Coin battery with aversive agent coating

Abstract

An aversive coating and an electrochemical cell having at least a portion of an outer surface coated with the aversive coating are provided to prevent a child from swallowing the electrochemical cell. Compositions and methods for making an electrochemical cell coated with an aversive coating are described, wherein the ratio of aversive gustatory agent to water soluble polymer is such that the aversive coating sufficiently adheres to the electrochemical cell.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to the following applications: U.S. non-provisional application No. 18 / 593,391, filed March 1, 2024, which claims priority to U.S. provisional application No. 63 / 508,777, filed June 16, 2023; U.S. non-provisional application No. 18 / 593,533, filed March 1, 2024, which claims priority to U.S. provisional application No. 63 / 508,745, filed June 16, 2023; and U.S. non-provisional application No. 18 / 593,527, filed March 1, 2024, which claims priority to U.S. provisional application No. 63 / 508,764, filed June 16, 2023, all of which are incorporated herein by reference in their entirety.

[0003] This application also claims priority interest in U.S. non-provisional application No. 18 / 593,561, filed March 1, 2024, which claims priority interest in U.S. provisional application No. 63 / 586,879, filed September 29, 2023, by reference to incorporated U.S. non-provisional application No. 18 / 593,561, filed March 1, 2024. Technical Field

[0004] This disclosure generally relates to coin or button-type electrochemical batteries. Background Technology

[0005] Coin cell batteries, or coin batteries, such as those described in International Patent Publication No. PCT / US2013 / 021430, filed January 14, 2013 (the entire contents of which are incorporated herein by reference), are small, disc-shaped batteries commonly used in a wide range of electronic devices, such as hearing aids, cochlear implant processors, calculators, remote controls, and watches. These battery cells and batteries are commonly referred to as button batteries due to their shape and size.

[0006] Ingesting coin batteries can cause serious injury and even death in children, partly because the current from the battery reacts with bodily fluids such as tissue fluid, mucus, esophageal lining fluid, and gastric juice, producing hydroxide (high pH) on the negative electrode. This hydroxide can cause alkali burns and esophageal perforation. Severe injury can occur within just two hours.

[0007] To address this issue, many manufacturers have incorporated anti-swallowing features. For example, an anti-swallowing feature is a raised border around the battery. This raised border makes it difficult for a child to swallow the battery. Other anti-swallowing features include a bitter coating on the battery surface, which prevents children from putting the battery in their mouths. However, if swallowed, coin or button batteries coated with a bitter agent or having a raised border can still cause an electrolytic reaction in the esophagus or stomach and result in serious injury. Therefore, it can be helpful to provide parents or other caregivers with a signal that a battery may have been swallowed. This signal can be achieved by using a coloring agent to stain the mouth, hands, or other areas that have been moistened with bodily fluids such as saliva that have come into contact with the lithium coin battery. Summary of the Invention

[0008] Various embodiments provide an aversion coating for electrochemical batteries, comprising an aversion taste agent to deter children from swallowing the electrochemical battery, and a water-soluble polymer as a binder. The dry weight composition of the aversion coating comprises 0.5% to 65% by weight of an aversion agent composition and 5% to 98.5% by weight of a water-soluble polymer. The aversion agent composition comprises at least one aversion taste agent and optionally a colorant. In some embodiments, the aversion taste agent is denaphalonium benzoate (DNB), capsaicin, allyl isothiocyanate, or piperine. For the aversion coating to adhere to the electrochemical battery, the ratio of the aversion taste agent to the water-soluble polymer is between 0.015 and 1.0. In some embodiments, the ratio of the aversion taste agent to the water-soluble polymer is approximately 0.15.

[0009] In some embodiments, the water-soluble polymer is selected from polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylamide, or polyethylene glycol (PEG). In some embodiments, the water-soluble polymer is PVA. In some embodiments, the PVA has a molecular weight of about 10,000 to about 150,000. In some embodiments, the PVA is about 80% to about 95% hydrolyzed. In some embodiments, the PVA has a molecular weight of about 75,000 and is about 88% hydrolyzed.

[0010] In some embodiments, the aversion coating further comprises 0.1 wt% to 5.0 wt% of an adhesion promoter. In some embodiments, the adhesion promoter is Lubrizol 2063, Lubrizol 2062, DowSil Z-6137, DowSil 3-6121, or PP-6. In some embodiments, the aversion coating comprises 2.0 wt% to 5.0 wt% of Lubrizol 2063. In some embodiments, the aversion coating further comprises 0.01 wt% to 1.0 wt% of a surfactant. In some embodiments, the surfactant is sodium dodecyl sulfate (SDS). In some embodiments, the aversion coating further comprises 0.01 wt% to 2.0 wt% of a viscosity modifier. In some embodiments, the viscosity modifier is carboxymethyl cellulose (CMC).

[0011] In some embodiments, the repulsive composition comprises a colorant, and the repulsive coating comprises 0.5% to 60% by weight of the colorant. In some embodiments, the colorant comprises: FD&C Blue No. 1 (Brilliant Blue FCF), FD&C Blue No. 2 (Indigo), FD&C Green No. 3 (Fixed Green FCF), FD&C Red No. 3 (Erythrosine), FD&C Red No. 40 (Allure Red AC), FD&C Yellow No. 5 (Tartrazine Yellow), or FD&C Yellow No. 6 (Sunset Yellow). In some embodiments, the colorant is FD&C Blue No. 1.

[0012] In some embodiments, the dry weight composition of the repulsive coating comprises approximately 5.0 wt% to approximately 7.0 wt% DNB, approximately 35 wt% to approximately 45 wt% PVA, and approximately 45 wt% to approximately 55 wt% FD&C Blue No. 1. In some embodiments, the dry weight composition of the repulsive coating comprises approximately 5.0 wt% to approximately 7.0 wt% DNB, approximately 35 wt% to approximately 45 wt% PVA, approximately 45 wt% to approximately 55 wt% FD&C Blue No. 1, and approximately 2.0 wt% to approximately 5.0 wt% Lubrizol 2063. In some embodiments, the dry weight composition of the repulsive coating comprises approximately 5.0 wt% to approximately 7.0 wt% DNB, approximately 35 wt% to approximately 45 wt% PVA, approximately 45 wt% to approximately 55 wt% FD&C Blue No. 1, approximately 2.0 wt% to approximately 5.0 wt% Lubrizol 2063, and approximately 0.4 wt% SDS.

[0013] Some embodiments provide an electrochemical battery with at least a portion of its outer surface coated with the aversion coating. In some embodiments, the electrochemical battery is a coin cell or button cell. In some embodiments, more than 50% of the area of ​​the outer surface of the positive and / or negative terminals is coated with the aversion coating. In some embodiments, the total amount of the aversion coating applied to the electrochemical battery is from about 0.1 mg to about 1.2 mg. In some embodiments, the total amount of the aversion coating applied to the electrochemical battery contains about 25 µg of aversion taste agent. In some embodiments, the electrochemical battery is packaged in child-proof packaging.

[0014] Various embodiments provide methods for manufacturing electrochemical cells coated with the said aversive coating. The method includes preparing a coating solution comprising 0.2% to 20% by weight of an aversive agent composition dissolved in one or more solvents and 0.2% to 14% by weight of a water-soluble polymer, applying the coating solution to at least a portion of the outer surface of the electrochemical cell, and drying the solution onto said portion of the outer surface of the electrochemical cell.

[0015] In some embodiments, the coating solution is prepared by dissolving 0.2% to 2.0% by weight of an aversive taste agent in one or more solvents. In some embodiments, the coating solution is prepared by dissolving 0.01% to 3.0% by weight of an adhesion promoter in one or more solvents.

[0016] In some embodiments, the coating solution is prepared by heating the PVA in water to about 95°C for about 60 minutes to dissolve it before adding the solution containing dissolved Lubrizol 2063. In some embodiments, the solution containing dissolved PVA is cooled before adding the irritant composition.

[0017] In some embodiments, the coating solution is prepared by dissolving 0.2 wt% to 18 wt% of a colorant in one or more solvents. In some embodiments, the coating solution is prepared by dissolving 0.01 wt% to 0.3 wt% of a surfactant in one or more solvents. In some embodiments, the coating solution is prepared by dissolving 0.01 wt% to 2.0 wt% of a viscosity modifier in one or more solvents.

[0018] In some embodiments, the coating solution is prepared by dissolving approximately 10 wt% PVA, approximately 1.5 wt% DNB, and approximately 12 wt% FD&C Blue No. 1 in one or more solvents. In some embodiments, the coating solution is prepared by dissolving approximately 10 wt% PVA, approximately 1.5 wt% DNB, approximately 12 wt% FD&C Blue No. 1, and approximately 1.0 wt% Lubrizol 2063 in one or more solvents. In some embodiments, the coating solution is prepared by dissolving approximately 10 wt% PVA, approximately 1.5 wt% DNB, approximately 12 wt% FD&C Blue No. 1, approximately 1.0 wt% Lubrizol 2063, and approximately 0.1% SDS in one or more solvents.

[0019] In some embodiments, the method of manufacturing an electrochemical cell further includes masking one or more portions of the electrochemical cell before applying the coating solution. In some embodiments, the method of manufacturing an electrochemical cell further includes cleaning the outer surface of the electrochemical cell before applying the coating solution. Attached Figure Description

[0020] Referring now to the accompanying drawings, which are not necessarily drawn to scale. The accompanying appendices, figures, graphs, images, etc., illustrate various exemplary, non-limiting, inventive aspects, embodiments, and features (“examples” or “illustrations”) according to this disclosure: Figure 1 This is a schematic diagram of a coin battery according to one embodiment, immersed in a saliva solution; Figure 2 These are perspective and cross-sectional views of an electrochemical coin cell according to one embodiment; and Figure 3 Is it like this? Figure 2 The image shows a two-dimensional cross-sectional view of an electrochemical coin cell.

[0021] Figure 4 This is a schematic diagram of a method for manufacturing an electrochemical cell coated with an aversive coating.

[0022] Figure 5 This demonstrates an electrochemical cell with an aversive coating applied to the negative terminal.

[0023] Figure 6 An exemplary child-proof package 600 according to one embodiment is shown. Detailed Implementation

[0024] Coin cells, also known as button cells, are small, single-cell batteries commonly used to power low-power devices such as watches, calculators, hearing aids, and small electronic devices. These batteries are small and compact, making them easy to use and store, and are available in a variety of sizes, chemistry, and rated voltages.

[0025] Originally developed for hearing aids, coin cells are now used in a variety of other applications and devices, such as watches, calculators, and other small electronic devices. A coin cell typically consists of a positive electrode (cathode), a negative electrode (anode), and an electrolyte that allows ions to flow between the electrodes. The electrodes and electrolyte are encapsulated in a small, round metal casing, usually made of stainless steel or nickel-plated brass.

[0026] The positive electrode is typically made of a metal oxide such as silver oxide or manganese dioxide and coated onto a metal mesh or foil. The negative electrode is typically made of a metal such as zinc or lithium and is also coated onto a metal mesh or foil. The electrolyte is typically a liquid or gel and is designed to allow ions to flow between the electrodes.

[0027] Depending on the battery chemistry and rated voltage, the electrodes and electrolyte are arranged in a specific configuration within a metal casing. For example, in a manganese dioxide-based battery, the positive electrode is placed in the center of the battery, while the negative electrode is placed around the outside of the positive electrode. This arrangement allows the battery to provide high voltage output while maintaining a small size.

[0028] The external components include a housing or shell that defines the internal volume in which the anode and electrodes are housed and physically separated by membranes such as ion-permeable membranes, electrolyte-permeable membranes, etc. The anode and cathode use different active materials, such as zinc and manganese dioxide, respectively. These materials are selected based on their electrochemical properties to facilitate the flow of electrons from one terminal to the other. The electrolyte is a liquid or gel substance that allows ions to move between the anode and cathode. Electrolytes are typically a combination of a salt (such as potassium hydroxide) and water.

[0029] Coin cells are available in a variety of chemistry, each with its own unique performance characteristics. For example, alkaline coin cells are the most common type of button cell and are typically used in low-power devices such as watches, calculators, and small electronic devices. These cells use an alkaline electrolyte and a zinc-based negative electrode and are available in a variety of sizes and rated voltages. Silver oxide coin cells are commonly used in high-power devices such as cameras, calculators, and medical devices. These cells use a silver oxide positive electrode and a zinc-based negative electrode and are designed to provide high current output and long lifespan. Zinc-air coin cells are commonly used in hearing aids and use a zinc-based negative electrode and air as the positive electrode. However, these battery chemistry types often have drawbacks such as venting risk, explosion risk, fire risk, shortened battery life, inconsistent discharge, and discharge temperature variation issues. Lithium is a popular alternative to other conventional battery chemistry types, especially for low-power devices such as watches, calculators, and small electronic devices that use coin cells. These cells typically use a manganese dioxide-based positive electrode and a lithium-based negative electrode.

[0030] The primary electrochemical reaction that occurs after ingesting a coin cell is the electrolysis of water due to the following factors: (a) the coin cell itself provides a DC voltage, ~3V OCV (open-circuit voltage); (b) an ionicly conductive medium (saliva) connects the anode (+) and cathode (-) terminals; and (c) these two terminals and the saliva conductive path complete the closed loop of the electrolytic cell. An electrochemical reaction will occur if the voltage supply to the electrolytic cell is high enough to overcome polarization and the 1.23V thermodynamic voltage window used for water electrolysis. In fact, the electrolytic reaction associated with ingesting lithium batteries may be more severe than that associated with ingesting alkaline batteries. This is because the driving force (the voltage difference between the battery voltage and the theoretical water electrolysis voltage of 1.23V) is much higher in the case of a 3V lithium battery than in the case of a 1.5V alkaline battery (3.0V - 1.23V = 1.77V in the case of a lithium battery, compared to 1.5V - 1.23V = 0.27V in the case of an alkaline battery).

[0031] It is worth noting that the nomenclature for electrolytic cells is the opposite of that used for batteries. Therefore, the terms "anode" and "electrolytic anode" refer to the electrode where the oxidation reaction occurs, while the terms "cathode" and "electrolytic cathode" refer to the electrode where the reduction reaction occurs. When assembling an electrolytic cell, such as a coin cell, and sealing the active electrochemical components within the cell, the negative terminal will be electrically connected to the anode or electrolytic anode, while the positive terminal will be electrically connected to the cathode or electrolytic cathode. It should also be noted that electrolysis requires the application of voltage, thus providing a direct contrast to corrosion that typically occurs naturally under environmental conditions.

[0032] Figure 1To illustrate the electrolytic reaction under discussion, a simulated Li-MnO2 electrochemical coin cell 6 is immersed in a saliva solution 5. The main reaction that occurs when a battery with these identical components is accidentally swallowed and becomes lodged in a person's esophagus is shown, although the battery electrodes are shown as discrete components. Specifically, the battery 6 operates at approximately 3V DC and includes a coin cell cup (e.g., positive electrode container) 12, a coin cell canister (e.g., negative electrode container) 20, an anode 40, and a cathode 50. The anode 40 and cathode 50 contain materials specifically chosen based on their compatibility with the expected electrochemical reaction; for example, xLi + MnO2 → Li-MnO2, where Mn is reduced as lithium ions enter the crystal lattice.

[0033] The outer surface of the coin cell cup 12 acts as the negative terminal (cathode in the electrolytic cell), and the outer surface of the coin cell canister 20 acts as the positive terminal (anode in the electrolytic cell). Hydrogen evolution occurs on the coin cell cup 12 by accepting electrons from the battery anode 40, which in this case includes lithium. At the coin cell canister 20 (anode in the electrolytic cell), various reactions occur, such as metal dissolution, oxygen evolution, and possible chloride oxidation, and these reactions compete with each other. The salivary solution 5 is kept charge-neutral by the movement of anions 8 from the coin cell cup 12 (negative terminal) to the coin cell canister 20 (positive terminal) and by the opposite movement of cations 7. When metal from the coin cell canister 20 oxidizes, it loses electrons to the battery cathode 50, which in this case is manganese dioxide. Ultimately, the final product at the coin cell canister 20 depends on its potential, and the solution pH is a result of the combined anodic and cathodic reactions. Furthermore, the solution pH reflects the real-time products generated in the reaction zone between the esophagus and the coin cell; therefore, the solution pH is localized and does not necessarily reflect the pH of the overall solution (i.e., the rest of the saliva not close to the reaction zone).

[0034] When a 3V lithium coin cell battery is immersed in a neutral or alkaline saliva solution, the possible electrochemical reactions at coin cell cup 12 (negative terminal) are shown below. Note that saliva is usually neutral.

[0035] (1) 2H₂O + 2e - H2↑ + 2OH - E0 = -0.83V

[0036] (2) O2 + 2H2O + 4e - 4OH - E0 = -0.4V

[0037] Typically, reaction (1) dominates because oxygen has limited solubility in water, resulting in a very low oxygen concentration in saliva. In either case, hydroxide ions (i.e., OH-) - The production of alkali raises the pH of saliva, potentially to the point of causing alkali burns to the esophagus.

[0038] Saliva can sometimes be acidic. In this case, the reaction at point 12 of the coin battery cup is as follows: (1a) 2H + + 2e - H2↑ E0 = - 0.0V (2a) O2 + 4H + + 4e - 2H₂O E₀ = 1.23 V In either case, the choice of material used at the negative terminal with a high hydrogen evolution overpotential will shift the dominant reaction from (1) and (2) to (1a) and (2a). This has the beneficial effect of reducing or eliminating the formation of hydroxyl groups that can cause localized alkali burns to esophageal tissue.

[0039] When a 3V lithium coin cell battery is immersed in saliva solution 5 and the coin cell battery can 20 contains nickel at least partially along its surface, the possible electrochemical reactions on the coin cell battery can 20 (positive terminal) are as follows.

[0040] (3) 4OH - - 4e - O2↑ + 2H2O

[0041] (4) Ni - 2e - + 2OH - Ni(OH)2

[0042] Reaction (4) typically dominates, causing the metallic components in the coin cell can 20 to oxidize. In practice, lithium-ion battery cans are typically nickel-plated, as illustrated by the oxidation of nickel in reaction (4). If the coin cell can 20 is made of other metals, such as stainless steel, the iron in these alloys could potentially oxidize in a similar reaction. Once the metallic surfaces of the coin cell can 20 have been passivated (i.e., by forming a dense oxide film on the bare metal surface), the oxygen evolution reaction (3) may dominate if the voltage is high enough.

[0043] Furthermore, as shown in (3a) and (4a) below, if an iron-based metal (typically some type of steel) is exposed, especially to the extent that hydroxides are present (e.g., through the aforementioned competing reaction) and / or in an acidic environment (e.g., through saliva), dissolution of the metal container 20 is also a possible outcome.

[0044] (3a) Fe - 2e - Fe 2+ (In acidic medium)

[0045] (4a) Fe - 2e - + 2OH - Fe(OH)2 (in alkaline medium)

[0046] Any combination of the cathodic processes in reactions (1) to (2a) and the anodic processes in reactions (3) to (4a) can be completed. Figure 1 Electrolytic cell 6 is depicted in the diagram. For example, the combination of (1) and (3) results in the following electrolytic reaction in water (i.e., water decomposition): (5) 2H2O H2↑ + O2↑ Ε0 = - 1.23 V Note that the electrolysis reaction (5) has a thermodynamic potential of 1.23 V, and the negative sign of ΔE0 indicates that the reaction is not spontaneous. Therefore, a DC power supply of at least 1.23 V is required to initiate and sustain reaction (5), and as... Figure 1 As shown, the coin battery 6 supplies 3V DC.

[0047] Furthermore, if the amount of sodium chloride (NaCl) in saliva is relatively high, the following electrolysis reaction may occur instead of the reaction (5) discussed earlier: (6) 2NaCl + 2H2O Cl2↑ + H2↑ + 2NaOH In reaction (6), one of the products is sodium hydroxide (NaOH), which is another factor contributing to the high solution pH and potentially alkaline solution that can burn human tissue.

[0048] In short, Figure 1The conventional electrochemical coin cell 6 described in the figure, and the reactions (1) to (6) associated with its immersion in saliva 5, demonstrate the formation of hydroxide ions by some kind of repetitive electrolysis. Therefore, burns and injuries resulting from an accidentally lodged coin cell in the esophagus could be caused by the high salivary pH formed during these reactions, but these reactions and their corresponding effects on pH could be highly localized and difficult to detect if the pH is not measured near the components involved. In other words, due to the limitations of mass transport in the esophagus, a person with a lodged coin cell might experience different pH values ​​in the tissue interacting with the coin cell canister 20 (positive end) and the tissue interacting with the coin cell cup 12 (negative end), where the solution with a higher pH faces the negative end (i.e., due to the limitations of liquid diffusion within the esophagus). Figure 1 (Coin battery cup 12).

[0049] Where certain aspects and basic concepts of various embodiments of this disclosure involve saliva and / or saliva-based aqueous solutions, saliva may be represented by the following composition: 0.4 g KCl; 0.4 g NaCl; 0.906 g CaCl2; 0.560 g Na3PO4. - 12H2O; 2 ml 10% H3PO4; 0.0016 g Na2S; 1 g urea; and the remainder deionized water constitute a 1-liter solution. Although this formulation is intended to mimic human saliva in a standardized manner, minor variations and / or actual human saliva may be used as substitutes, although in such cases, deviations from the representative formulation will be appropriately noted.

[0050] Figure 2 and Figure 3 An arrangement of an electrochemical coin cell 10 well suited to the aspects and embodiments of this disclosure is depicted, although the coin cell 10 may employ various alternative component orientations and arrangements. Furthermore, the specific devices and processes shown in the figures and described herein are exemplary embodiments of the inventive concept defined in the appended claims. Therefore, the precise dimensions and physical properties associated with the embodiments disclosed herein should not be considered limiting unless such dimensions or properties are inherent to producing the desired reaction.

[0051] like Figure 2 and 3As shown, the electrochemical coin cell 10 also includes a cathode terminal 20 (i.e., a battery canister), which includes a closed end 21, an open end 22 having a terminal edge 23, and a sidewall 24 extending between the closed end 21 and the open end 22. The cathode terminal 20 serves as the positive electrode of the coin cell. Furthermore, the cathode terminal 20 comprises a metallic material such as titanium, titanium alloy, titanium nitride, tantalum, niobium, stainless steel, gold, boron-doped diamond, or another electronic conductor. The closed end 21 may also have a composition comprising titanium metal, titanium alloy, titanium nitride, tantalum, niobium, stainless steel, gold, boron-doped diamond, or another electronic conductor.

[0052] The coin cell 10 further includes a sealing gasket 30 provided between the anode terminal 12 and the cathode terminal 20. Figure 2 and 3 Gasket 30 is typically made of a non-conductive elastomeric material capable of providing a compression seal between anode terminal 12 and cathode terminal 20. The material used for gasket 30 must also be selected with reference to its stability in the presence of an electrolyte, its resilience, and its resistance to cold flow. Suitable materials for gasket 30 include: nylon, polytetrafluoroethylene, fluorinated ethylene-propylene, trichlorofluoroethylene, perfluoroalkoxy polymers, polyethylene, polyethylene, polypropylene, polystyrene, polysulfone, etc.

[0053] The electrochemical coin cell 10 also includes an electrolyte 34. As will be understood by those skilled in the art, various materials can be used for the electrolyte 34. For example, the electrolyte 34 may consist of a composition of at least one lithium salt dissolved in an organic solvent or a blend of organic solvents. Suitable salts for lithium coin cells are lithium trifluoromethanesulfonate, lithium trifluoromethanesulfonylimide, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, or combinations thereof. Common organic solvents for lithium coin cells are propylene carbonate and 1,2-dimethoxyethane.

[0054] The electrochemical cell 10 also has an anode 40 electrically connected to the anode terminal 12. As will be understood by those skilled in the art, the anode 40 can be composed of various alkali metals and their alloys with aluminum or magnesium, provided that the composition is suitable for serving as the anode in the electrochemical cell. In one embodiment, the anode 40 is primarily composed of lithium material, which is suitable as the anode in an electrochemical cell having a cathode primarily composed of manganese dioxide.

[0055] The electrochemical cell 10 also includes a cathode 50 arranged in electrical connection with the cathode terminal 20. As will be understood by those skilled in the art, the cathode 50 can be composed of various materials suitable for use as a cathode in a lithium-based electrochemical cell. In one embodiment, the cathode 50 is primarily composed of manganese dioxide.

[0056] The electrochemical coin cell 10 further includes a separator 38 disposed between the anode 40 and the cathode 50 to provide insulation between them. The separator 38 may be composed of any of a variety of polymeric materials, such as those providing electrical insulation between the anode terminal 12 and the cathode terminal 20. For example, the separator 38 may be formed of a polypropylene or polyethylene nonwoven film with a thickness between about 20 μm and about 60 μm.

[0057] Similarly, Figure 2 and 3 As shown, the electrochemical cell 10 can be configured as a button cell or coin cell configuration with a total cell outer diameter 54 and a total cell height 58. The size of the total cell outer diameter 54 can be between approximately 5 mm and approximately 25 mm, and the total cell height 58 can be between approximately 0.5 mm and approximately 10 mm. It is generally understood that button cells or coin cells with these dimensions are most likely to become lodged in the esophagus after accidental ingestion. For example, the electrochemical cell 10 can be manufactured in a configuration such as CR2016 as defined by the International Electrotechnical Commission (TEC), where the total cell outer diameter 54 has a diameter of approximately 20 mm and the total cell height 58 has a thickness of approximately 1.6 mm.

[0058] Another aspect of the disclosed method relates to a method of constructing and / or manufacturing a coin battery having the features described herein. This method includes providing a lithium-containing negative electrode active material, disposing of said material in separate halves of a conductive container, and providing a non-aqueous organic liquid electrolyte prior to hermetically sealing these halves of the conductive container to form a battery.

[0059] Another aspect of the disclosed method is providing and / or manufacturing batteries to avoid damage associated with ingestion of said batteries, and methods to avoid damage caused by battery ingestion. In these aspects, any of the aforementioned battery designs and constructions can be provided. At its core, the method of the invention relates to manufacturing and providing said batteries for sale and / or consumer use.

[0060] As used throughout this specification, duplex stainless steel is any duplex steel exhibiting both ferritic and austenitic crystal structures. Any reference to a particular grade should be considered as reference to standards published by ASTM International, unless the context indicates some other reference known to a person skilled in the art of metallurgy.

[0061] Dislike coating

[0062] This disclosure relates to an aversion coating for electrochemical batteries. The aversion coating is formed by applying a solution comprising an aversion agent composition and a binder (such as a water-soluble polymer) to a surface (e.g., the surface of a battery) and allowing the solution to dry. The aversion agent composition comprises at least one aversion agent, which may be an aversion taste agent such as a bitter agent, an aversion odor agent, or a salivating agent. An "aversion taste agent" is a substance with a bitter, sour, spicy, peppery, or other undesirable flavor to deter children from swallowing the battery. An "aversion odor agent" is an odorous substance with an undesirable odor, such as ammonia or sulfur. A "salivating agent" is a substance that induces saliva production upon contact with the mouth. The aversion agent composition may also contain a coloring agent to warn parents that a child has attempted to swallow the battery.

[0063] In some embodiments, the repulsive coating comprises 0.5% to 65% by weight of an repulsive agent composition and 5% to 98.5% by weight of a water-soluble polymer. In some embodiments, the repulsive coating comprises one or more additives with a balanced dry weight composition.

[0064] The aversive agent composition comprises at least one aversive taste agent. In some embodiments, the aversive taste agent is selected from: denatonium benzoate (DNB), capsaicin, allyl isothiocyanate, or piperine. In some embodiments, the aversive taste agent is DNB. In some embodiments, the dry weight composition of the aversive coating comprises 0.5% to 8.0% by weight of an aversive taste agent (e.g., DNB). In some embodiments, the dry weight composition of the aversive coating comprises about 5.0% to about 7.0% by weight of DNB. In some embodiments, the dry weight composition of the aversive coating comprises about 6.1% by weight of DNB.

[0065] The aversion coating described herein has an aversion taste agent to binder (e.g., a water-soluble polymer) ratio advantageous for coating electrochemical batteries. Formulations are provided that contain sufficient binder to allow the coating to adhere adequately to the battery and sufficient aversion taste agent to prevent children from swallowing the battery. In some embodiments, the ratio of the aversion taste agent (e.g., DNB) to the water-soluble polymer is between 0.015 and 1.0 for strong adhesion to the surface of the electrochemical battery. In some embodiments, a small amount of aversion taste agent is required to achieve sufficient repulsive properties. In some embodiments, the ratio of the aversion taste agent (e.g., DNB) to the water-soluble polymer is between 0.02 and 1.0, between 0.02 and 0.5, between 0.05 and 0.5, between 0.1 and 1.0, between 0.1 and 0.5, between 0.1 and 0.2, or between 0.14 and 0.16. In some embodiments, the ratio of the aversion taste agent (e.g., DNB) to the water-soluble polymer is approximately 0.15.

[0066] The water-soluble polymer contained in the repulsive coating acts as a binder to adhere the repulsive composition to the electrochemical cell. In some embodiments, the dry weight composition of the repulsive coating comprises 10% to 98.5% by weight, 15% to 95% by weight, 20% to 90% by weight, 30% to 80% by weight, 35% to 70% by weight, 35% to 60%, 35% to 50% by weight, or 35% to about 45% by weight of a water-soluble polymer. In some embodiments, the dry weight composition of the repulsive coating comprises about 41% by weight of a water-soluble polymer.

[0067] In some embodiments, the water-soluble polymer is selected from polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylamide, or polyethylene glycol (PEG). In some embodiments, the water-soluble polymer is PVA. In some embodiments, the water-soluble polymer has a molecular weight of about 10,000 to about 150,000, about 10,000 to about 100,000, about 50,000 to about 100,000, about 60,000 to about 90,000, about 70,000 to about 80,000, or about 75,000. In some embodiments, PVA has a molecular weight of about 10,000 to about 150,000, about 10,000 to about 100,000, about 50,000 to about 100,000, about 60,000 to about 100,000, about 60,000 to about 90,000, about 70,000 to about 100,000, about 70,000 to about 90,000, or about 70,000 to about 80,000. In some embodiments, PVA has a molecular weight of about 75,000. All molecular weights are described as average mass in grams per mole.

[0068] Polyvinyl alcohol (PVA) is prepared from polyvinyl acetate by hydrolyzing the ester functional groups to hydroxyl functional groups. The degree of hydrolysis of PVA can vary. For 80% hydrolyzed PVA, approximately 80% of the monomer units contain hydroxyl groups, and approximately 20% of the monomer units contain acetate. In some embodiments, the PVA is approximately 70% to 100% hydrolyzed, approximately 70% to approximately 99% hydrolyzed, approximately 80% to approximately 99% hydrolyzed, approximately 85% to approximately 95% hydrolyzed, approximately 80% to approximately 90% hydrolyzed, or approximately 85% to approximately 90% hydrolyzed. In some embodiments, the PVA is approximately 80% to approximately 95% hydrolyzed. In some embodiments, the PVA is approximately 88% hydrolyzed. In some embodiments, the PVA has a molecular weight of approximately 75,000 and is approximately 88% hydrolyzed.

[0069] In some embodiments, one or more additives of the repulsive coating comprise an adhesion promoter. In some embodiments, the dry weight composition of the repulsive coating comprises 0.1 wt% to about 5.0 wt% of an adhesion promoter. In some embodiments, the adhesion promoter is Lubrizol 2063, Lubrizol 2062, DowSil Z-6137, DowSil 3-6121, PP-6 (PP water from Marabin Environmental Conservation Printing Ink Co. Ltd), BYK-4509, or BYK-4510. In some embodiments, the adhesion promoter is Lubrizol 2063, a hydroxyl and carboxyl-functionalized phosphate ester. In some embodiments, the dry weight composition of the repulsive coating comprises 2.0 wt% to 5.0 wt% of Lubrizol 2063. In some embodiments, the dry weight composition of the repulsive coating comprises about 4.1 wt% of Lubrizol 2063.

[0070] In some embodiments, one or more additives of the repulsive coating comprise a surfactant. The surfactant reduces the surface tension of the solution and can act as a wetting and dispersing agent to assist in applying the repulsive coating to the electrochemical cell. In some embodiments, the dry weight composition of the repulsive coating comprises 0.01% to about 1.0% by weight of a surfactant. In some embodiments, the surfactant is an alkyl sulfate, alkyl ether sulfate, alkylbenzene sulfonate, polyoxyethylene ether, phosphate ester, or carboxylate. In some embodiments, the surfactant is sodium dodecyl sulfate (SDS), sodium lauryl ether sulfate (SLES), sodium stearate, Triton X-100, polysorbate 20 (Tween® 20), or sodium dioctyl sulfosuccinate (DOSS). In some embodiments, the surfactant is sodium dodecyl sulfate (SDS). In some embodiments, the dry weight composition of the repulsive coating comprises about 0.4% by weight of SDS.

[0071] In some embodiments, one or more additives to the repulsive coating include a viscosity modifier to aid in the dispensing of the solution containing the repulsive coating. In some embodiments, the dry weight composition of the repulsive coating includes 0.01% by weight to about 2.0% by weight of a viscosity modifier. In some embodiments, the viscosity modifier is a high molecular weight synthetic polymer of carbomer, acrylic acid, and allyl sucrose or allyl pentaerythritol, such as Carbopol® (e.g., Aqua SF-1, Aqua SF-3, Aqua CC, Silk 100, SC-800, 980 polymer, Ultrez 10, Ultrez 21) or Pemulen™ (e.g., TR-1, TR-2, EZ-4U). In some embodiments, the viscosity modifier is polyethylene glycol (PEG), which may have various molecular weights, such as PEG-400. In some embodiments, the viscosity modifier is a natural polysaccharide, such as xanthan gum, guar gum, or cellulose gum. In some embodiments, the viscosity modifier is a cellulose derivative, such as carboxymethyl cellulose (CMC) or hydroxyethyl cellulose (HEC). Examples of viscosity modifiers include, but are not limited to, Viscolam®, Esaflor®, Ammonyx®, Ninol®, and Amphosol® thickeners. In some embodiments, the viscosity modifier is carboxymethyl cellulose (CMC).

[0072] In some embodiments, the aversive composition further comprises a colorant. In some embodiments, the dry weight composition of the aversive coating comprises 0.5% to 60% by weight of a colorant. In some embodiments, the dry weight composition of the aversive coating comprises 5% to 55% by weight, 10% to 55% by weight, 20% to 55% by weight, 30% to 55% by weight, 40% to 55% by weight, or 45% to 55% by weight of a colorant. In some embodiments, the colorant comprises FD&C Blue No. 1 (Brilliant Blue FCF), FD&C Blue No. 2 (Indigo), FD&C Green No. 3 (Fixed Green FCF), FD&C Red No. 3 (Erythrosine), FD&C Red No. 40 (Allure Red AC), FD&C Yellow No. 5 (Tartrazine Yellow), or FD&C Yellow No. 6 (Sunset Yellow). The colorant may also comprise a natural organic dye, such as Veg Blue WS180 or Veg Bright Yellow CWD25, available from FoodRGB, Inc. In some embodiments, the dry weight composition of the repulsive coating contains approximately 45% to approximately 55% FD&C Blue No. 1. In some embodiments, the dry weight composition of the repulsive coating contains approximately 50% FD&C Blue No. 1.

[0073] In some embodiments, the aversion coating comprises a colorant, and the ratio of an aversion taste agent (e.g., DNB) to a water-soluble polymer is between about 0.10 and about 0.20. In one embodiment, the dry weight composition of the aversion coating comprises about 5.0 wt% to about 7.0 wt% DNB, about 35 wt% to about 45 wt% PVA, and about 45 wt% to about 55 wt% FD&C Blue No. 1. In another embodiment, the dry weight composition of the aversion coating comprises about 5.0 wt% to about 7.0 wt% DNB, about 35 wt% to about 45 wt% PVA, 45 wt% to about 55 wt% FD&C Blue No. 1, and about 2.0 wt% to about 5.0 wt% Lubrizol 2063. In one embodiment, the dry weight composition of the repulsive coating comprises approximately 5.0 wt% to approximately 7.0 wt% DNB, approximately 35 wt% to approximately 45 wt% PVA, 45 wt% to approximately 55 wt% FD&C Blue No. 1, and approximately 0.4 wt% SDS. In another embodiment, the dry weight composition of the repulsive coating comprises approximately 5.0 wt% to approximately 7.0 wt% DNB, approximately 35 wt% to approximately 45 wt% PVA, 45 wt% to approximately 55 wt% FD&C Blue No. 1, approximately 2.0 wt% to approximately 5.0 wt% Lubrizol 2063, and approximately 0.4 wt% SDS.

[0074] In one embodiment, the dry weight composition of the aversive coating comprises about 5.0 wt% to about 6.0 wt% DNB, about 40 wt% to about 50 wt% PVA, 40 wt% to about 50 wt% FD&C Blue No. 1 and about 1 wt% to about 2 wt% CMC.

[0075] In one embodiment, the dry weight composition of the aversive coating comprises about 1.0 wt% to about 6.0 wt% capsaicin, about 40 wt% to about 50 wt% PVA and 40 wt% to about 50 wt% FD&C Blue No. 1.

[0076] In one embodiment, the dry weight composition of the aversive coating comprises about 5.0 wt% to about 6.0 wt% DNB, about 40 wt% to about 50 wt% PVA, 40 wt% to about 50 wt% FD&C Blue No. 1 and about 1.0 wt% to about 5.0 wt% DowSil Z-6137.

[0077] In some embodiments, the aversion coating does not contain colorants, and the ratio of the aversion taste agent (e.g., DNB) to the water-soluble polymer is between about 0.15 and about 0.25. In one embodiment, the dry weight composition of the aversion coating comprises about 13% to about 20% DNB and about 75% to about 87% PVA. In one embodiment, the dry weight composition of the aversion coating comprises about 13% to about 20% DNB, about 75% to about 87% PVA, and about 2.0% to about 3.0% Lubrizol 2063. In one embodiment, the dry weight composition of the aversion coating comprises about 13% to about 20% DNB, about 75% to about 87% PVA, and about 0.1% to about 0.5% SDS.

[0078] In one embodiment, the dry weight composition of the repulsive coating comprises about 2.0 wt% to about 6.0 wt% DNB, about 70 wt% to about 80 wt% polyacrylic acid (PAA), and about 5 wt% to about 28 wt% FD&C Blue No. 1. In another embodiment, the dry weight composition of the repulsive coating comprises about 2.0 wt% to about 6.0 wt% DNB, about 70 wt% to about 80 wt% polyacrylic acid (PAA), about 5 wt% to about 28 wt% FD&C Blue No. 1, and about 1 wt% to about 2 wt% CMC.

[0079] Electrochemical batteries

[0080] This disclosure relates to an electrochemical cell coated with the aversion coating described herein. The electrochemical cell includes a positive terminal defining a first portion of the cell's exterior; a negative terminal electrically insulated from the positive terminal and defining a second portion of the cell's exterior; an anode disposed inside the cell and electrically connected to the negative terminal; and a cathode disposed inside the cell, wherein the cathode is electrically isolated from the anode and electrically connected to the positive terminal. At least a portion of the outer surface of the electrochemical cell is coated with the aversion coating provided herein.

[0081] In some embodiments, the electrochemical battery is a button cell or a coin cell. In some embodiments, the electrochemical battery is a lithium coin cell. Lithium coin cells include, but are not limited to, CR1025, CR1216, CR1616, CR1620, CR1632, CR2016, CR2025, CR2032, CR2430, and CR2450 batteries. Coin cells typically have diameters of 10 mm, 12.5 mm, 16 mm, 20 mm, and 24 mm, which respectively provide approximately 79 mm².2 123 mm 2 201 mm 2 314 mm 2 and 452 mm 2 Terminal area.

[0082] In some implementations, positive and / or negative terminals with an area percentage greater than 2%, greater than 3%, greater than 4%, greater than 5%, greater than 10%, greater than 20%, greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80%, or greater than 90% are coated with an aversive coating.

[0083] Figure 5 An example of a coin cell showing an aversion coating applied to a portion of the outer surface of the negative terminal is illustrated. In the illustrated example, the aversion coating is applied in the form of a series of points 70 that collectively cover a portion of the negative terminal. The series of points is provided to form an arc on the surface of the cell. However, it should be understood that other patterns, such as stripes, rings, ovals, squares, rectangles, and rhombuses, can be used. To prevent or reduce interference with cell performance, the aversion coating may be located within approximately 14.0 mm of the diameter and outside approximately 8.2 mm of the diameter from the center of the coin cell terminal. In some embodiments, the aversion coating is not located on the sidewall 24 of the gasket 30.

[0084] In some implementations, more than 50% of the area of ​​the outer surface of the positive terminal is coated with an anti-repellent coating. The outer surface 25 of the positive terminal 20 is... Figure 2 and Figure 3 As shown in the image.

[0085] In some embodiments, more than 50% of the area of ​​the outer surface of the negative terminal is coated with an anti-repellent coating. The outer surface 17 of the negative terminal 12 is... Figure 2 and Figure 3 As shown in the image.

[0086] In some embodiments, the sidewalls of the gasket are not coated with an anti-repellent coating. The sidewalls 24 of the gasket 30 are... Figure 2 and Figure 3 As shown in the image.

[0087] In some embodiments, the total dry weight of the repulsive coating applied to the electrochemical cell is from about 0.1 mg to about 1.2 mg. In some embodiments, the total dry weight of the repulsive coating applied to the electrochemical cell is from about 0.2 mg to about 0.5 mg. In some embodiments, the total dry weight of the repulsive coating applied to the electrochemical cell is about 0.4 mg.

[0088] For sufficient aversive properties, at least 1 µg of the aversive taste agent is applied to each electrochemical cell. In some embodiments, the total amount of the aversive taste agent applied to the electrochemical cell is between 1 µg and 120 µg, between 1 µg and 50 µg, between 4 µg and 120 µg, between 5 µg and 100 µg, between 5 µg and 50 µg, between 5 µg and 40 µg, between 5 µg and 30 µg, between 10 µg and 50 µg, between 10 µg and 40 µg, between 10 µg and 30 µg, between 10 µg and 25 µg, between 20 µg and 40 µg, or between 20 µg and 30 µg. In some embodiments, the total amount of the aversive taste agent applied to the electrochemical cell is approximately 25 µg.

[0089] In some implementations, electrochemical batteries are packaged in child-proof packaging for sale. Figure 6 The illustrated implementation shows two batteries 610 housed within a child-proof package 600; however, it should be understood that in other exemplary embodiments, one or more batteries may be packaged within a single child-proof package. As shown, the child-proof package may specifically be a blister pack having a flat cardboard backing 601 and a thermoformed plastic layer 602 adhered to the surface of the flat cardboard backing 601. In the illustrated embodiment, the thermoformed plastic layer 602 includes a battery storage portion 603 shaped to hold the one or more batteries packaged within the package. The battery storage portion 603 has an open end and defines a recess sized such that the one or more batteries fit completely within the battery storage portion 603, allowing the flat cardboard backing 601 to be secured across the open end of the recess. Furthermore, the plastic layer 602 additionally includes a reinforcing ridge surrounding the battery storage portion 603. The reinforcing ridge 604 is hollow and extends in the same direction as the battery storage portion 603. The reinforced spine 604 provides additional rigidity to the child-proof package 600 to prevent children from bending the child-proof package 600 to release the battery stored inside.

[0090] The plastic layer 602 may comprise any of a variety of thermoplastics. For example, the plastic layer may be polyvinyl chloride (PVC), although other plastic materials may also be used. The plastic layer may be thick enough to prevent children from tearing it. For example, the plastic layer may have a thickness greater than 3 mils (e.g., between 3 and 7 mils).

[0091] As described above, the plastic layer 602 can be adhered to the flat cardboard backing 601 using an adhesive. For example, the adhesive can be a polyurethane-based adhesive, but other adhesives can also be used. More than 50% of the area of ​​the flat cardboard backing 601 can be adhered to the planar portion of the plastic layer 602. A higher percentage of the flat cardboard backing 601 adhered to the plastic layer 602 increases the difficulty for a child to remove the flat cardboard backing 601 from the plastic layer 602 and thus release the battery. Therefore, in some embodiments, more than 60%, more than 70%, more than 80%, or more than 90% of the flat cardboard backing 601 by area can be adhered to the plastic material 602.

[0092] In addition, such as Figure 6 As shown, the plastic layer 602 is sized to cover the entire area of ​​the flat cardboard backing 601. In this way, a child cannot bend the flat cardboard backing 601 to delaminate from the surface of the flat cardboard backing 601 or otherwise release the plastic layer 602.

[0093] Method for preparing electrochemical cells with aversion coating

[0094] A method for manufacturing an electrochemical cell coated with an irritant coating is described. The electrochemical cell disclosed herein can be manufactured according to any method known in the art. The method includes preparing a coating solution by dissolving an irritant composition and a water-soluble polymer in one or more solvents, applying the coating solution to at least a portion of the outer surface of the electrochemical cell, and drying the solution onto said portion of the outer surface of the electrochemical cell.

[0095] The coating solution comprises 0.2% to 20% by weight of an aversive agent composition dissolved in one or more solvents and 0.2% to 14% by weight of a water-soluble polymer. The water-soluble polymer and the aversive taste agent are dissolved in the solvent to provide a coating solution having a final concentration of 0.2% to 14% by weight of the water-soluble polymer and 0.2% to 2% by weight of the aversive taste agent. In some embodiments, the coating solution further comprises 0.01% to 3.0% by weight of an adhesion promoter. In some embodiments, the coating solution further comprises 0.2% to 18% by weight of a colorant. In some embodiments, the coating solution further comprises 0.01% to 0.3% by weight of a surfactant. In some embodiments, the coating solution further comprises 0.01% to 2.0% by weight of a viscosity modifier.

[0096] In some embodiments, the coating solution is prepared by dissolving approximately 10 wt% PVA, approximately 1.5 wt% DNB, and approximately 12 wt% FD&C Blue No. 1 in one or more solvents. In some embodiments, the coating solution is prepared by dissolving approximately 10 wt% PVA, approximately 1.5 wt% DNB, approximately 12 wt% FD&C Blue No. 1, and approximately 1 wt% Lubrizol 2063 in one or more solvents. In some embodiments, the coating solution is prepared by dissolving approximately 10 wt% PVA, approximately 1.5 wt% DNB, approximately 12 wt% FD&C Blue No. 1, approximately 1 wt% Lubrizol 2063, and approximately 0.1 wt% SDS in one or more solvents.

[0097] The water-soluble polymer can be heated to a suitable temperature for a period of time to completely dissolve in the coating solution. In some embodiments, the water-soluble polymer is PVA, and the PVA is heated to about 95°C for about 60 minutes to dissolve. In some embodiments, a solution of dissolved adhesion promoter (e.g., Lubrizol 2063) is added to the coating solution containing the dissolved water-soluble polymer. In some embodiments, the coating solution, heated to dissolve the water-soluble polymer, is cooled before the addition of an aversive composition containing an aversive taste agent and optionally a colorant.

[0098] like Figure 4 As shown, a method for manufacturing coated electrochemical cells on an assembly line may include introducing an electrochemical cell 100 into a tray after manufacturing, performing a pretreatment process 200, applying a coating solution 300, drying the coating 400 on the electrochemical cell, and removing the tray 500 for packaging.

[0099] The outer surface of the electrochemical cell can be cleaned after manufacturing, as part of pretreatment process 200, and before the application of coating solution 300. Removing grease or residues from the manufacturing process can promote adhesion of the coating solution to the electrochemical cell. In some embodiments, the electrochemical cell is sprayed with deionized water for a period of time (e.g., 5 to 10 seconds) before the coating solution is applied. In some embodiments, the electrochemical cell is rinsed at a temperature above room temperature (e.g., 27°C to 35°C). The electrochemical cell can be dried before the coating solution is applied. In some embodiments, the electrochemical cell is dried with hot air for a period of time (e.g., 1 to 5 seconds) after rinsing. In some embodiments, the electrochemical cell is dried with air at a temperature of approximately 25°C.

[0100] An aversive coating can be applied to an electrochemical cell using any method known in the art. In some embodiments, the coating solution is applied by immersion, spraying, printing, or dispensing onto the electrochemical cell. In some embodiments, a spray dispenser is used to apply the coating solution (e.g., dotting). Methods such as pad printing or screen printing can also be used to apply the coating solution. In embodiments where only a portion of the positive or negative terminals is coated with the aversive coating, a mask can be used to selectively apply the aversive coating to the desired portion of the electrochemical cell. The mask is a solid, non-absorbent material with holes or gaps having the desired pattern and is placed between the electrochemical cell and the device for dispensing the coating solution to allow the coating solution to deposit on specific portions of the electrochemical cell. The mask can be removed after the aversive coating has dried.

[0101] Example

[0102] As discussed herein, bittering agents, coloring agents, salivating agents, and / or other aversive agents can be added to at least a portion of the exterior of a coin cell. Aversive agents can include substances that cause a strong, unpleasant taste or odor, such as pungent, peppery, sour, bitter, or foul. Examples include capsaicin, allyl isothiocyanate, and piperine. For example, one or more aversive taste agents can be incorporated into a coating adhered to the outer surface of the battery. In one embodiment, a water-soluble polymer such as polyvinyl alcohol (PVA) is added to an aqueous aversive agent solution to encapsulate the aversive agent within a PVA network and apply it to the battery surface. As the water in the aversive agent solution evaporates, the polymer acts as a binder, adhering the aversive agent (and other active materials, such as coloring agents and / or salivating agents) to the battery surface. However, the coating remains soluble in water (or an aqueous solution, such as saliva) so that when a person (e.g., a child) puts the battery in their mouth, the aversive agent is released from the battery surface. The unpleasant taste of the aversive agent may cause a person to spit out the battery rather than swallow it.

[0103] In some embodiments, the PVA coating (or other polymer adhesive) is thin enough to enable electron tunneling. Therefore, the resulting coating does not affect the normal function of the battery. However, in embodiments where the PVC coating is provided on a portion of the battery not aligned with the center portion of the battery terminals, the coating can be thicker so that electron tunneling is not required.

[0104] For water-soluble polymers, such as, but not limited to, PVA and polyacrylic acid (PAA), the upper limit of the amount of polymer used (e.g., the resulting thickness of the polymer coating) is the amount of polymer that keeps the battery exterior conductive. The lower limit of the amount of polymer used is the amount of polymer that sufficiently binds the averse agent (e.g., denaphalonamine benzylbenzene (DNB), but may incorporate other colorants or catalytic agents). When applied in a wet formulation, PVA ranges from about 0.2% to 14%. The dry recombination of the averse coating yields about 5% to 98.5% PVA. The polymer can be a low molecular weight polymer (1-10 Ks), a medium molecular weight polymer (10-100 Ks), or a high molecular weight polymer (>100 Ks). Low molecular weight polymers have high water solubility, and the shorter chains provide less chain entanglement and higher molecular mobility. However, low molecular weight polymers tend to form beads rather than fibers in solution and provide a weaker material. High molecular weight polymers have low water solubility but exhibit a higher degree of chain entanglement and form films with high tensile strength. Higher molecular weight polymers tend to form tougher and more chemically resistant materials. Additionally, the viscosity of solutions containing polymers increases with molecular weight. Medium molecular weight polymers exhibit moderate water solubility, strength, and viscosity. Appropriately sized polymers can be selected in conjunction with additives such as adhesion promoters, surfactants, and viscosity modifiers to form a highly adhesive coating that adheres well to the surface of the electrochemical cell.

[0105] The amount of aversive taste agent can be selected to provide an unpleasant battery taste. For example, the amount of DNB can be selected between 1 and 120 µg (e.g., between 5 and 30 µg) for each coin cell battery.

[0106] The coating can be applied using any of a variety of different coating methods, such as providing small droplets of material (e.g., via a pipette). Other application methods include immersion rinsing of the battery, spray coating, pad printing onto the battery, screen printing onto the battery, needle dispensing onto the battery, and / or similar methods. Any method can be used as long as it uniformly deposits a thin layer.

[0107] In some embodiments, additional additives may be provided to further enhance the desired properties of the resulting coating. For example, surfactants may be added to the solution to improve the wettability of the coating. In some embodiments, the battery surface may also be treated by plasma sonication or other means to increase the surface energy for better coating acceptance.

[0108] When coating terminals (e.g., negative terminals), a portion of the terminal can be masked (e.g., the outermost 1-2 mm to prevent short circuits when wetted with the solution) so that the masked portion is not coated by the coating material. The coating material can then be sprayed onto the terminal, and the mask can be removed after the coating dries.

[0109] The coating solution itself may have the following components: solvent (including, for example, water, isopropanol, ethanol, mixtures thereof, and / or other organic solvent materials); DNB (or other anaerobic agents); optional additives (e.g., surfactants, adhesion promoters, etc.); optional low-concentration polymer binders (e.g., PVA, PAA, polyethylene glycol, polyacrylamide, and / or the like); and optional viscosity modifiers (e.g., carboxymethyl cellulose (CMC)) for better processability. The coating can be applied by spraying.

[0110] The polymer binder may be provided in the coating solution in an amount between about 0.00001% by weight and 14% by weight. In some embodiments, the colorant may be provided in the coating solution in an amount between about 0.01% by weight and 18% by weight. The viscosity improver (e.g., a thickener) may be provided in the solution in an amount between about 0% by weight and 2% by weight.

[0111] Before coating, the battery can be cleaned for a total of 8 seconds at 30°C using, for example, deionized water (e.g., recycled deionized water with a conductivity σ < 10 μS / cm). Hot air drying can then begin 0.5 seconds after rinsing. Hot air drying lasts for approximately 3 seconds at an air temperature of 25°C.

[0112] The coating can be sprayed onto a clean battery surface approximately one second after air drying is complete. The battery can then be dried (e.g., by hot air) to allow the coating to adhere to it. A mask (e.g., a solid, non-absorbent material with gaps of the desired shape) can be placed on the electrochemical battery to selectively apply the aversive coating solution to specific areas of the terminals. If a portion of the battery is masked, the mask can be removed after the coating has dried.

[0113] By spraying a coating material onto specific portions of a battery, the battery's conductivity can be maintained even if the coating's thickness impedes the transfer of electrons through it. In other words, if the coating is applied to battery portions where conductivity is not critical, the coating does not need to be thin enough to maintain conductivity. When a thick coating is provided on portions of the battery, the total loading of anaerobic agents (such as bittering agents) on the battery can be increased while preserving other uncoated portions of the battery.

[0114] As an example, the coating may be provided on the positive and / or negative terminals of the battery. The coating may be provided on a portion of the positive and / or negative terminals, leaving the remainder of the terminals exposed. As a non-limiting example, the coating may be provided on the positive and / or negative terminals in a centrally located annular configuration, wherein the center of the annulus is uncoated. As another example, one or more strips of coating material may be provided on the positive and / or negative terminals, wherein the strips (e.g., linear or non-linear strips) are eccentrically positioned relative to the positive and / or negative terminals (i.e., such that the center of the terminal remains uncoated).

[0115] An exemplary ratio of polymer binder to active material in the coating

[0116] This article discusses exemplary ratios between the levels of aversive agents and adhesives in coatings used to adhere aversive agents to battery surfaces. Coatings conforming to the ratios discussed herein ensure that the aversive agents remain adhered to the surface of the small battery during manufacturing, shipping, sales, and use. Each exemplary composition discussed above provides the adhesion benefits as described herein. This adhesion should remain strong during aging and exposure to humidity, friction, or other use or environmental factors. Existing adhesives used to adhere bittering agents to battery surfaces provide poor adhesion properties, and bittering agents or other aversive agents may be unintentionally removed from the battery during manufacturing or shipping before it reaches the end consumer.

[0117] Utilizing an aversive taster to binder ratio, as discussed herein, ensures proper release of the aversive agent (e.g., upon dissolution in saliva) while maintaining adequate "toughness" against accidental release during exposure to mechanical / physical forces (e.g., scratching, abrasion, physical pressure, etc.). In formulations using a lower aversive taster / binder ratio, a larger amount of aversive coating is required to achieve sufficient anti-feeding properties. A higher amount of binder can result in a thicker coating, which may interfere with battery performance. A sufficiently high aversive taster / binder ratio allows for a smaller total coating mass per battery, providing a thinner and / or smaller area of ​​coating to limit interference with conductivity. However, an excessively high aversive taster to binder ratio can lead to poor adhesion to the battery.

[0118] Some embodiments involve coatings with an aversive taste agent to binder ratio equal to or greater than 0.02, wherein the aversive agent does not include a colorant (note that colorants increase the viscosity of the coating). A coating (without colorant) having an aversive taste agent / binder ratio between approximately 0.25 and 0.5 can have a sufficiently low viscosity to provide a thin coating on the surface of the battery, with a coating thickness thin enough to maintain the conductivity of the battery through the coating (e.g., the coating can be thin enough to achieve an electron tunneling effect through the coating), while also retaining sufficient amount of aversive agent (e.g., bittering agent) to prevent children from swallowing the battery after placing it in their mouths.

[0119] It has been found that coatings (without colorants) having an aversive taste agent to binder ratio of approximately 0.015–0.1 (e.g., approximately 0.05–0.085, or more specifically, approximately 0.05–0.075) provide sufficient levels of aversive agent to prevent children from swallowing the battery while also providing adequate adhesion to the battery surface. However, to maintain the desired amount of aversive agent on the battery surface, coatings with an aversive agent to polymer ratio of approximately 0.02–0.2 can be provided in battery areas that do not substantially interfere with conductivity. For example, these coatings can be applied to portions of the outer surface of the battery while leaving at least a portion of the positive and negative terminals of the battery exposed for conductivity.

[0120] In embodiments where the aversive composition includes colorants and aversive taste agents, a higher functional additive / binder ratio still provides sufficient adhesion to the battery surface, sufficient aversive properties, and rapid staining of human tissues (e.g., lips, tongue, etc.) to indicate possible ingestion. For example, coatings with an aversive composition to binder ratio of 0.1-1.0 provide strong adhesion to the battery surface, sufficient aversive properties (to deter children from swallowing), and sufficiently rapid and intense color staining of the mouth, hands, and other surfaces moistened with bodily fluids such as saliva. Specifically, coatings with an aversive composition to binder ratio of 0.35 (in which the aversive composition includes colorants and aversive taste agents) provide strong adhesion to the battery. Other tested coatings with a functional additive (including colorants) to binder ratio of 1.0 maintained sufficient adhesion to the battery surface.

[0121] in conclusion

[0122] Benefiting from the teachings given in the foregoing description and accompanying drawings, those skilled in the art will conceive of numerous modifications and other embodiments of the embodiments set forth herein. Therefore, it is to be understood that this disclosure is not limited to the specific embodiments disclosed, and that modifications and other embodiments are intended to be included within the scope of the appended claims. Furthermore, although exemplary embodiments have been described in the foregoing description and accompanying drawings with respect to certain exemplary combinations of elements and / or functions, it should be recognized that different combinations of elements and / or functions can be provided by alternative embodiments without departing from the scope of the appended claims. In this regard, combinations of elements and / or functions different from those explicitly described above are also contemplated, for example, as may be set forth in some of the appended claims. Although specific terms are used herein, they are used only in a general and descriptive sense and not for limiting purposes.

[0123] Unless otherwise stated, all numerical values ​​used in the specification and claims to indicate amounts of components, reaction conditions, etc., should be understood to be modified by the term "about" in all cases. Therefore, unless indicated to the contrary, the numerical parameters given in this specification and the appended claims are approximate values ​​that may vary depending on the desired properties sought to be obtained through this application. Generally, when referring to quantities of measurable values ​​such as weight, time, dosage, etc., the term "about," as used herein, is intended to cover deviations of the specified quantity, such deviations as in one instance are ±20%, in another ±10%, in yet another ±5%, in another ±1%, and in yet another ±0.1%, because such variations are suitable for carrying out the disclosed methods.

[0124] All instances and / or embodiments are to be considered non-limiting throughout this disclosure. Furthermore, no inferences should be drawn about embodiments discussed herein in relation to those not discussed herein, except for purposes of reducing space and redundancy. For example, it is to be understood that the logical and / or topology of any combination of data flow sequences, program components (sets of components), other components, and / or any current feature set as described in the figures and / or throughout are not limited to a fixed order of operation and / or arrangement, but any disclosed order is exemplary, and this disclosure considers all equivalents, regardless of order. Furthermore, it is to be understood that these features and steps are not limited to sequential execution, but can be executed asynchronously, concurrently, in parallel, simultaneously, synchronously, etc., as contemplated by this disclosure. Therefore, some of these features may contradict each other, as they cannot coexist in a single embodiment. Similarly, some features apply to one aspect of the innovation but not others. Moreover, this disclosure includes other innovations that are disclosed and may not be explicitly described. Therefore, it should be understood that the advantages, embodiments, examples, functions, features, logic, operation, organization, structure, topology and / or other aspects of this disclosure should not be considered as limitations on this disclosure as defined by the embodiments, examples, and claims, or limitations on equivalents of the embodiments, examples and / or claims. It is to be understood that various embodiments or parts thereof of the coin battery described herein can be implemented according to the specific needs and / or characteristics of the electrochemical battery, such as a coin cell, etc., achieving great flexibility and customization.

Claims

1. An aversive coating for use in electrochemical cells, the dry weight composition of the aversive coating comprising: - 0.5% to 65% by weight of an aversive agent composition; and - 5% to 98.5% by weight of water-soluble polymers.

2. The aversive coating according to claim 1, wherein the aversive agent composition comprises at least one aversive taste agent selected from: denatonium benzoate (DNB), capsaicin, allyl isothiocyanate, or piperine.

3. The aversive coating according to claim 2, wherein the aversive taste agent is DNB.

4. The aversive coating according to claim 2, wherein the ratio of the aversive taste agent to the water-soluble polymer is between 0.015 and 1.

0.

5. The aversive coating according to claim 4, wherein the ratio of the aversive taste agent to the water-soluble polymer is approximately 0.

15.

6. The aversive coating according to claim 1, wherein the water-soluble polymer is selected from: polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylamide, or polyethylene glycol (PEG).

7. The aversive coating according to claim 6, wherein the water-soluble polymer is PVA.

8. The aversive coating of claim 7, wherein the PVA has a molecular weight of about 10,000 to about 150,000.

9. The aversive coating of claim 7, wherein the PVA is approximately 80% to approximately 95% hydrolyzed.

10. The aversive coating of claim 7, wherein the PVA has a molecular weight of about 75,000 and is about 88% hydrolyzed.

11. The aversive coating of claim 1, wherein the aversive coating further comprises 0.1% to 5.0% by weight of an adhesion promoter.

12. The aversive coating according to claim 11, wherein the adhesion promoter is Lubrizol 2063, Lubrizol 2062, DowSil Z-6137, DowSil 3-6121 or PP-6.

13. The aversive coating of claim 12, wherein the aversive coating further comprises 2.0 wt% to 5.0 wt% of Lubrizol 2063.

14. The aversive coating of claim 1, wherein the aversive coating further comprises 0.01% to 1.0% by weight of a surfactant.

15. The aversive coating of claim 14, wherein the surfactant is sodium dodecyl sulfate (SDS).

16. The aversive coating of claim 1, wherein the aversive coating further comprises 0.01% to 2.0% by weight of a viscosity improver.

17. The aversive coating of claim 16, wherein the viscosity improver is carboxymethyl cellulose (CMC).

18. The aversive coating of claim 1, wherein the aversive agent composition comprises a colorant, and the aversive coating comprises 0.5% to 60% by weight of the colorant.

19. The odor-causing coating of claim 18, wherein the colorant comprises: FD&C Blue No. 1, FD&C Blue No. 2, FD&C Green No. 3, FD&C Red No. 3, FD&C Red No. 40, FD&C Yellow No. 5, or FD&C Yellow No.

6.

20. The aversive coating of claim 19, wherein the colorant comprises FD&C Blue No.

1.

21. An aversive coating, comprising, by dry weight: Approximately 5.0% to approximately 7.0% by weight of DNB; Approximately 35% to approximately 45% PVA; and Approximately 45% to 55% by weight FD&C Blue No.

1.

22. The aversive coating of claim 21, wherein the aversive coating further comprises about 2.0 wt% to about 5.0 wt% Lubrizol 2063.

23. The aversive coating of claim 21, wherein the aversive coating further comprises approximately 0.4% by weight SDS.

24. An electrochemical battery comprising: The positive terminal of the first portion defining the exterior of the electrochemical cell; A negative terminal that is electrically insulated from the positive terminal and defines the exterior of the electrochemical cell; The anode is disposed inside the electrochemical cell and electrically connected to the negative terminal. and A cathode disposed inside the electrochemical cell, wherein the cathode is electrically isolated from the anode and electrically connected to the positive terminal. At least a portion of the outer surface of the electrochemical cell is coated with an aversive coating, wherein the dry weight composition of the aversive coating comprises: 0.5% to 65% by weight of an aversive agent composition; and 5% to 98.5% by weight of water-soluble polymers.

25. The electrochemical battery according to claim 24, wherein the electrochemical battery is a button cell or a coin cell.

26. The electrochemical cell of claim 24, wherein more than 50% of the area of ​​the outer surface of the positive terminal is coated with the aversive coating.

27. The electrochemical cell of claim 24, wherein more than 50% of the area of ​​the outer surface of the negative terminal is coated with the aversive coating.

28. The electrochemical cell of claim 24, wherein the total dry weight of the aversive coating applied to the electrochemical cell is from about 0.1 mg to about 1.2 mg.

29. The electrochemical cell of claim 24, wherein the total amount of the aversive coating applied to the electrochemical cell comprises about 25 µg of aversive taste agent.

30. The electrochemical battery of claim 24, wherein the electrochemical battery is packaged in child-proof packaging.

31. A method for preparing the electrochemical cell according to claim 24, the method comprising: A coating solution is prepared by dissolving an aversive agent composition and a water-soluble polymer in one or more solvents, wherein the coating solution comprises 0.2% to 20% by weight of the aversive agent composition and 0.2% to 14% by weight of the water-soluble polymer; The coating solution is applied to at least a portion of the outer surface of the electrochemical cell; and The solution is dried onto the portion of the outer surface of the electrochemical cell.

32. The method of claim 31, wherein the aversive composition comprises at least one aversive taste agent selected from: denatonium benzoate (DNB), capsaicin, allyl isothiocyanate, or piperine, and The preparation of the coating solution includes dissolving 0.2% to 2.0% by weight of the aversive taste agent in one or more solvents.

33. The method of claim 31, wherein preparing the coating solution further comprises dissolving 0.01% to 3.0% by weight of an adhesion promoter in one or more solvents.

34. The method of claim 33, wherein the water-soluble polymer is PVA and the adhesion promoter is Lubrizol 2063, and the preparation of the coating solution comprises heating the PVA in water to about 95°C for about 60 minutes to dissolve it before adding the solution containing dissolved Lubrizol 2063.

35. The method of claim 34, wherein preparing the coating solution further comprises cooling the solution containing dissolved PVA prior to adding the aversive composition.

36. The method of claim 31, wherein the aversive composition comprises a colorant, and The preparation of the coating solution further includes dissolving 0.2% to 18% by weight of the colorant in one or more solvents.

37. The method of claim 31, wherein preparing the coating solution further comprises dissolving 0.01% to 0.3% by weight of a surfactant in one or more solvents.

38. The method of claim 31, wherein preparing the coating solution further comprises dissolving 0.01% to 2.0% by weight of a viscosity modifier in one or more solvents.

39. The method of claim 31, wherein preparing the coating solution comprises dissolving approximately 10 wt% PVA, approximately 1.5 wt% DNB and approximately 12 wt% FD&C Blue No. 1 in one or more solvents.

40. The method of claim 39, wherein preparing the coating solution further comprises dissolving approximately 1.0 wt% Lubrizol 2063 in one or more solvents.

41. The method of claim 40, wherein preparing the coating solution further comprises dissolving approximately 0.1% by weight of SDS in one or more solvents.

42. The method of claim 31, wherein the application includes impregnating, spraying, printing or dispensing the coating solution onto the electrochemical cell.

43. The method of claim 31, wherein the method further comprises masking one or more portions of the electrochemical cell prior to applying the coating solution.

44. The method of claim 31, wherein the method further comprises cleaning the outer surface of the electrochemical cell prior to applying the coating solution.

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