more, as shown in the enlarged cathode case rim schematic of FIG. 14B . In other embodiments, the edge of the case is rolled toward the center of the case by an angle X°, where X° is measured relative to 0° parallel to the bottom 1401 of the case, and X° can range from 1° to 270°, 5° to 200°, 45° to 135°, 270° to 360°, or 360° to 720° (see, for example, FIGS. 14B and 14C ).
[0429] 14D, the top of the case is folded 180° to wrap the passivation layer 1404 over the rim 1414 of the case toward the center of the case 1401, and the folded portion continues down the wall of the case 1402. In this embodiment, the passivation layer covers the exterior, rim, and interior wall surfaces of the cathode case. The inner conductive layer 1403 is the inside surface of the bottom of the cathode case.
[0430] Another manufacturing method is shown in FIGS. 15A-15C. First, in FIG. 15A, an exemplary laminate 1500e, including an inner conductive layer 1503 and a passivation layer 1504, is stamped into a can shape. Next, an upper portion of the annular wall is drawn out by either a stamping, ironing, or rolling process to form an extended annular side 1501 and a lower annular side 1505. The drawn portion of the wall is then folded onto a rim toward the center of the case by incremental stamping steps. This results in a cathode case with a variable thickness and a passivation layer that extends over the surface of the rim 1502. Additional finishing steps, such as rolling or polishing, can be used to make the inner surface of the wall smoother and reduce the width and depth of the seam. In some embodiments, the drawn portion of the extended annular side is folded over the rim to form a hem fold and joined to itself by methods known in the art.
[0431] Figure 15B shows an SEM image of an example of a crack at the bend of a hemfold in the passivation layer that allows the internal conductive layer to be exposed to the ambient environment, and Figure 15C shows an SEM image of an example of a passivation layer with uniform or varying thickness that does not allow the internal conductive layer to be exposed to the ambient environment, particularly at the hemfold.
[0432] FIG. 16 illustrates another method for fabricating an exemplary cathode case. The conductive layer 1603 is punched into a circle, and the passivation layer 1604 is punched with a larger diameter than the conductive layer. These layers are centered with the passivation layer at the bottom to form stack 1600a. The stack is punched into a can shape with the conductive layer on the inside and an annular height shorter than that of the passivation layer 1600b. The passivation layer is then folded over to cover at least the top of the rim of the conductive layer 1600c. Using a similar process, the passivation layer 1604 can be extended downward toward the inner annular wall, partially or completely covering the inner wall of the conductive layer can shape, thus producing a cathode case with a two-layer stack, as shown in schematic diagrams 1601a-1601c.
[0433] One exemplary cathode case starts with a total laminate 1500e thickness of 200 μm and includes a 40 μm to 60 μm thick passivation layer 1504 coated on a 140 μm to 150 μm thick inner conductive layer 1503. During the stamping, ironing, and forming of the folded portion of the wall, there is a layer thickness reduction on the annular sidewall by 30% to 70% to about 12 μm to 45 μm during the extension process. Upon hemming the extension, the passivation layer extending onto the surface of the rim 1502 under tensile extension reduces the thickness of the passivation layer 1504 by 15% to 50%, further to 6 μm to 20 μm. With an initial passivation layer 1504 thickness of 60 μm or less, it may be possible to manufacture cathode cases with a passivation layer thickness at the rim 1502 of 20 μm or less and assemble them into batteries as disclosed herein. However, this thickness may be insufficient to prepare a fully functional battery as described herein under stamping, ironing, and folding steps, or during the process of handling and crimping the cathode case into a final functional battery. Figure 15B shows a microscope image of an exemplary cathode case 1500b, in which the passivation layer within the laminate has a 50 μm 1504 thickness and is stretched to less than 20 μm, exhibiting cracks at the rim 1502 after the hem folding process, thus compromising the continuity of the passivation layer 1504 and exposing a portion of the internal conductive layer 1503. To produce a cathode case that maintains a robust, continuous passivation layer 1504 at the rim portion 1502 after the hem folding and further crimping steps and does not expose the internal conductive layer 1503, in some embodiments, it is preferred to start with a laminate 1500e in which the passivation layer 1504 is greater than 60 μm thick. 15C shows a microscope image of an exemplary cathode case 1500c at the rim 1502, where the thickness of the passivation layer 1504 varies from 20 μm to 60 μm and is continuous and intact without exposing the inner conductive layer 1503. The passivation layer was 110 μm thick in the starting laminate.
[0434] In some embodiments, the thickness of the passivation layer will be twice the thickness of the internal conductive layer. In some embodiments, the thickness of the passivation layer will be three times the thickness of the internal conductive layer. In some embodiments, the thickness of the passivation layer will be four times the thickness of the internal conductive layer. In some embodiments, the thickness of the passivation layer will be selected from 1.1 to 4 times the thickness of the internal conductive layer. In some embodiments, the passivation layer and the internal conductive layer are produced from a coating laminate of sufficient thickness to allow for the recited thickness after the laminate is stamped or otherwise formed into a case or can. While tantalum, niobium, and rhenium are relatively ductile, tungsten alone is brittle, which can lead to cracking and make forming difficult. Titanium is known in the art to cause chatter or cracking in the coated layer when directly coated onto stainless steel. The addition of rhenium to tungsten improves ductility and aids in alloy formation. Additionally, niobium, vanadium, or copper can be used between the titanium and stainless steel to reduce cracking issues associated with coating and stamping. The addition of niobium to titanium improves the drawing and forming properties of the metal.
[0435] In one exemplary method, vapor deposition is used to deposit a passivation metal onto the inner conductive layer, such that either the anode case or the cathode case, or both, include the inner conductive layer and the passivation layer. FIG. 17 shows a schematic diagram of an exemplary method for assembling a cathode case 1700. In FIG. 17, the conductive layer 1703 is formed into a cup shape separately from the passivation layer 1704 and placed on a fixture 1701 that holds the part and masks certain sections of the inner conductive layer during processing. The inner conductive layer is then coated with a passivation layer 1704, including a film 1704b on the inner wall, a film 1704a1 on the bottom of the case, a film 1704a2 on the outer wall of the case, and a film 1704c on the rim of the case, with films 1704a1, 1704a2, 1704b, and 1704c all in electrical contact to form the two-layer cathode case 1700. The passivation layer 1704 can be applied by a vapor deposition process such as chemical vapor deposition, physical vapor deposition, deposition, or electroplating. In some embodiments, the passivation layer covers only the outer surface and rim. In other embodiments, the passivation layer covers all surfaces of the inner conductive layer.
[0436] In another exemplary method of manufacture, the cathode case comprises: a) forming the passivated metal into a passivated cup having a bottom, an annular side, and a rim, each of the bottom, annular side, and rim having an inner surface and an outer surface; b) forming the inner conductive metal into an inner conductive cup having a bottom, an annular side, and a rim, each of the bottom, annular side, and rim having an inner surface and an outer surface; and c) placing an inner conductive cup within the passivation cup, the outer surface of the inner conductive cup being in electrical contact with the inner surface of the passivation cup, thereby forming the cathode case.
[0437] In some embodiments, the annular side of the deactivation cup extends beyond the annular side of the inner conductive cup, further comprising folding the rim of the deactivation cup over the rim of the inner conductive cup.
[0438] In some embodiments, the rim of the passivation cup partially covers the rim of the inner conductive cup.In some embodiments, the rim of the passivation cup covers the rim of the inner conductive cup.
[0439] In some embodiments, forming the passivation cup and / or the inner conductive cup comprises a process selected from stamping, wire forming, metal casting, or metal injection molding.
[0440] In yet another exemplary method, vapor deposition is used to deposit a conductive layer on a passivated metal case, where the anode case, the cathode case, or both, include an inner conductive layer and a passivation layer. In this embodiment, the conductive layer is deposited on the inner surface of the case. In a further method, an outer coating is deposited on the outer surface of the passivation layer.
[0441] In some embodiments of the aforementioned manufacturing method, the inner conductive layer can be formed by casting a conductive metal to form a cup. In some embodiments, the cast conductive metal cup can conform to the inside of the cup-shaped passivation layer. In one embodiment, aluminum or an aluminum alloy can be cast to form a cup having a uniform or variable thickness of 5 μm to 300 μm, or 5 μm to 50 μm. Casting can advantageously prevent wrinkling that can occur during the stamping or molding process.
[0442] In another embodiment of the aforementioned manufacturing method, an internal support layer is provided, including a bottom, an annular side, a rim, an internal surface, and an external surface. First, a passivation layer is deposited on the internal surface, the external surface, and the rim surface of the internal support member. Next, a conductive material is deposited on the passivation layer on the internal surface and optionally on the rim, thereby forming the internal conductive layer. Finally, optionally, a second conductive material is deposited on the passivation layer on the external surface and optionally on the rim, thereby forming a second conductive layer.
[0443] In other embodiments, the battery is assembled using an anode case and a cathode case that include only the inner conductive layers. After assembly, the exterior surfaces of the battery can be coated with a passivation layer. For example, the battery can be coated with a passivation layer using physical vapor deposition (PVD) or chemical vapor deposition. Coated by chemical vapor deposition (CVD), 1nm~10 The passivation layer may be formed with a uniform or variable thickness of 0 pm, or 1 nm to 10 pm. The passivation layer may include Nb, Ta, Ti, Re, W, alloys thereof, or any combination thereof. The gasket may be protected by a removable mask during the deposition process to prevent short circuits between the anode and cathode cases.
[0444] In some embodiments, the cathode cases (or cathode cans) described herein are interchangeable with standard stainless steel cathode cases for manufacturing purposes and are made from approximately 200 pm thick laminates, e.g., cladding, with a passivation layer (e.g., 110 μm thick niobium) coated onto an inner conductive layer (e.g., 90 μm thick stainless steel 430), the passivation layer coated onto the inner conductive layer reducing or preventing cracking during 90 degree bends, 180 degree bends, or zero radius hem fold extension when the laminates are fabricated into the cathode cases or cathode cans described herein.
[0445] VI. Exemplary Battery Function in Devices During and After Immersion In further embodiments, oxides on the surface of the passivation layer of the cathode case can retain electrical conductivity while reducing or inhibiting electrolytic reactions at the terminals. The increase in dry internal resistance of a battery after brief immersion in a conductive aqueous medium can increase as described herein. Measurement of battery internal resistance is known in the art, and an example is described in Section VII. Test Procedure.
[0446] This continuous operation under these conditions can be useful in transformers, computers, and high performance batteries that require fluid cooling systems. Typical fluid cooling systems use a dielectric fluid such as propylene glycol so that the fluid does not react with the terminals. If the battery terminals and exposed contacts are made of passivated metal, the battery and device should still be able to operate even when a conductive aqueous medium is in direct contact.
[0447] In additional embodiments, the disclosed batteries can also continue to function electrically during exposure to a conductive aqueous medium, hi other embodiments, the disclosed batteries can function again after being removed from the conductive aqueous medium and dried.
[0448] VII. Test Procedures The resistance of the cathode case can be measured using a four-probe milliohmmeter (Extech Model #380580) for quality control. As shown in Figures 18A, 18B, and 18C, an exemplary cathode case 1802, including an inner conductive layer 1803 and a passivation layer 1804, is placed between two sets of radial probes 1840 and 1841. An example of a four-probe radial fixture is the Gamry Universal Battery Holder (Figure 18A). The resistance is measured from the inside of the inner conductive layer 1803 to the passivation layer 1804, as depicted in Figure 18C.
[0449] Measuring the internal resistance of a battery is known in the art. One method for measuring the internal resistance is to measure the AC impedance at 1 kHz using a Gamry potentiostat.
[0450] The operating conditions of a cell immersed in a conductive aqueous medium can be modeled by applying a potential difference of greater than 1.2 V to the cathode case, immersing the passivation layer in the conductive aqueous medium, and preventing the internal conductive layer from physical contact with the conductive aqueous medium. Using an external power source to apply the potential difference, it may be possible to measure the current and applied voltage under different simulated conditions.
[0451] In other embodiments, a conductive path is formed between the anode and cathode when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium.
[0452] In other embodiments, when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium, a conductive path is formed between the anode and cathode through the conductive aqueous medium, and this conductive path is reduced or inhibited upon continued contact with the conductive aqueous medium.
[0453] In other embodiments, the anode passivation layer and / or the cathode passivation layer oxidize when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium. In other embodiments, the passivation metal in the passivation layer oxidizes when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium. In some embodiments, oxidation of the passivation metal or passivation layer occurs within 2 hours, or within 1 hour, or within 30 minutes, or within 15 minutes of initial contact with the aqueous conductive medium.
[0454] In other embodiments, an electrolytic reaction occurs when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium, and the electrolytic reaction is suppressed or eliminated in less than 2 hours after initial contact with the conductive aqueous medium.
[0455] In further embodiments, contacting with the conductive aqueous medium comprises placing a hydrated tissue on the battery such that the hydrated tissue contacts both at least a portion of the anode case and at least a portion of the cathode case to form a conductive pathway. In other embodiments, the hydrated tissue is hydrated porcine esophageal tissue. In embodiments, contacting with the conductive aqueous medium comprises immersion in a 0.85% saline solution or a 25% Ringer's solution. 25% Ringer's solution contains 36.75 mM sodium chloride, 1.00 mM potassium chloride, and 0.75 mM calcium chloride in water.
[0456] In other embodiments, after immersion in 0.85% saline or 25% Ringer's solution for 120 minutes, or 60 minutes, or 20 minutes, or 10 minutes, the pH of the conductive aqueous medium is less than 9, or less than 8, or less than 7. In other embodiments, the conductive aqueous medium has a starting pH of 5 to 7.5, and the average pH of the conductive aqueous medium sampled at 5 minute intervals over a 60 minute period after immersion of the cell in saline does not exceed an average pH of 10, 9.5, 9, 8.5, or 8.
[0457] In another embodiment, tests can be performed to simulate the suitability of a cathode case. For example, a cathode case can be crimped with an empty anode cup with a 5 mm hole in the center and gasket. This sample battery case can then be immersed to cover only the bottom, outer annular portion, and rim of the cathode case, bridging the gasket to the anode case with a grommet sealing the anode hole. The anode and cathode cases are connected to a power supply monitor unit to provide the desired potential and measure the resulting current in the circuit. Use of this sample battery case allows for measurement of the current output of the cathode case in a simulated cell.
[0458] In some embodiments, the sample battery case comprises a cathode case and an anode case described herein, with at least the cathode case including a passivation layer and an inner conductive layer.
[0459] In some embodiments, a sample battery case is immersed in a conductive aqueous medium and a potential difference of greater than 1.2 V is applied to the cathode case. The sample battery case is immersed so that the passivation layer contacts the conductive aqueous medium, but the internal conductive layer does not contact the conductive aqueous medium. Using an external power source to apply the potential difference, the current across the cathode case and the applied voltage can be measured under different conditions.
[0460] In other embodiments, a conductive path is formed between the anode case and the cathode case of the sample battery case when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium.
[0461] In other embodiments, when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium, a conductive path is formed between the anode case and the cathode case of the sample battery case through the conductive aqueous medium, and this conductive path is reduced or inhibited upon continued contact with the conductive aqueous medium.
[0462] In other embodiments, the passivation metal in the passivation layer oxidizes when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium. In other embodiments, the passivation layer oxidizes when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium. In some embodiments, oxidation of the passivation metal or passivation layer occurs within 2 hours, or within 1 hour, or within 30 minutes, or within 15 minutes of initial contact with an aqueous conductive medium.
[0463] In other embodiments, an electrolytic reaction occurs when at least a portion of the anode case and a portion of the cathode case of the sample battery case contact a conductive aqueous medium, and the electrolytic reaction is suppressed or eliminated in less than 2 hours after initial contact with the conductive aqueous medium.
[0464] In further embodiments, contacting with the conductive aqueous medium includes placing the sample battery case over a hydrated tissue such that the hydrated tissue contacts both at least a portion of the anode case and at least a portion of the cathode case to form a conductive pathway. In other embodiments, the hydrated tissue is hydrated porcine esophageal tissue. In embodiments, contacting with the conductive aqueous medium includes immersion in a 0.85% saline solution or a 25% Ringer's solution. 25% Ringer's solution contains 36.75 mM sodium chloride, 1.00 mM potassium chloride, and 0.75 mM calcium chloride in water.
[0465] In other embodiments, after immersion in 0.85% saline or 25% Ringer's solution for 120 minutes, or 60 minutes, or 20 minutes, or 10 minutes, the pH of the conductive aqueous medium is less than 9, or less than 8, or less than 7. In other embodiments, the conductive aqueous medium has a starting pH of 5 to 7.5, and the average pH of the conductive aqueous medium sampled at 5 minute intervals over a 60 minute period after immersion of the battery in saline does not exceed an average pH of 10, 9.5, 9, 8.5, or 8. [Example]
[0466] Example 1 A. Comparative Testing of Control Metals and Exemplary Battery Case Materials The results of exposing the control metal and example battery materials to conductive aqueous media and hydrated ham are reported below. These tests simulate the activity of the battery under biological conditions (e.g., after being swallowed and interacting with living tissue).
[0467] i) Exemplary cathode case passivation layer materials are immersed in 25% Ringer's solution and simulated gastric juice solution under electrical potential. In this experiment, different candidate metal foils for the cathode case passivation layer were subjected to potentials of 1.5 V and 3.3 V, the nominal voltages of 1.5 V and 3 V batteries, respectively, as the positive electrode, and immersed in 25% Ringer's solution and simulated gastric fluid. In this experimental setup, current was measured over time, which correlates with the rate of water electrolysis. As the current decreased, the reaction rate decreased, producing fewer hydroxide ions over a given period of time. Therefore, a lower current suggests less potential damage to biological tissue.
[0468] Figure 19 shows plots of current versus time for each metal after immersion in 25% Ringer's solution. The Ringer's solution contained 147 mM sodium chloride, 4 mM potassium chloride, and 3 mM calcium chloride, with an initial pH of 5.5-6, simulating the type of environment that would be present in the mouth or esophagus. The metals tested on the positive electrode were tantalum (Ta), hafnium (Hf), tungsten (W), molybdenum (Mo), niobium (Nb), vanadium (V), zirconium (Zr), chromium (Cr), graphite (C), titanium (Ti), and stainless steel 304 (SS304). Only Mo was tested at 1.5 V; all other samples were tested at 1.5 V and 3.3 V. The metals were cut into rectangular shims approximately 5 mm wide and 10 mm long, except for chromium, which was tested as similarly sized pieces from an ingot. In all cases except for tantalum and chromium, the metal thickness was approximately 0.25 mm. The thickness of the tantalum shim was approximately 0.127 mm. The metal for the negative electrode was a stainless steel 304 (SS304) shim measuring 0.25 mm thick, 5 mm wide, and 10 mm long; the same SS304 was used for all negative electrode runs. A DC voltage was applied across two metal shims, with the negative electrode simulating the anode case of the battery and the positive electrode simulating the cathode case of the battery. The two electrodes were positioned approximately 10 mm apart when immersed in 25% Ringer's solution. The experiment lasted approximately 5 to 10 minutes. Additionally, pH was measured at the beginning and end of the run near the designated electrodes, as shown in Table 1.
[0469] [Table 1]
[0470] As shown in Figure 19, changing the metal on the positive electrode showed differences in the amount of current flow through the system. Tantalum (Ta) shims had the lowest current at both 1.5 V (dashed black line) and 3.3 V (solid black line) of all the metals tested. Hafnium (Hf), tungsten (W), titanium (Ti), and niobium (Nb) also showed significantly reduced current at 1.5 V and 3.3 V compared to stainless steel 304 (SS304). Vanadium (V), zirconium (Zr), and chromium (Cr) maintained a current of approximately 5–10 mA at 3.3 V, which is not a significant reduction in current compared to the control stainless steel shim. In fact, Zr and V shims maintained a higher current than SS304 at 3.3 V. Graphite (C) maintained a current of approximately 5 mA at 1.5 V and 3.3 V, similar to Cr and SS304. Molybdenum (Mo) maintained a current below 1 mA at 1.5 V (two runs at 1.5 V are shown). At 1.5 V, Mo performed similarly to V and SS430, with some of the highest currents at an applied voltage of 1.5 V in the experiments.
[0471] When the current was greater than 1 mA, the pH of the solution near the negative terminal increased to a minimum of 6–8, suggesting that a higher concentration of hydroxyl ions was produced, consistent with the current output. The intensity of hydrogen gas evolution, observed as bubbles at the negative terminal, was also significantly greater for samples that exhibited higher currents.
[0472] The experiments described above were carried out in simulated gastric fluid (SGF) and The experiment was repeated with a series of modified metals, including gold (Au), Ti, Ta, Hf, W, Mo, Nb, V, Zr, and C for the positive and negative electrodes. The negative electrode was also SS304 for all runs. Each electrode metal was run at 1.5 V as the positive electrode and again at 3.3 V for up to 5 minutes. The current versus time data was plotted and is shown in Figure 20. The SGF solution contained 2.0 g / L sodium chloride and approximately 2.917 g / L HCl, with a pH of approximately 1.1 to 1.3. This experiment was designed to simulate the response of a battery in the stomach. The pH, measured at the beginning and end of the run, remained below 3 for all runs.
[0473] Under these acidic conditions, the currents for SS304, Hf, Mo, and V increased compared to the currents when immersed in 25% Ringer's solution (compare Figure 20 and Figure 19). At 3.3 V under these acidic conditions, the currents reached 30 mA, the maximum allowable current of the power supply for the SS304, Hf, Mo, Au, and V runs, suggesting very fast reaction rates for the electrolysis. Even at a lower potential of 1.5 V, the Au, Hf, Mo, V, and Zr shims maintained currents above 1 mA under these acidic conditions.
[0474] Runs with Ti, Ta, W, and Nb maintained lower currents that dropped below 0.1 mA within 400 seconds at 3.3 V. Ta showed the most significant current reduction at 1.5 V and 3.3 V, while Nb performed similarly at 3.3 V.
[0475] Overall, this experiment demonstrates that Ta and Nb metals are well suited as passivation layers to reduce or inhibit oxidation half-reactions on the positive terminal of a battery. Ti and W may also be suitable for reducing oxidation half-reactions.
[0476] The graph in Figure 30 shows the change in current output in the circuit under applied potentials of 1.5 V, 3, and 3.3 V using nickel (Ni), gold (Au), niobium (Nb), and stainless steel 430 (SS430) as the cathode electrode and stainless steel 430 as the anode, immersed in 25% Ringer's solution. The lines showing 3000 ohms and 6600 ohms represent the resistance at 3.3 V and 1.5 V, respectively. The current generated under these conditions (0.5 mA) is considered acceptable to GI tissue, as this is the current determined to minimize hydroxyl production and therefore tissue damage.
[0477] While measuring the potential difference, the corresponding output electrolysis current was measured. Each metal started at a specific oxidation resistance, determined as the ratio of the potential difference to the measured current (V = IR), at 1.5 V, 3, or 3.3 V. Over time, resistance decreased for both nickel and stainless steel 430 due to their continued oxidation. These two metals allowed current to continue flowing, generating an ongoing or unabated electrolysis reaction that caused an increase in hydroxyl ion concentration (pH) at the anode. For gold, some oxidation resistance was observed at 1.5 V. However, no oxidation resistance was observed at an applied potential of 3 V. This metal also allowed current to continue flowing, generating an ongoing or unabated electrolysis reaction that ultimately led to a dangerous increase in pH. In contrast, niobium showed an increase in oxidation resistance at both 1.5 V and 3 V. The continued increase in resistance over time is consistent with the growth of an oxide layer on the surface. The oxide layer eventually creates enough oxidation resistance to slow the rate of hydroxyl ion formation at the anode. This example demonstrates that batteries containing niobium in or on surfaces that come into contact with GI tissue (or a conductive aqueous environment) are less likely to create a hazardous condition for those GI tissues than batteries with gold, nickel, or stainless steel in or on their surfaces. A similar ongoing and destructive electrolytic reaction occurs when a portion of the battery surface has a crack or worn area that exposes the underlying stainless steel (or other conductive metal that does not form an electrolysis-inhibiting oxide layer) and allows contact with GI tissue (or a conductive aqueous environment).
[0478] ii) Tantalum cathode case scratched in 25% Ringer's solution. An empty battery casing was crimped from a tantalum cathode case with a stainless steel 430 (SS430) anode case. The casings were then connected to a circuit using one tantalum strip pressed against the top of the anode case and another tantalum strip pressed against the bottom of the cathode case. A DC voltage of 3.3 V was then applied between them to form a capacitor-like circuit. The results are shown in Figure 21.
[0479] For each measurement, the empty battery casing was attached vertically to a clip that held the battery horizontally, with the bottom of the cathode facing left and the top of the anode facing right. The empty battery casing was lowered into the 25% Ringer's solution so that it was approximately 25% immersed, covering approximately the bottom 3–5 mm of the empty battery casing.
[0480] The resulting circuit current was measured with a 10 kOhm resistor and immersed in 25% Ringer's solution as described above. The sample was pre-oxidized in Ringer's at 3.3 V, with a current spike of less than 0.5 mA, which very quickly returned to the baseline of 0.4 mA current in less than 30 seconds. The experiment was repeated by drying the same empty battery casing and then scratching it with steel wool. This resulted in a significantly larger spike in current of approximately 1.2 mA, followed by a return to the baseline parallel load current within 30 seconds. This result suggests that when, or if, a new layer of tantalum is exposed, the amount of hydroxyl ion generation is significantly reduced within about 30 seconds, thus minimizing changes in the solution pH.
[0481] iii) Immerse the empty crimped exemplary battery under an electrical potential and operating load. Figures 22 and 23 show the performance of control and treated cells fabricated with and without a conductive path created between the cathode and anode cases by partial immersion in solution, and exposed to different parallel load resistances of 1 kOhm, 3.9 kOhm, 10 kOhm, and 15 kOhm.
[0482] Figure 22 shows the results of the following experiment. Three empty battery cases were crimped from stainless steel 304 (SS304), titanium, and tantalum cathode cases with a stainless steel 430 (SS430) anode case. Tantalum leads were then used to connect the anode and cathode cases to an external power supply providing 3.3 V DC. The resulting circuit current was measured. Prior to crimping, the metal cases were measured for total resistance from the inside bottom of the case to the outside bottom using a four-point probe milliohm (mOhm) meter. The resistance was less than 1 mOhm. In a control run, the current was measured for the circuit without the parallel resistor, and the baseline current was 10 -3 ~10 -4 The current was very low, in the mA range. Adding parallel resistors and decreasing the resistance from 15k ohms to 10k ohms to 3.9k ohms to 1k ohm changed the current accordingly. The values at each resistance were consistent across all three circuits.
[0483] The experiment continued with the same circuit setup, but with partial immersion in 25% Ringer's solution. For each measurement, an empty cell casing was partially immersed in 25% Ringer's solution, covering approximately 3 mm of the anode and cathode cases, essentially forming a resistive load through the Ringer's solution. The resulting circuit current was measured without the parallel resistor and then with the parallel resistance sequentially reduced from 15 kOhm to 10 kOhm, 3.9 kOhm, and 1 kOhm, as described above. Prior to immersion, baseline current was measured for all samples. After partial immersion in the stainless steel cathode case condition, the measured current spiked to approximately 3.5 mA and remained at this approximate level for the duration of the test. In the titanium cathode case condition, the current spiked to 3.3 mA and then dropped to approximately 1 mA within 6 minutes. In contrast, in the tantalum cathode case, the current dropped to less than 0.5 mA in approximately the same time period. The external voltage was turned off during the resistance change. With each additional load, starting at 15 kOhm, this pattern repeated itself; essentially, the current in the case of stainless steel 304 was shifted by the parallel load current, then spiked and remained high at partial immersion. For titanium, there was a spike followed by a drop to the baseline parallel load current after approximately 2-4 minutes. For tantalum, on the other hand, the spike dropped more rapidly after approximately 10-30 seconds. This may be due to oxide formation. There was a visible color change in the cases of titanium and tantalum exposed to Ringer's solution after the experiment. However, the resistance of the exposed Ti and Ta metals did not appear to change significantly when tested with two-probe resistance measurements before and after the experiment.
[0484] iv) Exposure of tantalum shims to hydrated ham using an external power source. In this experiment, a tantalum metal shim was used to model the passivation layer of the anode or cathode case. The counter electrode was SS430. The electrodes were arranged parallel to each other with a gap of approximately 1 mm, as shown in Figures 24A and 24B. While the Ta foil was the positive electrode, it was subjected to 3.3 V (Run 2401 - 3.3 V) and 10 V (Run 2407 - 10 V) using an external power supply, and the current was measured. While the Ta foil was the negative electrode, it was subjected to 3.3 V (Run 2402 - 3.3 V). Ham samples were first cut into approximately 2 cm x 4 cm rectangles and hydrated in 20 mL of 25% Ringer's solution in a shallow Petri dish for 30 minutes before testing. The ham slices were placed between the two electrodes. The pH of the ham surface under the positive and negative electrodes was measured after experimental periods ranging from 30 to 120 minutes. The results are shown in Table 2.
[0485] [Table 2]
[0486] When a Ta shim was used as the positive electrode, simulating a passivation layer on the cathode case, it showed no signs of hum damage at 3.3 V for 120 minutes (Run 2401-3.3V) (FIG. 24A) or at 10 V for 60 minutes (Run 2407-10V). The pH data shown in Table 2 and the low current shown in FIG. 24C suggest that a Ta shim as the positive electrode reduces or inhibits the kinetics of water electrolysis.
[0487] When a Ta shim was the negative electrode, simulating the passivation layer of the anode case, it showed signs of hum damage at 3.3 V for 30 minutes (Run 2402-3.3 V) (FIG. 24B). The pH data shown in Table 1 and the higher current shown in FIG. 24C support that a Ta shim alone as the negative electrode does not reduce the kinetics of water electrolysis as much as a Ta shim as the positive electrode.
[0488] v) Tantalum, titanium, gold, and SS430 shims are exposed to hum using a CR2032 commercial battery as the power source. In this experiment, tantalum, titanium, gold, and SS430 metal shims were used as positive electrodes to model the passivation layer of a cathode case. The negative electrode was SS430. Each positive electrode was placed parallel to an SS430 shim with a gap of approximately 1 mm, forming four pairs of shims. A commercially available 3.3 V CR2032 Li metal coin cell battery was used to apply a voltage to the shim pairs, and the voltage was monitored using a Graphtec 10-channel data logger (Figure 25). Ham samples were first cut into approximately 2 cm x 4 cm rectangles and hydrated in 20 mL of 25% Ringer's solution in a shallow Petri dish for at least 30 minutes before testing. The starting pH of the ham was approximately 5. Slices of ham were placed across each electrode pair. The pH of the ham surface under the positive and negative electrodes was measured 70 and 180 minutes during and after the experiment, respectively. The drop in voltage at 70 minutes for each sample was due to removal of the ham at this time for pH and damage measurements. The results are shown in Table 3.
[0489] [Table 3]
[0490] The Ta (Run 2503) and Ti (Run 2504) samples showed no visible signs of damage on the ham. However, the pH of the Ti sample, like the gold sample (Run 2505), decreased on the positive side of the ham and increased on the negative side of the ham. The pH of the Ta sample remained unchanged from its initial reading of 5 even after 180 minutes.
[0491] The Au, Ta, and Ti treatments all reduce the current compared to the SS430 control. These results suggest that during prolonged exposure to moist tissue, a Ta passivation layer on the cathode case reduces the current and therefore causes less damage than an Au or Ti coating.
[0492] vi) Tantalum and titanium cathode case exposure to hydrated ham using CR1616 Test cells were constructed using a CR2032 cathode case made of stainless steel 304, titanium, and tantalum, and a CR2032 anode case made of stainless steel 430. The test cells were powered by inserting a commercially available CR1616 coin cell battery into the casing and using nickel foil to fill any voids and provide a current path from anode to anode. The case was crimped using an MTI hand crimper with a CR2032 crimping die.
[0493] Several thick slices of frozen boar head ham were thawed and cut into six 2" x 2.5" pieces. 10 mL of 25% Ringer's solution was then added to hydrate the ham 1 hour before the experiment began.
[0494] The test cell was then placed anode side down on one slice of ham and covered with an additional slice of ham to cover the cathode side. A 200g weight was added on top of the layer to ensure good contact between the test cell and the ham.
[0495] After 24 hours of contact (Figure 26), the control cell with stainless steel 304 as the cathode case showed significant damage to the ham on both the anode and cathode sides, while neither the cells with titanium or tantalum cathode cases caused significant damage. The test cell with the titanium cathode case showed minimal signs of damage on the ham in direct contact with the cathode case, but showed obvious discoloration, an indicator of damage, of the tissue in direct contact with the anode case.
[0496] The setup was disassembled, and as soon as the test cell was flipped over to the side facing the anode, a strip of pH paper (ranging from 1 to 13) was placed on the area of the humidor that was in direct contact with the cell anode case (Figure 27). For the stainless steel 304 cathode case test cell, the pH of the humidor reached 8.5 in 30 minutes and was 12.5 after 24 hours. The titanium cathode case test cell showed a slight increase in pH from 5.5 to 6.5 within 30 minutes and remained at a pH of 6.5 after 24 hours. Meanwhile, for the tantalum cathode case test cell, the pH did not change at 30 minutes or 24 hours.
[0497] vii) Exposure to high temperatures and relative humidity for multiple days To determine how the batteries would perform after accelerated aging conditions, the lithium control, laboratory-made control, and exemplary batteries were exposed to high temperature and humidity conditions.
[0498] Figure 28 shows the results of the following experiment. Test batteries were constructed using a CR2032 cathode case made of stainless steel 304, titanium, and tantalum, and a CR2032 anode case made of stainless steel 430. The test batteries were powered by inserting a commercially available CR1616 coin cell battery into the casing and using nickel foil to fill any voids and provide a current path from anode to anode. The case was crimped using an MTI hand crimper with a CR2032 crimping die. A commercially available Maxell CR2032 battery was used as a commercial control. Because the laboratory-constructed test batteries contained no electrolyte (apart from that contained in the commercially available CR1616), weight loss was not expected, but the test batteries also did not gain additional weight from moisture intrusion over this period. There was no significant change in the mass of the test batteries, which may indicate static conditions during high-temperature, high-humidity storage.
[0499] Figure 29 shows the results of the following experiment. Test batteries were constructed using a CR2032 cathode case made of stainless steel 304, titanium, and tantalum, and a CR2032 anode case made of stainless steel 430. The test battery was powered by inserting a commercially available CR1616 coin cell battery into the casing and using nickel foil to fill any voids and provide a current path from anode to anode. The case was crimped using an MTI hand crimper with a CR2032 crimping die. A commercially available Maxell CR2032 battery was used as a commercial control. To measure the load voltage, a resistor was connected in parallel and a timer was immediately turned on. The closed-circuit voltage, measured with a DC multimeter, was recorded at 5 seconds. The open-circuit voltage (OCV), 15 kOhm, and 3.9 kOhm voltages remained relatively stable throughout the test conditions. The 1 kOhm resistance condition decreased slightly but was similar to the commercial control and in all cases remained above 3 V. After storage at 60° C. and 90% RH, there was no substantial increase in the resistance of any of the cells.
[0500] Prototype batteries constructed according to the present disclosure exhibit similar heat and humidity stability as control and commercial batteries.
[0501] equivalent The foregoing specification is sufficient to enable one skilled in the art to practice the embodiments. The foregoing description and examples detail certain embodiments and explain the best mode contemplated by the inventors. However, no matter how detailed the above appears in text, it will be understood that the embodiments can be practiced in many ways and should be construed in accordance with the appended claims and any equivalents thereof. The present invention provides, for example, the following items. (Item 1) A battery, a) an anode case; b) a cathode case containing a passivated metal; c) an electrochemical cell comprising an anode, a cathode, and a separator positioned between the anode and the cathode; d) a gasket between the anode case and the cathode case; A battery wherein the passivating metal is present in a layer having a uniform or varying thickness between 100 nm and 400 μm. (Item 2) Item 10. The battery of item 1, wherein the passivating metal comprises Nb, Ta, an alloy thereof, or any combination thereof. (Item 3) The inactivated metal has a size of 100 nm to 1 μm, 100 nm to 3 μm, 100 nm to 5 μm, 100 nm to 10 μm, 1 μm to 400 μm, 3 μm to 100 μm, 3μm~50μm, 15μm~300μm, 14μm~200μm, 25μm~50μm, 50μm~400μm, 50μm~300μm, 50μm~200 3. The battery of claim 1, wherein the cations of ... (Item 4) 4. The battery of any one of items 1 to 3, wherein the cathode case consists essentially of a layer comprising the passivation metal, and the layer has a uniform or variable thickness of 15 μm to 300 μm, 14 μm to 200 μm, or greater than 50 μm to 300 μm. (Item 5) 5. The battery according to any one of items 1 to 4, wherein the cathode case comprises a layer comprising the passivation metal, and the layer has a uniform or variable thickness of 15 μm to 300 μm, 14 μm to 200 μm, or greater than 50 μm to 300 μm. (Item 6) 6. The battery of any one of items 1 to 5, wherein the battery further comprises an exterior coating on an exterior surface of the anode case, or an exterior surface of the cathode case, or both, and the exterior coating comprises Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof. (Item 7) 7. The battery of any one of items 1 to 6, wherein the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof, and wherein the exterior coating has a uniform or varying thickness of 100 nm to 7 μm, 100 nm to 5 μm, or 100 nm to 200 nm. (Item 8) the cathode case includes a cathode inner conductive layer; and a cathode passivation layer comprising the passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact. (Item 9) the cathode case includes a cathode inner conductive layer; and a cathode passivation layer comprising the passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact; and the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof, and wherein the exterior coating and the cathode passivation layer are in electrical contact. (Item 10) the cathode case includes a cathode inner conductive layer; and a cathode passivation layer comprising the passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact. (Item 11) The cathode case is a cathode inner conductive layer; a cathode passivation layer comprising the passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact. (Item 12) 12. The battery of any one of items 8 to 11, wherein the cathode passivation layer has a uniform or varying thickness of 1 μm to 400 μm, 15 μm to 300 μm, 14 μm to 200 μm, or greater than 50 μm to 400 μm, or greater than 50 μm to 300 μm, or greater than 50 μm to 200 μm, or greater than 50 μm to 175 μm. (Item 13) 13. The battery of any one of items 8 to 12, wherein the cathode passivation layer has a uniform or varying thickness of 1 μm to 400 μm, 15 μm to 300 μm, 14 μm to 200 μm, or greater than 50 μm to 400 μm, or greater than 50 μm to 175 μm, and the cathode internal conductive layer has a uniform or varying thickness of 75 μm to 350 μm, or 125 μm to 350 μm, or 200 μm to 300 μm, or 25 μm to 100 μm. (Item 14) For example, the ratio of the thickness of the cathode passivation layer to the thickness of the internal conductive layer is 8:1 to 1:5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:5, or 6:1 to 1:3, or 6:1 to 1:2, or 6:1 to 1:1.1, or 6:1 to 1:1, 3:1 to 1:5, or 3:1 to 1:3, at least at a point in the bottom portion of the cathode case. , or 3:1 to 1:2, or 3:1 to 1:1.1, or 3:1 to 1:1, or 2:1 to 1:5, or 2:1 to 1:3, or 2:1 to 1:2, or 2:1 to 1:1.1, or 2:1 to 1:1, or 8:1 to 1:2.5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:2, or 3:1 to 1:2. (Item 15) 15. The battery of any one of items 8 to 14, wherein the outer coating has a uniform or varying thickness of 100 nm to 200 nm. (Item 16) 16. The battery of any one of items 9 to 15, wherein the outer coating comprises Ni. (Item 17) 17. The battery of any one of items 8-16, wherein a surface of the cathode internal conductive layer in electrical contact with the cathode passivation layer is not exposed to the ambient environment after fabrication. (Item 18) 0.01 mm of the surface of the cathode inner conductive layer that is in electrical contact with the cathode passivation layer 2 Less than or equal to 0.05 mm 2 Less than or 0.1 mm 2 Less than or 0.5 mm 2 Less than or 1.0 mm 2 Less than or 1.5 mm 2 18. The battery of claim 17, wherein less than 10% of the battery is exposed to the ambient environment after manufacture. (Item 19) the cathode case is prepared from a coating laminate comprising a passivation layer having a uniform or variable thickness of 60 μm to 200 μm and a conductive layer having a uniform or variable thickness of 50 μm to 190 μm; 19. The battery of any one of items 1 to 18, wherein the cathode case has a uniform or variable thickness of 200 μm to 250 μm, the cathode case includes a hemfold, the hemfold includes a first side and a second side, each of the first and second sides further including a passivation layer having a uniform or variable thickness of 14 μm to 75 μm, the hemfold has a total thickness of 200 μm to 250 μm, and the first side of the hemfold contacts the second side of the hemfold. (Item 20) 20. The battery of any one of items 1 to 19, wherein the cathode case comprises a hemfold structure. (Item 21) 21. The battery of any one of items 8-20, wherein the cathode passivation layer comprises a first layer comprising a first passivation metal and a second layer comprising a second passivation metal. (Item 22) 22. The battery of any one of items 8-21, wherein the cathode passivation layer comprises a first layer comprising Ta or an alloy thereof. (Item 23) 23. The battery of any one of items 8-22, wherein the cathode passivation layer comprises a first layer comprising Ta or an alloy thereof, and the first layer has a uniform or varying thickness of 1 μm to 3 μm. (Item 24) 24. The battery of any one of items 8-23, wherein the cathode passivation layer comprises a second layer comprising Nb or an alloy thereof. (Item 25) 25. The battery of any one of items 8-24, wherein the cathode passivation layer comprises a second layer comprising Nb or an alloy thereof, and the second layer has a uniform or varying thickness from 10 μm to 250 μm. (Item 26) 26. The battery of any one of items 8 to 25, wherein the cathode internal conductive layer has a uniform or varying thickness of 100 μm to 350 μm. (Item 27) 27. The battery of any one of items 1 to 26, wherein the anode case comprises a passivation metal, the passivation metal being present in a layer having a uniform or varying thickness from 100 nm to 400 μm. (Item 28) 28. The battery of any one of items 1-27, wherein the anode case comprises a passivating metal comprising Nb, Ta, an alloy thereof, or any combination thereof. (Item 29) the anode case has an anode inner conductive layer; an anode passivation layer comprising the passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact. (Item 30) the anode case has an anode inner conductive layer; and an anode passivation layer comprising the passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact; and the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof, and wherein the exterior coating and the anode passivation layer are in electrical contact. (Item 31) The anode case is an anode inner conductive layer; an anode passivation layer comprising the passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact. (Item 32) the anode case has an anode inner conductive layer; an anode passivation layer comprising the passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact. (Item 33) The anode passivation layer may have a thickness of 100 nm to 1 μm, 100 nm to 3 μm, 100 nm to 5 μm, 100 nm to 10 μm, 1 μm to 400 μm, 3 μm to 100 μm, 3 μm to 50 μm, 15 μm to 300 μm, 14 μm to 200 μm, 25 μm to 50 μm, 50 μm to 400 μm, 50 μm to 300 μm, 50 μm to 2 33. The battery of any one of items 29 to 32, having a uniform or varying thickness of 00 μm, 50 μm to 175 μm, 55 μm to 400 μm, 55 μm to 300 μm, 55 μm to 200 μm, 60 μm to 400 μm, 60 μm to 300 μm, 60 μm to 200 μm, 200 μm to 300 μm, or 300 μm to 400 μm. (Item 34) 34. The battery of any one of items 29 to 33, wherein the anode passivation layer has a uniform or varying thickness of 15 μm to 300 μm, 14 μm to 200 μm, or greater than 50 μm to 300 μm, and the anode inner conductive layer has a uniform or varying thickness of 75 μm to 350 μm, or 125 μm to 350 μm, or 200 μm to 300 μm, or 25 μm to 100 μm. (Item 35) 35. The battery of any one of items 29-34, wherein the anode passivation layer comprises a first layer comprising a first passivation metal and a second layer comprising a second passivation metal. (Item 36) the anode passivation layer is 36. The battery of any one of items 29 to 35, comprising a first layer comprising Ta or an alloy thereof. (Item 37) the anode passivation layer is 37. The battery of any one of items 29 to 36, comprising a first layer comprising Ta or an alloy thereof, the first layer having a uniform or varying thickness of 1 μm to 3 μm. (Item 38) the anode passivation layer is 38. The battery of any one of items 29 to 37, comprising a second layer comprising Nb or an alloy thereof. (Item 39) 39. The battery of any one of items 35 to 38, wherein the second layer has a uniform or varying thickness of 10 μm to 250 μm. (Item 40) 33. The battery of any one of items 22 to 32, wherein the anode internal conductive layer has a uniform or varying thickness of 100 μm to 350 μm. (Item 41) Item 10. The battery of item 1, wherein the passivating metal comprises Re, W, or an alloy thereof. (Item 42) The inactivation metal has a size of 100nm to 1μm, 100nm to 3μm, 100nm to 5μm, 100nm to 10μm, 1μm to 400μm, 3μm to 100μm , 3μm~50μm, 15μm~300μm, 14μm~200μm, 25μm~50μm, 50μm~400μm, 50μm~300μm, 50μm~20 42. The battery of item 41, wherein the cations of the cations of the present invention are present in a layer having a uniform or varying thickness of 0 μm, 50 μm to 175 μm, 55 μm to 400 μm, 55 μm to 300 μm, 55 μm to 200 μm, 60 μm to 400 μm, 60 μm to 300 μm, 60 μm to 200 μm, 200 μm to 300 μm, or 300 μm to 400 μm. (Item 43) 43. The battery of item 41 or 42, wherein the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, and the exterior coating comprises Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof. (Item 44) 44. The battery of any one of items 41 to 43, wherein the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, the exterior coating comprising Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof, and the exterior coating has a uniform or varying thickness of 100 nm to 7 μm, 100 nm to 5 μm, or 100 nm to 200 nm. (Item 45) the cathode case includes a cathode inner conductive layer; and a cathode passivation layer comprising the passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact. (Item 46) the cathode case includes a cathode inner conductive layer; and a cathode passivation layer comprising the passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact; and the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof, and wherein the exterior coating and the cathode passivation layer are in electrical contact. (Item 47) the cathode case includes a cathode inner conductive layer; and a cathode passivation layer comprising the passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact. (Item 48) The cathode case is a cathode inner conductive layer; and a cathode passivation layer comprising the passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact. (Item 49) 49. The battery of any one of items 45-48, wherein the cathode passivation layer has a uniform or varying thickness of 15 μm to 300 μm, 14 μm to 200 μm, or greater than 50 μm to 400 μm, or greater than 50 μm to 300 μm, or greater than 50 μm to 200 μm, or greater than 50 μm to 175 μm. (Item 50) 50. The battery of any one of items 45 to 49, wherein the cathode passivation layer has a uniform or varying thickness of 15 μm to 300 μm, 14 μm to 200 μm, or greater than 50 μm to 400 μm, or greater than 50 μm to 175 μm, and the cathode internal conductive layer has a uniform or varying thickness of 75 μm to 350 μm, or 125 μm to 350 μm, or 200 μm to 300 μm, or 25 μm to 100 μm. (Item 51) For example, the ratio of the thickness of the cathode passivation layer to the thickness of the internal conductive layer is 8:1 to 1:5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:5, or 6:1 to 1:3, or 6:1 to 1:2, or 6:1 to 1:1.1, or 6:1 to 1:1, 3:1 to 1:5, or 3:1 to 1:3, at least at a point in the bottom portion of the cathode case. 51. The battery according to any one of items 45 to 50, wherein the ratio of the ionic current density (OCD) of the battery is 8:1 to 1:2.5, or 3:1 to 1:2, or 3:1 to 1:1.1, or 3:1 to 1:1, or 2:1 to 1:5, or 2:1 to 1:3, or 2:1 to 1:2, or 2:1 to 1:1.1, or 2:1 to 1:1, or 8:1 to 1:2.5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:2, or 3:1 to 1:2. (Item 52) 52. The battery of any one of items 45 to 51, wherein the outer coating has a uniform or varying thickness of 100 nm to 200 nm. (Item 53) Item 54. The battery according to any one of Items 45 to 52, wherein the outer coating contains Ni. 54. The battery of any one of items 45-53, wherein a surface of the cathode internal conductive layer in electrical contact with the cathode passivation layer is not exposed to the ambient environment after fabrication. (Item 55) 0.01 mm of the surface of the cathode inner conductive layer that is in electrical contact with the cathode passivation layer 2 Less than or equal to 0.05 mm 2 Less than or 0.1 mm 2 Less than or 0.5 mm 2 Less than or 1.0 mm 2 Less than or 1.5 mm 2 55. The battery of any one of items 45 to 54, wherein less than 100% of the battery is exposed to the ambient environment after manufacture. (Item 56) the cathode case is prepared from a coating laminate comprising a passivation layer having a uniform or variable thickness of 60 μm to 200 μm and a conductive layer having a uniform or variable thickness of 50 μm to 190 μm; 56. The battery of any one of items 45 to 55, wherein the cathode case has a uniform or varying thickness of 200 μm to 250 μm, the cathode case includes a hemfold, the hemfold includes a first side and a second side, each of the first and second sides further including a passivation layer having a uniform or varying thickness of 14 μm to 75 μm, the hemfold has a total thickness of 200 μm to 250 μm, and the first side of the hemfold contacts the second side of the hemfold. (Item 57) 57. The battery of any one of items 45 to 56, wherein the cathode case comprises a hemfold structure. (Item 58) 58. The battery of any one of items 45-57, wherein the cathode passivation layer comprises a first layer comprising a first passivation metal and a second layer comprising a second passivation metal. (Item 59) the cathode passivation layer is 59. Any one of items 45 to 58, including a first layer containing Re, W, or an alloy thereof. Battery as described. (Item 60) the cathode passivation layer is 60. The battery of any one of items 45 to 59, comprising a first layer comprising Re, W, or an alloy thereof, the first layer having a uniform or varying thickness of 1 μm to 25 μm. (Item 61) the cathode passivation layer is 61. The battery of any one of items 45 to 60, comprising a second layer comprising Nb or an alloy thereof. (Item 62) the cathode passivation layer is 62. The battery of any one of items 45 to 61, comprising a second layer comprising Nb or an alloy thereof, the second layer having a uniform or varying thickness of 5 μm to 250 μm. (Item 63) 63. The battery of any one of items 45 to 62, wherein the cathode inner conductive layer has a uniform or varying thickness of 100 μm to 350 μm. (Item 64) 64. The battery of any one of items 41 to 63, wherein the anode case comprises a passivation metal, the passivation metal being present in a layer having a uniform or varying thickness from 100 nm to 400 μm. (Item 65) 65. The battery of any one of items 41-64, wherein the anode case comprises a passivating metal comprising Re, W, or an alloy thereof. (Item 66) the anode case has an anode inner conductive layer; an anode passivation layer comprising the passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact. (Item 67) the anode case has an anode inner conductive layer; and an anode passivation layer comprising the passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact; and the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof, and wherein the exterior coating and the anode passivation layer are in electrical contact. (Item 68) The anode case is an anode inner conductive layer; and an anode passivation layer comprising the passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact. (Item 69) The anode case is an anode inner conductive layer; and an anode passivation layer comprising the passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact. (Item 70) The anode passivation layer may have a thickness of 100 nm to 1 μm, 100 nm to 3 μm, 100 nm to 5 μm, 100 nm to 10 μm, 1 μm to 400 μm, 3 μm to 100 μm, 3 μm to 50 μm, 15 μm to 300 μm, 14 μm to 200 μm, 25 μm to 50 μm, 50 μm to 400 μm, 50 μm to 300 μm, 50 μm to 2 70. The battery of any one of items 66 to 69, having a uniform or varying thickness of 00 μm, 50 μm to 175 μm, 55 μm to 400 μm, 55 μm to 300 μm, 55 μm to 200 μm, 60 μm to 400 μm, 60 μm to 300 μm, 60 μm to 200 μm, 200 μm to 300 μm, or 300 μm to 400 μm. (Item 71) 71. The battery of any one of items 66-70, wherein the anode passivation layer has a uniform or varying thickness of 15 μm to 300 μm, 14 μm to 200 μm, or greater than 50 μm to 300 μm, and the anode inner conductive layer has a uniform or varying thickness of 75 μm to 350 μm, or 125 μm to 350 μm, or 200 μm to 300 μm, or 25 μm to 100 μm. (Item 72) 72. The battery of any one of items 66-71, wherein the anode passivation layer further comprises a first layer comprising a first passivation metal and a second layer comprising a second passivation metal. (Item 73) 73. The battery of any one of items 66-72, wherein the anode passivation layer further comprises a first layer comprising Re, W, or an alloy thereof. (Item 74) 73. The battery of any one of items 66-72, wherein the anode passivation layer further comprises a first layer comprising Re, W, or an alloy thereof, the first layer having a uniform or varying thickness from 1 μm to 3 μm. (Item 75) 73. The battery of any one of items 66-72, wherein the anode passivation layer further comprises a second layer comprising Nb or an alloy thereof. (Item 76) 73. The battery of any one of items 66-72, wherein the anode passivation layer further comprises a second layer comprising Nb or an alloy thereof, the second layer having a uniform or varying thickness from 10 μm to 250 μm. (Item 77) 73. The battery of any one of items 66 to 72, wherein the anode internal conductive layer has a uniform or varying thickness of 100 μm to 350 μm. (Item 78) Item 1. The battery of item 1, wherein the passivating metal comprises Ti or an alloy thereof, and the battery optionally comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Al, Cu, Cr, or Zn, an alloy thereof, or any combination of two or more thereof. (Item 79) 80. The battery of item 78, wherein the passivating metal is present in a layer having a uniform or varying thickness of greater than 50 μm to 300 μm, or greater than 50 μm to 200 μm, 200 μm to 300 μm, or 300 μm to 400 μm. (Item 80) 81. The battery of item 78 or 80, wherein the cathode case consists essentially of a layer comprising the passivation metal, the layer having a uniform or varying thickness of greater than 50 μm to 300 μm. (Item 81) 81. The battery of item 78 or 80, wherein the cathode case consists of a layer comprising the passivation metal, the layer having a uniform or varying thickness of greater than 50 μm to 300 μm. (Item 82) 82. The battery of any one of items 78-81, wherein the exterior coating is present on both the outer surface of the anode case and the outer surface of the cathode case. (Item 83) 82. The battery of any one of items 78-81, wherein the exterior coating is on the exterior surface of the anode case. (Item 84) 84. The battery of any one of items 78-83, wherein the exterior coating is on the exterior surface of the cathode case. (Item 85) 85. The battery of any one of items 78 to 84, wherein the outer coating has a uniform or varying thickness of 100 nm to 7 μm, 100 nm to 5 μm, or 100 nm to 200 nm. (Item 86) the cathode case includes a cathode inner conductive layer; and a cathode passivation layer comprising the passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact. (Item 87) the cathode case includes a cathode inner conductive layer; and a cathode passivation layer comprising the passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact; and the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof, and wherein the exterior coating and the cathode passivation layer are in electrical contact. (Item 88) The cathode case is a cathode inner conductive layer; and a cathode passivation layer comprising the passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact. (Item 89) the cathode case includes a cathode inner conductive layer; and a cathode passivation layer comprising the passivation metal, wherein the cathode inner conductive layer and the cathode passivation layer are in electrical contact. (Item 90) 90. The battery of any one of items 86-89, wherein the cathode passivation layer has a uniform or varying thickness of greater than 50 μm to 400 μm, or greater than 50 μm to 300 μm, or greater than 50 μm to 200 μm, or greater than 50 μm to 175 μm. (Item 91) 91. The battery of any one of items 86-90, wherein the cathode inner conductive layer has a uniform or varying thickness of 75 μm to 350 μm, or 125 μm to 350 μm, or 200 μm to 300 μm, or 25 μm to 100 μm. (Item 92) For example, the ratio of the thickness of the cathode passivation layer to the thickness of the internal conductive layer is 8:1 to 1:5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:5, or 6:1 to 1:3, or 6:1 to 1:2, or 6:1 to 1:1.1, or 6:1 to 1:1, 3:1 to 1:5, or 3:1 to 1:3, at least at a point in the bottom portion of the cathode case. , or 3:1 to 1:2, or 3:1 to 1:1.1, or 3:1 to 1:1, or 2:1 to 1:5, or 2:1 to 1:3, or 2:1 to 1:2, or 2:1 to 1:1.1, or 2:1 to 1:1, or 8:1 to 1:2.5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:2, or 3:1 to 1:2. (Item 93) 93. The battery of any one of items 86 to 92, wherein the outer coating has a uniform or varying thickness of 100 nm to 200 nm. (Item 94) The battery according to any one of items 86 to 93, wherein the outer coating comprises Ni. 95. The battery of any one of items 86-94, wherein a surface of the cathode internal conductive layer in electrical contact with the cathode passivation layer is not exposed to the ambient environment after fabrication. (Item 96) 0.01 mm of the surface of the cathode inner conductive layer that is in electrical contact with the cathode passivation layer 2 Less than or equal to 0.05 mm2 Less than or 0.1 mm 2 Less than or 0.5 mm 2 Less than or 1.0 mm 2 Less than or 1.5 mm 2 96. The battery of any one of items 86-95, wherein less than 100% of the battery is exposed to the ambient environment after manufacture. (Item 97) the cathode case is prepared from a coating laminate comprising a passivation layer having a uniform or variable thickness of 60 μm to 200 μm and a conductive layer having a uniform or variable thickness of 50 μm to 190 μm; 96. The battery of any one of items 86-95, wherein the cathode case has a uniform or varying thickness of 200 pm to 250 pm, the cathode case includes a hemfold, the hemfold includes a first side and a second side, each of the first and second sides further including a passivation layer having a uniform or varying thickness of 14 μm to 75 μm, the hemfold has a total thickness of 200 μm to 250 μm, and the first side of the hemfold contacts the second side of the hemfold. (Item 98) 98. The battery of any one of items 86 to 97, wherein the cathode case comprises a hemfold structure. (Item 99) 99. The battery of any one of items 86-98, wherein the anode case comprises a passivation metal, the passivation metal being present in a layer having a uniform or varying thickness of greater than 50 μm to 400 μm. (Item 100) 99. The battery of any one of items 86-99, wherein the anode case comprises a passivating metal comprising Ti or an alloy thereof, and the battery optionally comprises an exterior coating on an exterior surface of the anode case, or an exterior surface of the cathode case, or both, the exterior coating comprising Al, Cu, Cr, or Zn, an alloy thereof, or any combination of two or more thereof. (Item 101) the anode case has an anode inner conductive layer; an anode passivation layer comprising the passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact. (Item 102) the anode case has an anode inner conductive layer; and an anode passivation layer comprising the passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact; and the battery further comprises an exterior coating on the exterior surface of the anode case, or the exterior surface of the cathode case, or both, wherein the exterior coating comprises Al, Cu, Cr, Zn, an alloy thereof, or a combination of two or more thereof, and wherein the exterior coating and the anode passivation layer are in electrical contact. (Item 103) The anode case is an anode inner conductive layer; and an anode passivation layer comprising the passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact. (Item 104) The anode case is an anode inner conductive layer; an anode passivation layer comprising the passivation metal, wherein the anode inner conductive layer and the anode passivation layer are in electrical contact. (Item 105) 105. The battery of any one of items 101-104, wherein the anode passivation layer has a uniform or varying thickness of 50 μm to 100 μm. (Item 106) 106. The battery of any one of items 101 to 105, wherein the anode inner conductive layer has a uniform or varying thickness of 100 μm to 350 μm. (Item 107) 107. The battery of any one of items 1-106, further comprising at least one tie layer disposed between the cathode internal conductive layer and the cathode passivation layer, between the anode internal conductive layer and the anode passivation layer, or both, wherein the internal conductive layer and the passivation layer remain in electrical contact. (Item 108) 108. The battery of any one of items 1-107, further comprising at least one tie layer disposed between the cathode internal conductive layer and the cathode passivation layer, between the anode internal conductive layer and the anode passivation layer, or both, wherein the internal conductive layer and the passivation layer remain in electrical contact, and the at least one tie layer comprises a conductive material. (Item 109) 109. The battery of any one of items 1-108, further comprising at least one tie layer disposed between the cathode internal conductive layer and the cathode passivation layer, between the anode internal conductive layer and the anode passivation layer, or both, wherein the internal conductive layer and the passivation layer remain in electrical contact, and the at least one tie layer comprises a metal. (Item 110) 110. The battery of any one of items 1-109, further comprising at least one tie layer disposed between the cathode internal conductive layer and the cathode passivation layer, between the anode internal conductive layer and the anode passivation layer, or both, wherein the internal conductive layer and the passivation layer remain in electrical contact, and the at least one tie layer comprises an adhesive. (Item 111) Items 1 to 11 further include at least one tie layer disposed between the cathode internal conductive layer and the cathode passivation layer, between the anode internal conductive layer and the anode passivation layer, or both, wherein the internal conductive layer and the passivation layer remain in electrical contact, and the at least one tie layer includes an adhesive, wherein the adhesive includes a pressure sensitive adhesive, a rubber adhesive, an epoxy, a polyurethane, a silicone adhesive, a phenolic resin, a UV curable adhesive, an acrylate adhesive, a laminating adhesive, a fluoropolymer, or any combination of two or more thereof. 10. The battery of any one of claims 1 to 8. (Item 112) Item 112. The battery of item 111, wherein the lamination adhesive comprises low or high density polyethylene, polyolefin, polyolefin derivative, acid-containing adhesive, ionomer, terpolymer of ethylene, acrylate, or ethylene-vinyl acetate. (Item 113) Item 113. The battery of item 112, wherein the acid-containing adhesive comprises EAA, EMAA, an ionomer, a terpolymer of ethylene, an acid, or an acrylate. (Item 114) 114. The battery of any one of items 107-113, wherein the at least one bonding layer has a uniform or varying thickness of 100 nm to 400 μm, 100 nm to 350 μm, 1 μm to 350 μm, 200 μm to 350 μm, 1 μm to 50 μm, 5 μm to 50 μm, 50 μm to 250 μm, or 5 μm to 200 μm. (Item 115) 115. The battery of any one of items 1-114, wherein the anode inner conductive layer and / or the cathode inner conductive layer comprises aluminum, stainless steel, chromium, gold, vanadium, nickel, silver, copper, magnesium, zinc, an alloy thereof, or a combination of any two or more thereof. (Item 116) 116. The battery of any one of items 1-115, wherein the anode inner conductive layer and / or the cathode inner conductive layer comprises stainless steel. (Item 117) 117. The battery of any one of items 1-116, wherein the stainless steel comprises SS304, SS316, SS430, duplex 2205, duplex 2304, duplex 2507, or one or more other steels having a chromium content of 10% by weight or more and / or a nickel content of 0.1% by weight or more. (Item 118) 118. The battery of any one of items 1 to 117, comprising the passivation metal in a passivation layer. (Item 119) 119. The battery of any one of items 1-118, comprising the passivation metal in a passivation layer, the passivation layer comprising a first layer comprising a first passivation metal and a second layer comprising a second passivation metal. (Item 120) 120. The battery of any one of items 1-119, wherein the passivating metal is a substantially pure metal. (Item 121) 121. The battery of any one of items 1 to 120, wherein the passivating metal is an alloy. (Item 122) 122. The battery of any one of items 1-121, wherein the passivating metal comprises an alloy of at least two passivating metals. (Item 123) 123. The battery of any one of items 1 to 122, wherein the anode case has a uniform or variable thickness of 50 μm to 400 μm. (Item 124) 124. The battery of any one of items 1 to 123, wherein the cathode case has a uniform or variable thickness of 50 μm to 400 μm, or 200 μm to 250 μm. (Item 125) 125. The battery of any one of items 1-124, further comprising a water-impermeable coating disposed on and covering the rim of the cathode case, and optionally disposed on a portion of the outer surface of the anode case and / or a portion of the outer surface of the cathode case. (Item 126) 126. The battery of any one of items 1-125, further comprising a water-impermeable coating disposed on a portion of an exterior surface of the anode case and / or a portion of an exterior surface of the cathode case and covering a rim of the cathode case, the water-impermeable coating being selected from natural rubber, TFE, Exxon Butyl, chloroprene, epichlorohydrin, ethylene-propylene, fluorosilicone, hydrogenated nitrile, liquid silicone rubber, medical-grade ethylene propylene, silicone, nitrile, perfluoroelastomer, polyacrylate, polyurethane, styrene butadiene, Teflon®, Vamac, PTFE, and Viton. (Item 127) 127. The battery of any one of items 1-126, further comprising a water-impermeable coating disposed on and covering the rim of the cathode case, and optionally disposed on a portion of the outer surface of the anode case and / or a portion of the outer surface of the cathode case, wherein the water-impermeable coating is the same material as the gasket. (Item 128) a cathode inner conductive layer including an outer bottom surface, an outer annular surface, and a rim surface; the outer bottom surface is covered by a cathode passivation layer; 128. The battery of any one of items 1-127, wherein the outer annular surface and the rim surface are encased by the cathode passivation layer, the gasket, a water-impermeable coating, or any combination of any two or more thereof. (Item 129) 129. The battery of any one of items 1-128, wherein the gasket comprises an elastomeric material or plastic such as nylon, polytetrafluoroethylene, fluorinated ethylene-propylene, chlorotrifluoroethylene, perfluoroalkoxy polymer, polyvinyl, polyethylene, polyethylene terephthalate, polypropylene, polystyrene, polysulfone, polyacrylicate, polyurethane, silicone rubber, and any combination of any two or more thereof. (Item 130) 130. The battery of any one of items 125-129, wherein the water impermeable coating comprises rubber, Buna, silicone, silicone rubber, PTFE, Viton, or an elastomeric material, or a plastic such as nylon, polytetrafluoroethylene, fluorinated ethylene-propylene, chlorotrifluoroethylene, perfluoroalkoxy polymer, polyvinyl, polyethylene, polyethylene terephthalate, polypropylene, polystyrene, polysulfone, polyacrylicate, polyurethane, and any combination of any two or more thereof. (Item 131) 1. A coin cell or cylindrical battery comprising a battery case, the battery case comprising a sealing cup, a bottom can, and a gasket, wherein an outer diameter of the sealing cup is smaller than an inner diameter of the bottom can, at least a portion of the sealing cup is positioned inside the bottom can with the gasket between the sealing cup and the bottom can, and an annular wall of the bottom can is crimped against the annular wall of the sealing cup, and the battery case comprises a passivated metal. (Item 132) Item 132. The battery of item 131, wherein the sealing cup is an anode case and the bottom can is a cathode case, and further wherein the bottom can comprises a passivated metal. (Item 133) Item 1, wherein the sealing cup is a cathode case and the bottom can is an anode case, and both the bottom can and the sealing cup comprise a passivated metal. 32. The battery according to claim 31. (Item 134) 131. The battery of any one of items 1 to 130, wherein the battery is a button or coin cell battery. (Item 135) 135. The battery of any one of items 1 to 134, wherein the electrochemical cell has a voltage of 10 V or less, 5 V or less, 3 V or less, or 1 V or less. (Item 136) 136. The battery of any one of items 1 to 135, which is a 3 volt or 1.5 volt button or coin cell battery. (Item 137) The battery is a CR927, CR1025, CR1130, CR1216, CR1220, CR1225, CR1616, CR1620, CR1625, CR1632, CR2012, CR2016, CR2025, CR2032, CR2320, CR2335, CR2354, CR2412, CR2430, CR2450, CR2477, CR2507, CR3032, or CR11108 lithium coin cell, or a SR 137. The battery of any one of items 1-136, which is an SR41, SR43, SR44, SR45, SR48, SR54, SR55, SR57, SR58, SR59, SR60, SR63, SR64, SR65, SR66, SR67, SR68, SR69, S516, SR416, SR731, SR512, SR714, SR712 silver oxide coin cell, or an LR41, LR44, LR54, or LR66 alkaline coin cell battery. (Item 138) 138. The battery of any one of items 1-137, wherein the battery is a CR2032, CR2016, or CR2025 lithium coin cell battery. (Item 139) 139. The battery of any one of items 1-138, wherein the battery is an AAAA, AAA, AA, A, B, C, D, E 90 / N, 4001, 810, 910A, AM5, LR1, MN9100, or UM-5 cylindrical battery. (Item 140) 139. The battery of any one of items 1 to 139, wherein a conductive path is formed between the anode and the cathode when at least a portion of the anode case and a portion of the cathode case are in electrical contact via a conductive aqueous medium. (Item 141) 141. The battery according to any one of items 1 to 140, wherein when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium, a conductive pathway is formed between the anode and the cathode via the conductive aqueous medium, and further, the conductive pathway is reduced or inhibited upon continuous contact with the conductive aqueous medium. (Item 142) 142. The battery of any one of items 1-141, wherein a conductive pathway is formed between the anode and the cathode through the conductive aqueous medium when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium, and further wherein the conductive pathway is reduced or inhibited in less than 2 hours, or less than 1 hour, or less than 30 minutes after initial contact with the conductive aqueous medium. (Item 143) 143. The battery of any one of items 1-142, wherein the anode passivation layer and / or the cathode passivation layer oxidizes when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium. (Item 144) 144. The battery of any one of items 1-143, wherein the anode passivation layer and / or the cathode passivation layer oxidize to form an oxide layer when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium, and the battery provides a current of less than 1.5 mA, or less than 1 mA, or less than 0.5 mA, or less than 0.3 mA after the oxide layer is formed. (Item 145) 145. The battery of any one of items 1-144, wherein the anode passivation layer and / or the cathode passivation layer oxidize to form an oxide layer when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium, and the battery provides a current of less than 1.5 mA, or less than 1 mA, or less than 0.5 mA, or less than 0.3 mA after the oxide layer is formed, and further wherein the oxide layer is formed in less than 2 hours, or less than 1 hour, or less than 30 minutes after initial contact with the conductive aqueous medium. (Item 146) 146. The battery of any one of items 1-145, wherein an electrolysis reaction occurs when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium, and the electrolysis reaction is inhibited or reduced in less than 2 hours, or less than 1 hour, or less than 30 minutes after initial contact with the conductive aqueous medium. (Item 147) 147. The battery of any one of items 140-146, wherein the contacting with the conductive aqueous medium comprises placing the battery on the hydrated tissue such that the hydrated tissue contacts both at least a portion of the anode case and a portion of the cathode case to form a conductive pathway. (Item 148) Item 148. The battery of item 147, wherein the hydrated tissue is hydrated porcine esophageal tissue. (Item 149) 147. The battery of any one of items 140 to 146, wherein the contact with the conductive aqueous medium comprises immersion in 25% Ringer's solution. (Item 150) Item 149. The battery of item 149, wherein after immersion in 25% Ringer's solution for 120 minutes, or 60 minutes, or 20 minutes, or 10 minutes, the pH of the 25% Ringer's solution is less than 9, or less than 8, or less than 7. (Item 151) Item 151. The battery of item 149 or 150, wherein the 25% Ringer's solution has a starting pH of 5 to 7.5, and the average pH of the 25% Ringer's solution sampled at 5-minute intervals over a 60-minute period after immersion of the battery in the 25% Ringer's solution does not exceed an average pH of 10, 9.5, 9, 8.5, or 8. (Item 152) a cathode inner conductive layer; a cathode passivation layer comprising a passivation metal comprising Ta, Nb, Re, W, Ti, alloys thereof, or any combination thereof; The cathode case, wherein the cathode passivation layer has a uniform or variable thickness between 1 μm and 400 μm. (Item 153) Item 153. The cathode case of item 152, further comprising an exterior coating on an exterior surface of the cathode case, the exterior coating comprising Ni, Al, Cu, Cr, Zn, an alloy thereof, or any combination of two or more thereof. (Item 154) Item 154. The cathode case according to item 153, wherein the outer coating has a uniform or variable thickness of 100 nm to 7 pm or 100 nm to 5 μm. (Item 155) 155. The cathode case according to item 153 or 154, wherein the outer coating has a uniform or varying thickness between 100 nm and 200 nm. (Item 156) 156. The cathode case of any one of items 153 to 155, wherein the outer coating comprises Ni. (Item 157) 157. The cathode case of any one of items 152 to 156, wherein the cathode passivation layer has a uniform or variable thickness between 14 μm and 200 μm. (Item 158) 158. The cathode case of any one of items 152 to 157, wherein the passivating metal comprises Nb or an alloy thereof. (Item 159) 158. The cathode case of any one of items 152 to 157, wherein the passivating metal comprises Ta or an alloy thereof. (Item 160) 158. The cathode case of any one of items 152 to 157, wherein the passivating metal comprises W or an alloy thereof. (Item 161) 158. The cathode case of any one of items 152 to 157, wherein the passivating metal comprises Ti or an alloy thereof. (Item 162) 158. The cathode case of any one of items 152 to 157, wherein the passivating metal comprises Re or an alloy thereof. (Item 163) 1163. The cathode case of any one of items 152 to 1162, wherein the cathode inner conductive layer has a uniform or varying thickness of 100 μm to 350 μm. (Item 164) 164. The cathode case of any one of items 152 to 163, wherein the cathode inner conductive layer comprises aluminum, stainless steel, chromium, gold, vanadium, nickel, silver, copper, magnesium, zinc, an alloy thereof, or a combination of any two or more thereof. (Item 165) 165. The cathode case of any one of items 152 to 164, wherein the cathode interior conductive layer comprises stainless steel. (Item 166) For example, the ratio of the thickness of the cathode passivation layer to the thickness of the internal conductive layer is, at least at some point in the bottom portion of the cathode case, 8:1 to 1:5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:5, or 6:1 to 1:3, or 6:1 to 1:2, or 6:1 to 1:1.1, or 6:1 to 1:1, 3:1 to 1:5, or 3:1 to 1:3, or 3 166. The cathode case according to any one of items 152 to 165, wherein the cathode case has a mol / L / L ratio of 8:1 to 1:2, or 3:1 to 1:1.1, or 3:1 to 1:1, or 2:1 to 1:5, or 2:1 to 1:3, or 2:1 to 1:2, or 2:1 to 1:1.1, or 2:1 to 1:1, or 8:1 to 1:2.5, or 8:1 to 1:3, or 8:1 to 1:2, or 8:1 to 1:1.1, or 8:1 to 1:1, or 6:1 to 1:2, or 3:1 to 1:2. (Item 167) 167. The cathode case of any one of items 152 to 166, wherein the cathode passivation layer oxidizes to form an oxide layer when at least a portion of the anode case and a portion of the cathode case contact a conductive aqueous medium, and the battery provides a current of less than 1.5 mA, or less than 1 mA, or less than 0.5 mA, or less than 0.3 mA after the oxide layer is formed, and further wherein the oxide layer is formed in less than 2 hours, or less than 1 hour, or less than 30 minutes after initial contact with the conductive aqueous medium. (Item 168) (i) the surface of the cathode internal conductive layer that is in electrical contact with the cathode passivation layer is not exposed to the ambient environment after fabrication, or (ii) within 0.01 mm of the surface of the cathode internal conductive layer that is in electrical contact with the cathode passivation layer 2 Less than or equal to 0.05 mm 2 Less than or 0.1 mm 2 Less than or 0.5 mm 2 Less than or 1.0 mm 2 Less than or 1.5 mm 2 168. The cathode case of any one of items 152 to 167, wherein less than 100% of the cathode case is exposed to the ambient environment after manufacture. (Item 169) 169. The cathode case according to any one of items 1 to 168, wherein the cathode case comprises a hemfold structure. (Item 170) 170. The cathode case of any one of items 152 to 169, wherein the cathode inner conductive layer and the cathode passivation layer both comprise a coating laminate. (Item 171) the cathode case is prepared from a coating laminate comprising a passivation layer having a uniform or variable thickness of 60 μm to 200 μm and a conductive layer having a uniform or variable thickness of 50 μm to 190 μm; 171. The cathode case according to any one of items 152 to 170, wherein the cathode case has a uniform or variable thickness of 200 μm to 250 μm, the cathode case comprises a hemfold, the hemfold comprises a first side and a second side, each of the first and second sides further comprising a passivation layer having a uniform or variable thickness of 14 μm to 75 μm, the hemfold has a total thickness of 200 μm to 250 μm, and the first side of the hemfold contacts the second side of the hemfold. (Item 172) 171. The cathode case of any one of items 152 to 170, which is interchangeable with the cathode case of a commercially manufactured button cell battery or coin cell battery. (Item 173) A laminate, a conductive layer having a uniform or variable thickness between 10 μm and 400 μm; a passivation layer comprising a passivation metal selected from Ta, Nb, Re, W, Ti, alloys thereof, and combinations thereof, the passivation layer having a uniform or varying thickness between 10 μm and 400 μm; The stack, wherein the stack is for use in an anode case or a cathode case. (Item 174) Item 174. The laminate of item 173, further comprising an outer coating. (Item 175) Item 175. The laminate according to item 173 or 174, wherein the conductive layer has a uniform or varying thickness of 175 μm to 300 μm. (Item 176) 176. The laminate of any one of items 173 to 175, wherein the passivation layer has a uniform or varying thickness of 1 μm to 100 μm. (Item 177) 177. The laminate of any one of items 174 to 176, wherein the outer coating has a uniform or varying thickness of 100 nm to 7 μm, 100 nm to 5 μm, or 100 nm to 200 nm. (Item 178) 178. The laminate according to any one of items 173 to 177, wherein the laminate has a uniform or variable thickness of 50 μm to 330 μm. (Item 179) A method of manufacturing a laminate for use in an anode case or a cathode case, the laminate comprising: a conductive layer; a passivation layer comprising a passivation metal selected from Ta, Nb, Re, W, Ti, alloys thereof, and combinations thereof; The method comprises: laminating the conductive layer and the passivation layer. (Item 180) A method of manufacturing a laminate for use in an anode case or a cathode case, the laminate comprising: a conductive layer having a uniform or variable thickness between 10 μm and 400 μm; a passivation layer comprising a passivation metal selected from Ta, Nb, Re, W, Ti, alloys thereof, and combinations thereof, the passivation layer having a uniform or varying thickness between 10 μm and 400 μm; The method comprises: coating the conductive layer and the passivation layer. (Item 181) Item 181. The method according to item 179 or 180, wherein the conductive layer has a uniform or variable thickness of 50 μm to 100 μm, or 75 μm to 200 μm, or 175 μm to 300 μm. (Item 182) 182. The method according to any one of items 179 to 181, wherein the passivation layer has a uniform or variable thickness of 1 μm to 75 μm, or 50 μm to 100 μm, or 75 μm to 200 μm, or 175 μm to 300 μm. (Item 183) 183. The method of any one of items 179 to 182, wherein the thickness of the laminate is uniform or variable between 75 μm and 400 μm. (Item 184) 184. The method of any one of items 179 to 183, wherein the method further comprises laminating an outer coating to the passivation layer of the laminate. (Item 185) 184. The method of any one of items 179 to 183, wherein the method further comprises applying the outer coating to the passivation layer of the laminate. (Item 186) 184. The method of any one of items 179 to 183, wherein the method further comprises depositing the outer coating onto the passivation layer of the laminate. (Item 187) 172. A method for producing a laminate for use in an anode case or a cathode case of the battery according to any one of items 1 to 171, comprising: a conductive layer; a passivation layer; The method comprises: laminating the conductive layer and the passivation layer; The method optionally includes laminating an outer coating to the passivation layer, the passivation layer being disposed between the conductive layer and the outer coating. (Item 188) A method for producing a laminate for use in an anode case or a cathode case of the battery according to any one of items 1 to 171, comprising: a conductive layer; a passivation layer; The method comprises: coating the conductive layer and the passivation layer; The method optionally includes applying an outer coating to the passivation layer, the passivation layer being disposed between the conductive layer and the outer coating. (Item 189) A laminate produced by the method according to any one of Items 179 to 188. (Item 190) 189. The laminate of any one of items 173 to 178 or 189, wherein the conductive layer comprises stainless steel. (Item 191) 1. A method of manufacturing a cathode case, comprising: stamping the laminate of any one of items 173 to 178 or 189 to form a cathode case comprising a bottom, an annular side, and a rim; the conductive layer forms the inner surface of the cathode case; The method wherein the passivation layer forms an exterior surface of the cathode case. (Item 192) 1. A method of manufacturing a cathode case, comprising: stamping the laminate of any one of items 173 to 178 or 189 to form a cathode case comprising a bottom, an annular side, and a rim; the conductive layer forms the inner surface of the cathode case; the exterior coating forms an exterior surface of the cathode case, and a passivation layer is between the conductive layer and the exterior coating, the passivation layer being in electrical contact with both the conductive layer and the exterior coating. (Item 193) extending the annular side portion of the cathode case to form an extended annular side portion of the cathode case and a lower annular side portion of the cathode case, the extended annular side portion having a thickness less than the lower annular side portion; 193. The method of claim 191 or 192, further comprising folding the extended annular side portion toward the center of the cathode case to form a hem fold. (Item 194) 1. A method of manufacturing a cathode case, comprising: providing an internal support member including a bottom, an annular side, a rim, an inner surface, and an outer surface; depositing a passivation layer on the outer surface of the internal support member; and depositing a first conductive material on the inner surface of the internal support member and optionally on the rim to form an internal conductive layer. (Item 195) 1. A method of manufacturing a cathode case, comprisi...
Claims
[Claim 1] The invention described in the present specification.
Citation Information
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