Rechargeable battery with internal current limiter and internal current interrupter

Abstract

To provide a high energy density rechargeable (HEDR) battery capable of preventing the thermal runaway in the event of internal discharge or other disruption of a separator.SOLUTION: An improved high energy density rechargeable battery comprises: a first electrode; a first current collector for transferring electrons; a current interrupter 8 interposed between the first electrode and the first current collector, where the current interrupter 8 comprises a heat sensitive material configured to generate a gas upon activation by at least a temperature trigger, where the generation of the gas forms a nonconductive gap between the first electrode and the first current collector, and where the formation of the nonconductive gap electrically decouples the first electrode from the first current collector; a second electrode having a polarity opposite to that of the first electrode; and a separator 2 interposed between the first electrode and the second electrode. Preferably, the battery further comprises a current limiter.SELECTED DRAWING: Figure 6D

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority not only to U.S. Patent Application No. 14 / 714,160, filed on 15 May 2015, titled “Rechargeable Battery with Internal Current Limiter and Internal Current Interrupter,” but also to the following five provisional applications: U.S. Provisional Application No. 62 / 084,454, filed on 25 November 2014, titled “Battery Safety Device”; and U.S. Provisional Application No. 9, filed on 9 February 2015, titled “Rechargeable Battery with Resistive Layer for Enhanced Safety.” U.S. Provisional Application No. 62 / 114,001; U.S. Provisional Application No. 62 / 114,006, filed on 9 February 2015, titled “Rechargeable Battery with Temperature-Activated Current Interrupter”; U.S. Provisional Application No. 62 / 114,007, filed on 9 February 2015, titled “Voltage-Current Interrupter”; and U.S. Provisional Application No. 62 / 114,508, filed on 10 February 2015, titled “Rechargeable Battery with Internal Current Limiter and Internal Current Interrupter”. All disclosures thereof are incorporated herein by attribution.

[0002] This disclosure relates to an internal current limiter or internal current interrupter used to protect a battery from thermal runaway caused by an internal short circuit or overcharge. In particular, it relates to a safer high-energy-density rechargeable (HEDR) battery. [Background technology]

[0003] There is a need for highly reliable rechargeable battery systems that possess high energy density and are therefore capable of storing and supplying large amounts of electrical energy per unit volume and / or unit weight. Such stable, high-energy battery systems have significant utility in many applications, including military equipment, communication equipment, and robotics.

[0004] A commonly used example of a high-energy-density rechargeable (HEDR) battery is the lithium-ion battery. [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Lithium-ion batteries are rechargeable batteries in which lithium ions move from the negative electrode to the positive electrode during discharge and in the reverse direction during charging. Lithium-ion batteries are dangerous under certain conditions and pose safety problems. The fire energy content (electrical + chemical) of lithium cobalt oxide batteries is approximately 100-150 kJ per ampere-hour, most of which is chemical. Overcharging or overheating can cause lithium-ion batteries to experience thermal runaway and cell rupture. In extreme cases, this can lead to combustion. Also, if the battery is short-circuited externally or internally, it can overheat and ignite.

[0006] overcharging In lithium-ion batteries, useful work is performed when electrons flow through a closed external circuit. However, to maintain charge neutrality, for each electron flowing through the external circuit, there must be a corresponding lithium ion that moves from one electrode to the other. The electrical potential that facilitates this movement is obtained by oxidizing a transition metal. For example, cobalt (Co) is used during charging. 3+ From Co 4+ It changes to Co during discharge. 4+ From Co 3+ It is reduced to Li. Conventionally, Li 1-x CoO2 is used, where the coefficient x is the lithium ion and the oxidation state of CoO2, i.e., Co 3+ or Co 4+ This represents the mole fractions of both and . Using these conventions, the positive electrode half-reaction of a lithium-cobalt battery can be expressed as follows: The negative electrode half-reaction in TIFF0007888685000001.tif7150 is expressed as follows: The cobalt electrode reaction is reversible if limited to x < 0.5 and restricted to an acceptable depth of discharge due to cycle life issues and the stability of LiCoO2. Overcharging leads to the formation of cobalt(IV) oxide as follows: LiCoO2 decomposes into CoO2, releasing a large amount of heat and oxygen. The released oxygen oxidizes the electrolyte, leading to thermal runaway. This process is irreversible. Therefore, a device or structure is needed that can decompose the cell before or after the actual decomposition. This device could protect the cell from thermal expansion.

[0007] thermal runaway When the heat generated by a lithium-ion battery exceeds its heat dissipation capacity, the battery becomes susceptible to thermal runaway, leading to overheating and potentially destructive consequences such as fire or explosion. Thermal runaway is a positive feedback loop in which an increase in temperature causes the system to change in a way that further increases the temperature. Excessive heat can be caused by battery mishandling, battery failure, accidents, or other factors. However, excessive heat generation is often due to increased Joule heating resulting from excessive internal current or exothermic reactions between the positive and negative electrodes. There are various causes of excessive internal current, but one possible cause is a decrease in internal resistance due to a short circuit in the separator caused by conductive particles penetrating the separator. The heat resulting from the short circuit in the separator causes further damage within the separator, leading to mixing of the reagents in the negative and positive electrodes and, as a result, the generation of further heat due to exothermic reactions.

[0008] Internal short circuit Lithium-ion batteries use a separator between the positive and negative electrodes to electrically isolate the two electrodes while allowing lithium ions to pass through. The lithium-ion permeability of the separator allows the battery to close the circuit when it performs its work by allowing electrons to pass through an external circuit. Short circuits across the separator can result from improper charging and discharging, or manufacturing defects such as metal impurities and metal fragment formation during electrode production. More specifically, improper charging can cause metallic lithium dendrites to deposit on the surface of the negative electrode, which can grow through the separator, providing a pathway for electron conduction from one electrode to the other. Furthermore, improper discharging below 1.5V can cause copper dissolution, ultimately leading to the formation of metallic copper dendrites on the surface of the negative electrode, which can grow through nanopores and penetrate the separator. The low resistance of these conductive paths results in rapid discharge and the generation of significant Joule heat, leading to overheating and thermal runaway.

[0009] To avoid fire and / or explosion, a combination of an internal current limiter and an internal current interrupter was required. This would first limit internal discharge caused by an internal short circuit to reduce the generation of Joule heat if the rate of internal discharge was insufficiently limited, and then interrupt the internal short circuit to further suppress the rate of internal discharge regardless of temperature rise. [Means for solving the problem]

[0010] In a first aspect, an improved high-energy-density rechargeable (HEDR) battery is provided, as described in some embodiments of this specification, the rechargeable battery comprising two electrodes of opposite polarity, each electrode characterized by resistance, a safe operating temperature range, and a safe charging voltage, and a separator that separates the two electrodes and prevents internal discharge between them. The HEDR battery comprises at least one electrode using a current collector for moving electrons, the separator is hazardous for short circuits, the short circuits potentially allow for a short circuit between the two electrodes, the rapid internal discharge between the two electrodes allows for rapid generation of Joule heat, and the rapid generation of Joule heat potentially allows for thermal runaway. In the HEDR battery, the two electrodes are hazardous for overcharging above the safe charging voltage, thereby forming a short circuit, and the two electrodes are hazardous for thermal runaway above the safe operating temperature range. The HEDR battery may include improvements to slow the rate of internal discharge due to short circuits, slow the generation of Joule heat therefrom, and reduce the risk of thermal runaway, the improvements including a current limiter that forms an electrical coupling between one electrode and a corresponding current collector, the current limiter having resistivity for resistively blocking the current passing through, for diverting the current from the electrode current collector to which it is connected if the separator forms a short circuit, and for reducing the rate of internal discharge between the two electrodes, and a current interrupter having an engaged configuration, an unengaged configuration, and a gas generating element that switches the current interrupter from the engaged configuration to the unengaged configuration. The gas generating element may have a trigger for generating gas, the trigger being selected from the group consisting of a temperature trigger and a voltage trigger, the temperature trigger being able to operate beyond the safe operating temperature range. In the engaged configuration, the voltage trigger is operable even when the safety charging voltage is exceeded, and the current interrupter electrically connects one of the electrodes to its corresponding current collector using a stacked connection. In the unengaged configuration, the stacked connection is separated, and the current interrupter forms a non-conductive gap that breaks the electrical connection between the electrode and its corresponding current collector.The current interrupter, in response to a trigger, initiates the operation of a gas generating element, transitioning from an engaged configuration to an unengaged configuration. The generated gas delaminates the laminated structure to break the electrical coupling between the electrode and its corresponding current collector. Using a current limiter and current interrupter in combination reduces the risk of separator short circuits, electrode overcharging, and thermal runaway due to electrode overheating.

[0011] The following features may be present in any suitable combination within an improved high-energy-density rechargeable (HEDR) battery: A current limiter and a current interrupter can be simultaneously incorporated by lamination in a protective layer interposed between the same electrode and current collector. An HEDR battery may include two current collectors, including a first current collector and a second current collector, and two electrodes, including a first electrode and a second electrode, where the first electrode includes a first portion and a second portion, and the second portion of the first electrode is interposed between the first portion of the first electrode and the first current collector. The improvements are further characterized as follows: a current limiter is laminated between the first portion of the first electrode and the second portion of the first electrode, and a current interrupter is laminated between the second portion of the first electrode and the first current collector. A current limiter can be stacked between a second portion of a first electrode and a first current collector, and a current interrupter can be stacked between a first portion of a first electrode and a second portion of a first electrode. An HEDR battery can include two current collectors, including a first current collector and a second current collector, and two electrodes, including a first electrode and a second electrode, and a current limiter can be stacked between a first electrode and a first current collector, and a current interrupter can be stacked between a second electrode and a second current collector. In an HEDR battery, each electrode may have a temperature range and internal resistivity for safe operation, and a current limiter may have a resistivity greater than the internal resistivity of the electrode stacked with the current limiter, within the temperature range for safe operation. The current limiter may lack a resistivity transition switch at temperatures within the temperature range for safe operation. An HEDR battery may have each electrode having a temperature range for standard operation, and the current limiter may have a resistivity transition where the resistivity is lower than the internal resistivity of the electrode within the standard operating temperature range and higher than the internal resistivity of the electrode above the standard operating temperature range. An HEDR battery may have each electrode having a temperature range for standard operation, and the current interrupter may be configured to operate at temperatures above the standard operating temperature range.In some embodiments, the HEDR battery may be of a type in which each electrode has a temperature range for standard operation and a temperature range for safe operation, and the current interrupter operates at a temperature above the temperature range for standard operation but within the temperature range for safe operation. In some embodiments, the HEDR battery may be of a type in which each cell has an internal resistance within the temperature range for safe operation, and the current limiter has a resistivity greater than the internal resistivity of the electrode laminated with the current limiter within the temperature range for safe operation. The current limiter and current interrupter can be simultaneously incorporated by lamination in a protective layer interposed between the same electrode and the current collector. The HEDR battery may be of a type in which each electrode has a voltage range for standard operation, and the current interrupter is activated at a voltage above the voltage range for standard operation. The HEDR battery may be of a type in which each cell has a voltage range for standard operation and a voltage range for safe operation, and the current interrupter is activated at a voltage above the voltage range for standard operation but within the voltage range for safe operation. The current limiter and current interrupter can be simultaneously incorporated by lamination into a protective layer interposed between the same electrode and current collector.

[0012] In a related embodiment, an improved high-energy-density rechargeable (HEDR) battery is provided as described herein, the rechargeable battery comprising two electrodes of opposite polarity, a separator separating the two electrodes, and at least one current collector electrically coupled to one of the two electrodes, wherein the separator prevents internal discharge between the two electrodes, and failure of the separator potentially results in internal discharge between the two electrodes, the internal discharge resulting in the generation of Joule heat as a potential hazard, and the rechargeable battery comprises a thermally operated current interruptor and a voltage-operated current interruptor. A thermally operated current interrupter can be laminated between one of the current collectors and one of the electrodes by a lamination method. When the thermally operated current interrupter is not operating, it electrically couples the current collector to the electrode laminated with the current collector, while when operating, it forms a non-conductive gap to separate the current collector from the electrode laminated with the current collector, thereby separating it from the current collector. This electrical separation slows down the rate of internal discharge between the two electrodes if the separator is damaged. A voltage-operated current interrupter can be laminated between one of the current collectors and one of the electrodes by a lamination method. When the voltage-operated current interrupter is not operating, it electrically couples the current collector to the electrode laminated with the current collector, while when operating, it forms a non-conductive gap to separate the current collector from the electrode laminated with the current collector, thereby separating it from the current collector. This electrical separation slows down the rate of internal discharge between the two electrodes if the separator is damaged. In HEDR batteries, in the event of separator failure, the activation of either a thermally actuated or voltage-actuated current interrupter can slow down the generation of Joule heat to reduce the potential hazard.

[0013] In further relevant embodiments, some embodiments described herein provide a method for avoiding thermal runaway inside a high-energy-density rechargeable battery in which internal discharge occurs due to separator failure, the method comprising separating the electrodes inside the battery from the current collector by generating a gas from a heat-sensitive gas-generating material in a barrier layer interposed between the electrodes and the current collector, thereby electrically separating the electrodes from the current collector and slowing the rate of internal discharge.

[0014] In a first aspect, the Specified Provisions provide an improved high-energy-density rechargeable (HEDR) battery, the rechargeable battery comprising an anode energy layer, a cathode energy layer, a separator disposed between the anode energy layer and the cathode energy layer to prevent internal discharge, at least one current collector exchanging electrons with either the anode energy layer or the cathode energy layer, and a resistive layer interposed between the separator and one of the current collectors, wherein the anode energy layer and the cathode energy layer each have an internal resistivity, and the HEDR battery has a preferred temperature range for discharging current and an upper temperature safety limit. The resistive layer has a limit, and is configured to limit the rate of internal discharge through the separator in the event of separator failure and the resulting generation of Joule heat, and the resistive layer has a constant resistivity at temperatures between a preferred temperature range and an upper temperature safety limit, and the constant resistivity of the resistive layer is greater than the internal resistivity of any energy layer, and the resistive layer is intended to avoid temperatures exceeding the upper temperature safety limit in the event of separator failure.

[0015] The following features can be incorporated into an HEDR battery by appropriate combination. In some embodiments, the resistive layer of the HEDR battery may be porous and include ceramic powder defining void spaces, a binder partially filling the void spaces to bind the ceramic powder, and a conductive component dispersed within the binder to impart resistivity to the resistive layer, wherein the void spaces are partially unfilled to impart porosity and permeability to the resistive layer. The resistive layer can be compressed to reduce unfilled void spaces and increase the binding of the ceramic powder by the binder. The resistive layer may contain more than 30% by weight of ceramic powder. The resistive layer may contain more than 50% by weight of ceramic powder. The resistive layer may contain more than 70% by weight of ceramic powder. The resistive layer may contain more than 75% by weight of ceramic powder. The resistive layer may contain more than 80% by weight of ceramic powder. The resistive layer of the HEDR battery may be permeable to the movement of ionic charge carriers. The resistive layer may be porous and may include a composition comprising a nonconductive filler, a binder binding the nonconductive filler, and a conductive component dispersed in the binder to impart resistivity to the resistive layer. The resistive layer may be impermeable to the movement of ionic charge carriers. The constant resistivity of the resistive layer of the HEDR battery may be at least twice the internal resistivity of any of the energy layers. The constant resistivity of the resistive layer of the HEDR battery may be at least five times the internal resistivity of any of the energy layers. The constant resistivity of the resistive layer of the HEDR battery may be at least ten times the internal resistivity of any of the energy layers. The resistive layer may not require solid-to-non-solid phase conversion to convert the resistivity of the resistive layer from low resistivity to high resistivity at temperatures between the maximum operating temperature and the upper temperature safety limit. The resistive layer may be non-sacrificial at temperatures below the upper temperature safety limit. The resistive layer may be sacrificial at temperatures above the upper temperature safety limit. The resistive layer may contain ceramic powder that chemically decomposes at temperatures above the upper temperature safety limit to generate flame-retardant gases. The resistive layer may contain ceramic powder that chemically decomposes at temperatures above the upper temperature safety limit in order to generate gas that separates the current collector from the resistive layer.The current collector may include an anode current collector for exchanging electrons with the anode energy layer, and a resistive layer is interposed between the separator and the anode current collector. The resistive layer may be interposed between the anode current collector and the anode energy layer. The resistive layer may be interposed between the anode energy layer and the separator. In some embodiments, the anode energy layer of the HEDR battery includes a first anode energy layer and a second anode energy layer interposed between the first anode energy layer and the separator, and a resistive layer is interposed between the first anode energy layer and the second anode energy layer. The current collector may include a cathode current collector for exchanging electrons with the cathode energy layer, and a resistive layer is interposed between the separator and the cathode current collector. The resistive layer may be interposed between the cathode current collector and the cathode energy layer. The resistive layer may be interposed between the cathode energy layer and the separator. The cathode energy layer may include a first cathode energy layer and a second cathode energy layer interposed between the first cathode energy layer and a separator, and the resistive layer is interposed between the first cathode energy layer and the second cathode energy layer. In some embodiments, the HEDR battery may include two current collectors, the two current collectors including an anode current collector that exchanges electrons with the anode energy layer and a cathode current collector that exchanges electrons with the cathode energy layer, and the resistive layer includes an anode resistive layer and a cathode resistive layer, the anode resistive layer being interposed between the separator and the anode current collector and the cathode resistive layer being interposed between the separator and the cathode current collector.

[0016] In a related embodiment, a method is provided herein for limiting the rate of internal discharge of an energy layer due to separator failure within a high-energy-density rechargeable (HEDR) battery, the method comprising resisting the internal discharge using a resistive layer, the resistive layer interposed between a separator and a current collector in the HEDR battery, the resistive layer having a constant resistivity at a temperature between a preferred temperature range for discharging the energy layer and an upper temperature safety limit, the constant resistivity of the resistive layer being greater than the internal resistivity of the energy layer.

[0017] In some embodiments described herein, a high-energy-density rechargeable (HEDR) metal-ion battery is provided, the battery comprising an anode energy layer, a cathode energy layer, a separator separating the anode energy layer from the cathode energy layer, at least one current collector exchanging electrons with either the anode energy layer or the cathode energy layer, and a shut-off layer that, when exposed to a temperature of or above an upper temperature safety limit, has an upper temperature safety limit to avoid thermal runaway, the shut-off layer is interposed between the separator and one of the current collectors, and the shut-off layer is, When not in operation, the separator is stacked between the separator and one of the current collectors of the current collector, allowing current to flow. When in operation, it is peeled off to interrupt the current flowing through the high-energy-density rechargeable metal-ion battery. The interrupting layer contains a thermosensitive decomposable component that decomposes when exposed to a temperature at or above the upper temperature safety limit. The thermosensitive decomposable component generates gas upon decomposition, and the generated gas peels off the interrupting layer to interrupt the current flowing through the high-energy-density rechargeable metal-ion battery. The high-energy-density rechargeable metal-ion battery avoids thermal runaway by activating the interrupting layer by exposing it to a temperature at or above the upper temperature safety limit to interrupt the current within the high-energy-density rechargeable metal-ion battery.

[0018] The following features can be appropriately combined to be present in an HEDR metal-ion battery. The barrier layer may be porous. The temperature-sensitive decomposable component may include ceramic powder. The barrier layer may include a composition comprising ceramic powder, a binder, and a conductive component. The ceramic powder may define void spaces. The binder may partially fill the void spaces to bind the ceramic powder. The conductive component may be dispersed within the binder to impart conductivity to the barrier layer. The void spaces may be partially unfilled to impart porosity and permeability to the barrier layer. The barrier layer may contain more than 30% by weight of ceramic powder. The barrier layer may contain more than 50% by weight of ceramic powder. The barrier layer may contain more than 70% by weight of ceramic powder. The barrier layer may contain more than 75% by weight of ceramic powder. The barrier layer may contain more than 80% by weight of ceramic powder. The barrier layer may be permeable to the movement of ion charge carriers. The barrier layer may be porous and may include a composition comprising a nonconductive filler, a binder binding the nonconductive filler, and a conductive component dispersed in the binder to impart resistivity to the barrier layer. The barrier layer may be impermeable to the movement of ionic charge carriers. The barrier layer may be sacrificial at temperatures above the upper temperature safety limit. The barrier layer may include ceramic powder that chemically decomposes at temperatures above the upper temperature safety limit to generate a flame-retardant gas. The current collector may include an anode current collector for exchanging electrons with the anode energy layer, and the barrier layer is interposed between the separator and the anode current collector. The barrier layer may be interposed between the anode current collector and the anode energy layer. The barrier layer may be interposed between the anode energy layer and the separator. The anode energy layer of the HEDR battery includes a first anode energy layer and a second anode energy layer interposed between the first anode energy layer and a separator, and a blocking layer interposed between the first anode energy layer and the second anode energy layer.The current collector may include a cathode current collector for exchanging electrons with the cathode energy layer, and the blocking layer is interposed between the separator and the cathode current collector. The blocking layer may be interposed between the cathode current collector and the cathode energy layer. The blocking layer may be interposed between the cathode energy layer and the separator. The cathode energy layer may include a first cathode energy layer and a second cathode energy layer interposed between the first cathode energy layer and the separator, and the blocking layer is interposed between the first cathode energy layer and the second cathode energy layer. The HEDR battery may further include two current collectors, the two current collectors including an anode current collector that exchanges electrons with the anode energy layer and a cathode current collector that exchanges electrons with the cathode energy layer, and the blocking layer includes an anode blocking layer and a cathode blocking layer, the anode blocking layer being interposed between a separator and the anode current collector and the cathode blocking layer being interposed between a separator and the cathode current collector.

[0019] In a related embodiment, a method is provided for interrupting the current flowing through a high-energy-density rechargeable metal-ion battery by exposing it to a temperature at or above an upper temperature safety limit in order to avoid thermal runaway, the method comprising raising the temperature of the high-energy-density rechargeable metal-ion battery above the upper temperature safety limit and activating a blocking layer that interrupts the current flowing through the high-energy-density rechargeable metal-ion battery. A high-energy-density rechargeable metal-ion battery includes an anode energy layer, a cathode energy layer, a separator separating the anode energy layer from the cathode energy layer, a current collector that exchanges electrons with either the cathode energy layer or the anode energy layer, and a blocking layer, wherein the blocking layer is interposed between the separator and one of the current collectors, and when not in operation, the blocking layer is stacked between the separator and one of the current collectors to allow current to flow, while when in operation, it is peeled off to interrupt the current flowing through the lithium-ion battery, and the blocking layer includes a thermosensitive decomposable component that decomposes when exposed to a temperature at or above the upper temperature safety limit, and when the thermosensitive decomposable component decomposes, it generates a gas, and the generated gas peels off the blocking layer, interrupting the current flowing through the high-energy-density rechargeable metal-ion battery, thereby preventing thermal runaway of the high-energy-density rechargeable metal-ion battery by interrupting the current flowing through the battery.

[0020] In some embodiments of this specification, a high-energy-density rechargeable (HEDR) metal-ion battery is provided, the battery comprising an anode energy layer, a cathode energy layer, a separator separating the anode energy layer from the cathode energy layer, an anode current collector exchanging electrons with the anode energy layer, and a cutoff layer that acts to cut off the current in the high-energy-density rechargeable metal-ion battery when exposed to a voltage exceeding a maximum safety voltage, the high-energy-density rechargeable metal-ion battery is rechargeable and characterized by a maximum safety voltage to avoid overcharging, and the cutoff layer acts to cut off the current in the cathode The interrupting layer is sandwiched between the anode energy layer and the cathode current collector. When not in operation, the interrupting layer is stacked on the anode current collector and conducts current, while when in operation, it peels off from the anode current collector and interrupts the current. The interrupting layer contains a voltage-sensitive decomposable component that decomposes when exposed to a voltage exceeding the maximum safe voltage. The voltage-sensitive decomposable component generates gas when it decomposes, and the generated gas peels the interrupting layer off the anode current collector, interrupting the current. As a result, when the high-energy-density rechargeable metal-ion battery is exposed to a voltage exceeding the maximum safe voltage, the interrupting layer activates and interrupts the current, thereby preventing overcharging.

[0021] The following features, when appropriately combined, can be present in a high-energy-density rechargeable metal-ion battery. The barrier layer of the HEDR battery may be porous and may also contain a composition comprising ceramic powder defining void spaces, a binder partially filling the void spaces to bind the ceramic powder, and a conductive component dispersed within the binder to impart conductivity to the barrier layer, wherein the void spaces are partially unfilled to impart porosity and permeability to the barrier layer. The barrier layer can be compressed to reduce unfilled void spaces and increase the binding of the ceramic powder by the binder. The barrier layer may contain more than 30% by weight of ceramic powder. The barrier layer may contain more than 50% by weight of ceramic powder. The barrier layer may contain more than 70% by weight of ceramic powder. The barrier layer may contain more than 75% by weight of ceramic powder. The barrier layer may contain more than 80% by weight of ceramic powder. The barrier layer may be permeable to the movement of ion charge carriers. The shielding layer of the HEDR battery may be porous, or it may contain a composition comprising a nonconductive filler, a binder binding the nonconductive filler, and a conductive component dispersed in the binder to impart resistivity to the shielding layer. The shielding layer may be impermeable to the movement of ionic charge carriers. The shielding layer may be sacrificial at a voltage exceeding the maximum safe voltage for recharging. The shielding layer may contain ceramic powder that is chemically decomposed at a voltage exceeding the maximum safe voltage to generate a gas. The gas may be a flame-retardant gas.

[0022] In a related embodiment, a method is provided for interrupting the recharging process of a high-energy-density rechargeable metal-ion battery when exposed to a voltage of or above a maximum safe voltage in order to avoid overcharging, wherein the high-energy-density rechargeable metal-ion battery includes an anode energy layer, a cathode energy layer, a separator separating the anode energy layer from the cathode energy layer, and an anode current collector that exchanges electrons with the anode energy layer. The method includes overcharging the high-energy-density rechargeable metal-ion battery to increase the voltage to exceed a maximum safe voltage for recharging, and interrupting the overcharging by generating a gas by decomposition of a voltage-sensitive decomposable component in a blocking layer laminated on the anode current collector, wherein the generated gas peels the blocking layer away from the anode current collector, thereby interrupting the overcharging of the high-energy-density rechargeable metal-ion battery by the peeling of the blocking layer away from the anode current collector due to gas generation in the blocking layer.

[0023] One aspect of the present disclosure relates to an improved high-energy-density rechargeable (HEDR) battery of a type comprising two electrodes (12 and 14) of opposite polarity. Each electrode is characterized by its resistivity, its safe operating temperature range, and its safe charging voltage. The HEDR further comprises a separator 2 that separates the two electrodes (12 and 14) and prevents internal discharge between the two electrodes, and at least one electrode (12 or 14) using a current collector 4 for transferring electrons. The separator 2 is subject to the risk of forming a short circuit. A short circuit may result in a rapid internal discharge between the two electrodes (12 and 14), which may result in a rapid generation of Joule heat, which may lead to thermal runaway. The two electrodes (12 and 14) are subject to the risk of overcharging above the safe charging voltage and the resulting formation of a short circuit. The two electrodes (12 and 14) are subject to the risk of thermal runaway at temperatures above the safe operating temperature range.

[0024] Improvements to the first aspect of this disclosure can be used to slow down the rate of internal discharge caused by short circuits, slow down the generation of Joule heat caused thereby, and reduce the risk of thermal runaway.

[0025] The improvement includes adding a current limiter 6 to the HEDR battery in combination with the current interrupter 8.

[0026] The current limiter 6 forms an electrical coupling between one of the electrodes (12 or 14) and the corresponding current collector 4. The current limiter 6 has resistivity, which resistively blocks the current and, when the separator 2 forms a short circuit, diverts the current from the coupled electrode current collector 4 and reduces the rate of internal discharge between the two electrodes (12 and 14).

[0027] The current interrupter 8 has an engaged configuration, an unengaged configuration, and a gas generating element that transitions the current interrupter 8 from the engaged configuration to the unengaged configuration. The gas generating element has a trigger for generating gas. The trigger is selected from the group consisting of a temperature trigger and a voltage trigger.

[0028] The temperature trigger activates at temperatures exceeding the safe operating temperature range.

[0029] The voltage trigger activates at a voltage exceeding the safe charging voltage.

[0030] In the engagement configuration, the current interrupter 8 electrically connects one of its electrodes (12 or 14) to the corresponding current collector 4 via a stacked connection.

[0031] In the non-engaged configuration, the lamination is separated, and the current interrupter 8 forms a non-conductive gap, interrupting the electrical coupling between the electrode (12 or 14) and the corresponding current collector 4.

[0032] The current interrupter 8 transitions from an engaged configuration to an unengaged configuration by initiating the operation of the gas generating element in response to a trigger. The generated gas delaminates the lamination connection to break the electrical coupling between the electrode (12 or 14) and the corresponding current collector 4.

[0033] In a first aspect of this disclosure, the current limiter 6 and the current interrupter 8 are configured in combination to reduce the risk of thermal runaway caused by short circuits of the separator, overcharging of the electrodes, and overheating of the electrodes.

[0034] In one embodiment of the first aspect of this disclosure, the current limiter 6 and the current interrupter 8 are simultaneously incorporated into a protective layer by being interposed in a stacked manner between the same electrode (12 or 14) and the current collector 4.

[0035] In another embodiment of the first aspect of the present disclosure, the battery is of a type that includes two current collectors 4, including a first current collector 4 and a second current collector 4. Two electrodes (12 and 14) include a first electrode and a second electrode. The first electrode includes a first portion and a second portion. The second portion of the first electrode is interposed between the first portion of the first electrode and the first current collector 4. Further features of the improvements of this embodiment of the present disclosure include the stacking of a current limiter 6 between the first portion of the first electrode and the second portion of the first electrode, and the stacking of a current interrupter 8 between the second portion of the first electrode and the first current collector 4. In a sub-embodiment of the first aspect of the present disclosure, the current limiter 6 is stacked between the second portion of the first electrode and the first current collector 4, and the current interrupter 8 is stacked between the first portion of the first electrode and the second portion of the first electrode.

[0036] In another embodiment of the first aspect of the present disclosure, the battery is of a type comprising two current collectors 4, including a first current collector 4 and a second current collector 4, and two electrodes (12 and 14), including a first electrode and a second electrode, and improvements have further features. In this embodiment, a current limiter 6 is stacked between the first electrode and the first current collector 4, and a current interrupter 8 is stacked between the second electrode and the second current collector 4.

[0037] In another embodiment of the first aspect of the present disclosure, the battery is of a type in which each electrode (12 or 14) has a temperature range and internal resistivity for safe operation. In this embodiment, the current limiter 6 has a resistivity greater than the internal resistivity of the electrode (12 or 14) stacked with the current limiter 6, within the temperature range for safe operation.

[0038] In another embodiment of the first aspect of this disclosure, a further feature of the improvement is that, at temperatures within the temperature range for safe operation, the current limiter 6 lacks a resistivity transition switch.

[0039] In another embodiment of the first aspect of the present disclosure, the battery is of a type in which each electrode (12 and 14) has a temperature range for standard operation. In this embodiment, the current limiter 6 performs resistivity transitions with a resistivity lower than the internal resistivity of the electrodes (12 and / or 14) within the temperature range for standard operation, and with a resistivity higher than the internal resistivity of the electrodes (12 and / or 14) at temperatures above the temperature range for standard operation.

[0040] In another embodiment of the first aspect of the present disclosure, the battery is of a type in which each electrode (12 and 14) has a temperature range for standard operation. In this embodiment, the current interrupter 8 operates at temperatures exceeding the temperature range for standard operation.

[0041] In another embodiment of the first aspect of the present disclosure, the battery is of a type in which each electrode (12 and 14) has a temperature range for standard operation and a temperature range for safe operation. In this embodiment, the current interrupter 8 operates at a temperature that is above the temperature range for standard operation and within the temperature range for safe operation.

[0042] In another embodiment of the first aspect of this disclosure, the battery is such that each battery (12 and 14) has an internal resistivity within a temperature range for safe operation. In this embodiment, the current limiter 6 has a resistivity higher than the internal resistivity of the electrode (12 or 14) laminated with the current limiter 6, within the temperature range for safe operation. Alternatively, the current limiter 6 and the current interrupter 8 are simultaneously incorporated in a protective layer laminated between the same electrode (12 or 14) and the current collector 4.

[0043] In another embodiment of the first aspect of the present disclosure, the battery is of a type in which each electrode (12 and 14) has a voltage range for standard operation. In this embodiment, the current interrupter 8 operates at a voltage exceeding the voltage range for standard operation.

[0044] In another embodiment of the first aspect of this disclosure, the battery has electrodes (12 and 14) each having a voltage range for standard operation and a voltage range for safe operation. In this embodiment, the current interrupter 8 operates at a voltage that is above the voltage range for standard operation but within the voltage range for safe operation. As an alternative to this embodiment, the current limiter 6 and the current interrupter 8 are simultaneously incorporated in a protective layer interposed by lamination between the same electrode (12 or 14) and the current collector 4.

[0045] A second aspect of the present disclosure is another improved high-energy-density rechargeable battery of the type having two electrodes (12 and 14) of opposite polarity, a separator 2 separating the two electrodes (12 and 14), and at least one current collector 4 electrically coupling one of the electrodes (12 or 14). The separator 2 prevents internal discharge between the two electrodes (12 and 14). Damage to the separator 2 may result in internal discharge between the two electrodes (12 and 14). Internal discharge results in the generation of Joule heat, which is a potential hazard.

[0046] Improvements of a second aspect of this disclosure include a thermally operated current interrupter 8 and a voltage-operated current interrupter 8.

[0047] The thermally operated current interrupter 8 is laminated between one of the current collectors 4 and one of the electrodes (12 or 14) using a lamination method. When not in operation, the thermally operated current interrupter 8 electrically couples the current collector 4 to the electrode (12 or 14) with which it is laminated. When in operation, the thermally operated current interrupter 8 delaminates from the current collector 4 to form a non-conductive gap that electrically isolates the current collector 4 from the electrode (12 or 14) with which it was laminated. This electrical isolation slows down the rate of internal discharge between the two electrodes (12 and 14) in the event of separator failure.

[0048] A voltage-operated current interrupter 8 is laminated between one of the current collectors 4 and one of the electrodes (12 or 14) using a lamination method. When not operating, the voltage-operated current interrupter 8 electrically couples the current collector 4 to the electrode (12 or 14) with which it is laminated. When operating, the voltage-operated current interrupter 8 delaminates from the current collector 4 to form a non-conductive gap that electrically isolates the current collector 4 from the electrode (12 or 14) with which it was laminated. This electrical isolation slows down the rate of internal discharge between the two electrodes (12 and 14) in the event of separator failure. In a second aspect of this disclosure, when the separator fails, either a thermal-operated current interrupter 8 or a voltage-operated current interrupter 8 can be activated to slow down the generation of Joule heat and reduce the potential hazard.

[0049] A second aspect of this disclosure relates to a method for avoiding thermal runaway in a high-energy-density rechargeable battery that suffers internal discharge due to separator failure. The method includes a step of separating the electrode (12 or 14) in the battery from the current collector 4 by generating gas from a heat-sensitive gas generating material in a barrier layer interposed between the electrode (12 or 14) and the current collector 4. The separation electrically isolates the electrode (12 or 14) from the current collector in order to slow the rate of internal discharge.

[0050] A third aspect of this disclosure relates to a method for avoiding thermal runaway in a high-energy-density rechargeable battery that is at risk of separator damage due to voltage overcharging. The method includes a step of separating the electrode (12 or 14) in the battery from the current collector 4 by generating gas from a heat-sensitive gas generating material in a barrier layer interposed between the electrode (12 or 14) and the current collector 4. The separation electrically isolates the electrode (12 or 14) from the current collector in order to interrupt voltage overcharging.

[0051] A fourth aspect of this disclosure relates to a method for avoiding thermal runaway in a high-energy-density rechargeable battery that is at risk of separator damage due to voltage overcharging. The method includes a step of separating the electrodes (12 or 14) in the battery from the current collector 4 by generating a gas from a voltage-sensitive or temperature-sensitive material that indirectly forms a gas via a decomposition compound (at high voltage) that reacts with battery elements such as the electrolyte and electrodes (12 or 14). This voltage-sensitive or temperature-sensitive material, also called a gas generator, may be included in a barrier layer interposed between the electrodes (12 or 14) and the current collector 4. The separation electrically isolates the electrodes (12 or 14) from the current collector to interrupt voltage overcharging.

[0052] This disclosure is described in more detail by reference to the accompanying drawings, which illustrate several exemplary embodiments of this disclosure. As will be understood by those skilled in the art, the embodiments described can be modified in various different ways without departing from the spirit or scope of this disclosure. Accordingly, the drawings and description should be considered illustrative and not restrictive. In the drawings, the thicknesses of layers and areas are exaggerated for clarity. [Brief explanation of the drawing]

[0053] [Figure 1] Figure 1A-1G is a schematic diagram illustrating an exemplary configuration of a film-type lithium-ion battery having one or more resistive layers that function as a current limiter 6, which protects the battery from overheating in the event of an internal short circuit and, in combination with a thermally activated current interrupter 8 that reacts to rising temperatures, irreversibly interrupts the self-discharge process if the battery overheats or reaches a dangerous temperature. [Figure 2]Figures 2A-2B are schematic diagrams illustrating an exemplary configuration of a film-type lithium-ion battery having one or more layers that function as a combination of a current limiter 6 and a current interrupter 8. In the event of an internal short circuit, the battery is protected from overheating and, in combination with the current interrupter 8 which can be voltaically activated by an increase in voltage, irreversibly interrupts the self-discharge process if the battery becomes overcharged. [Figure 3] Figures 3A and 3B are schematic diagrams illustrating an exemplary configuration of a film-type lithium-ion battery having one or more resistive layers that function as a current limiter 6 to protect the battery from overheating in the event of an internal short circuit. Combined with a thermally activated current interrupter 8 that reacts to rising temperatures, it irreversibly shuts off the self-discharge process when the battery is overheating or reaches a dangerous temperature. Furthermore, combined with a current interrupter 8 that reacts to voltage increases, it irreversibly shuts off the self-discharge process when the battery is overcharged. [Figure 4] Figures 4A-4D show cross-sectional views of a prior art film-type lithium-ion battery (Figures 4A, 4B) and a film-type lithium-ion battery of the present disclosure (Figures 4C, 4D). [Figure 5] Figures 5A-5D show cross-sectional views of a prior art film-type lithium-ion battery (Figures 5A, 5B) and a film-type lithium-ion battery of the present disclosure (Figures 5C, 5D). [Figure 6] Figures 6A-6D show cross-sectional views of a prior art film-type lithium-ion battery (Figures 6A, 6B) and a film-type lithium-ion battery of the present disclosure (Figures 6C, 6D). [Figure 7] Figures 7A-7D show cross-sectional views of a prior art film-type lithium-ion battery (Figures 7A, 7B) and a film-type lithium-ion battery of the present disclosure (Figures 7C, 7D). [Figure 8] Figures 8A-8D show cross-sectional views of a prior art film-type lithium-ion battery (Figures 8A, 8B) and a film-type lithium-ion battery of the present disclosure (Figures 8C, 8D). [Figure 9] Figures 9A-9D show cross-sectional views of a prior art film-type lithium-ion battery (Figures 9A, 9B) and a film-type lithium-ion battery of the present disclosure (Figures 9C, 9D). [Figure 10] Figures 10A-10D show cross-sectional views of a prior art film-type lithium-ion battery (Figures 10A, 10B) and a film-type lithium-ion battery of the present disclosure (Figures 10C, 10D). [Figure 11] Figures 11A-11D show cross-sectional views of a prior art film-type lithium-ion battery (Figures 11A, 11B) and a film-type lithium-ion battery of the present disclosure (Figures 11C, 11D). [Figure 12] Figures 12A-12C show exemplary structures of the combined current limiter 6 and current interrupter 8. [Figure 13] Figures 13A and 13B show exemplary cell compositions.

[0054] [Figure 14] Figure 14 shows various compositions of positive electrode 14 used for measuring chemical decomposition voltage. [Figure 15] Figure 15 shows the baseline resistance of cell No. 2 at 3.6V versus graphite as the temperature rises. The resistance decreases by approximately 10 times as the temperature rises. [Figure 16] Figure 16 shows the resistance of cell No. 4 (positive electrode 14 with Al2O3 and CaCO3 ceramic layers) at 0V and 3.655V versus graphite as the temperature rises. The resistance increases slightly at zero voltage and significantly at 3.646V and 4.11V. [Figure 17] Figure 17 shows the resistance of cell No. 3 (positive electrode 14 with a CaCO3 ceramic layer) at 0V, 3.646V, and 4.11V versus graphite as the temperature rises. The resistance increases slightly at zero voltage and significantly at 3.655V. [Figure 18] Figure 18 shows the relationship between cell voltage and the discharge capacity of baseline cell No. 1 (without a resistive layer) at 1A, 3A, 6A, and 10A. [Figure 19] Figure 19 shows the relationship between cell voltage and the discharge capacity of baseline cell No. 3 (85.2% CaCO3-based resistive layer 6) at 1A, 3A, 6A, and 10A. When using this particular resistive layer 6, the cell's discharge capacity decreases significantly with increasing cell discharge current. [Figure 20] Figure 20 summarizes the cell impedance and discharge capacity at 1A, 3A, 6A, and 10A, and the ratio of the capacity at 3A, 6A, or 10A to the capacity at 1A for cells No. 1 (reference), 3, 4, 5, and 6. The cell impedance at 1kHz increases in the presence of resistance and gas generation layers. The discharge capacity of the cells depends on the individual case, but the impedance of all cells with resistance layer 6 increases, indicating that resistance layer 6 leads to an increase in cell impedance. [Figure 21] Figure 21 shows the impact test. [Figure 22] Figure 22 shows the cell temperature profiles during the impact test for cells No. 1 (reference), 3, 5, and 6. When the steel rod struck the cells, the voltage of all tested cells immediately dropped. All cells with resistance and gas generation layers passed the test, but cells without resistance layer 6 failed the test (they ignited). The maximum cell temperatures during the impact test are summarized in Figure 23. [Figure 23] Figure 23 summarizes the maximum cell temperatures during the impact tests for cells No. 1 (reference), 3, 4, 5, and 6. [Figure 24] Figure 24 shows the relationship between the impact test time, cell voltage, and temperature for cell No. 6. The impact start time was set to 2 minutes. As soon as the cell was impacted, the cell voltage dropped to zero. It can be seen that the cell temperature rose rapidly. [Figure 25]Figure 25 shows the relationship between overcharging time, cell voltage, and temperature for cell No. 3 (without protective layer). The cell voltage gradually increased until 40 minutes, then decreased slightly, and jumped sharply to the maximum charging voltage at approximately 56 minutes, at which point the cell temperature rose significantly to over 600°C. Upon disconnection, the cell voltage and temperature decreased to very small values, and the cell ignited. The overcharging current was 2A until the cell ignited, then decreased to 0.2A for 1-2 minutes, and then returned to 2A as the cell short-circuited. The cell burned. [Figure 26] Figure 26 shows the relationship between overcharging time, cell voltage, and temperature for cell No. 3 (CaCO3 layer). The cell voltage gradually increased up to 40 minutes, then rapidly increased to the maximum charging voltage of 12V at approximately 55 minutes. The cell temperature rose to over 80°C at approximately 40 minutes from the start, and then rapidly decreased. At 55°C, the overcharging current decreased significantly and remained at 0.2A for the remainder of the test time. After the test, the cell was noticeably swollen. [Figure 27] Figure 27 shows the relationship between overcharging time, cell voltage, and temperature for cell No. 5 (Na2O7Si3 + Al2O3 layer). The cell voltage gradually increased up to 40 minutes, then rapidly increased to the maximum charging voltage of 12V at approximately 75 minutes. The overcharging profile of the cell differed significantly from that of CaCO3-based resistive layer 6, indicating the difference between the decomposition of CaCO3 and the decomposition of Na2O7Si3. The cell temperature rose significantly to over 75°C at approximately 40 minutes from the start, and then gradually decreased. At 75 minutes, the overcharging current decreased significantly and remained at 1A for the remainder of the test time. After the test, the cell was noticeably swollen. [Figure 28] Figure 28 summarizes the maximum cell temperatures during the overcharge test (2A / 12V) for cells No. 1 (reference), 3, 4, 5, and 6. [Figure 29] Figure 29 shows the cycle life of cell No. 3 (CaCO3 resistive layer 6). After 100 cycles, the cell showed a loss of approximately 1.8%, which is lower than the case of cells without a resistive layer (average, ~2.5%, not shown). [Figure 30]Figure 30 shows the cycle life of cell No. 4 (CaCO3 and Al2O3 resistive layer 6). After 100 cycles, the cell showed a loss of approximately 1.3%, which is lower than that of cells without a resistive layer (average, ~2.5%, not shown). [Figure 31] Figure 31 shows the current-to-voltage profiles at room temperature for compounds containing different anions (gas generators) that can be used in rechargeable batteries with different operating voltages. The peak current and peak voltage are shown in Figure 32. Cu(NO3)2 had the highest peak current, while CaCO3 had the lowest peak current. Cu(NO3)2 had the lowest peak voltage, while CaCO3 had the highest peak voltage. Therefore, Cu(NO3)2 is useful in lithium-ion batteries with relatively low operating voltages (typical maximum charging voltage of 3.7V), such as lithium-ion cells using lithium iron phosphate cathodes. CaCO3 is useful in high-operating-voltage lithium-ion cells (typical maximum charging voltage of 4.2V) using high-voltage cathodes such as lithium cobalt oxide, or high-operating-voltage lithium-ion cells (typical maximum charging voltage of 4.3 or 4.4V) using high-voltage cathodes such as lithium nickel cobalt manganese oxide. [Figure 32] Figure 32 summarizes the peak currents and peak voltages of compounds containing different anions. [Figure 33]Figure 33 shows the current-to-voltage profiles for polymers (organic gas generators) with and without different anions, which may be used in rechargeable batteries with different operating voltages. PVDF was used for comparison. Peak current and peak voltage are shown in Figure 34. The peak currents for Carbopol, AI-50, and PVDF were similar, with CMC being the lowest. Carbopol had the lowest peak voltage, while CMC had the highest. Therefore, Carbopol, containing the CO3 2-anion, is useful in lithium-ion batteries with relatively low operating voltages (typical maximum charging voltage of 3.7V), such as lithium-ion cells using lithium iron phosphate cathodes. CMC is useful in high-operating-voltage lithium-ion cells using high-voltage cathodes such as lithium cobalt oxide (typical maximum charging voltage of 4.2V) or high-operating-voltage lithium-ion cells using high-voltage cathodes such as lithium nickel cobalt manganese oxide (typical maximum charging voltage of 4.3 or 4.4V). Water is one of the CMC decomposition compounds, and not only does it become vapor or gas at temperatures above 100°C, but it also reacts with the intercalated lithium in the electrolyte and negative electrode graphite electrode to generate gases such as hydrogen fluoride (HF) and oxygen (O2). [Figure 34] Figure 34 summarizes the peak current and peak voltage with and without different anions. [Figure 35] Figure 35 shows the cell temperature and overcharge voltage profiles during a 2A / 12V overcharge test at room temperature. [Figure 36] Figure 36 shows the impedance and capacitance of cells 1, 3, 4, 5, and 6, as described in Examples 9 to 12 below, at different currents. [Figure 37] Figure 37 shows the change in resistance between 3.6V and graphite in cell 2 (reference, without a resistive layer) as the temperature rises. With increasing temperature, the resistance decreased by approximately 10 times. [Figure 38] Figure 38 shows the change in resistance between 4.09V and graphite in cell 3 with respect to temperature increase. With increasing temperature, the resistance decreased slightly, then increased by approximately three times, and then decreased by approximately three times. [Figure 39] Figure 39 shows the relationship between cell voltage and discharge capacity of cell 4 at 1A, 3A, 6A, and 10A. With this particular resistance layer, the cell discharge capacity decreased significantly with increasing cell discharge current. [Figure 40] Figure 40 shows the cell temperature profiles during the impact test for cells 1, 3, 4, 5, and 6 described in Examples 9-12. All cells with a resistance layer passed the test, but all cells without a resistance layer failed (ignited). Figure 41 shows the highest cell temperature during the impact test. [Figure 41] Figure 41 shows the maximum temperatures during the impact tests for cells 1, 3, 4, 5, and 6 described in Examples 9-12. [Figure 42] Figure 42 shows the cycle life of cell 3. After 100 cycles, the cell lost approximately 2%, which was similar to the value for a cell without a resistive layer (average, ~2.5%; not shown). [Modes for carrying out the invention]

[0055] High-energy-density rechargeable batteries, including lithium-ion batteries, that are safe, long-lasting, and capable of extended operation are the goals of battery manufacturers. One aspect of safe battery operation is controlling the heat generated by the rechargeable battery. As mentioned above, many factors, such as battery damage, accidents, and excessive internal current, can increase the heat generated by a rechargeable battery beyond its heat dissipation capacity. When the heat generated by a battery exceeds its heat dissipation capacity, the battery becomes susceptible to thermal runaway, overheating, or even fire or violent explosion. The following describes devices and methods related to thermally operated internal current interrupters that prevent thermal runaway by interrupting the internal circuitry of a rechargeable battery.

[0056] Another aspect of safe battery operation is controlling the reactions at the electrodes of these rechargeable batteries during both charging and discharging. As described above, during use, current flows to the outside of the battery through the external circuit, causing ions to move from one electrode to the other. In some cases, overcharging can occur, leading to thermal runaway within the battery. Below, we describe devices and methods related to internal current limiters that limit the rate of internal discharge of a rechargeable battery in the event of an internal short circuit.

[0057] A further aspect of safe battery operation is controlling the discharge of these rechargeable batteries. As described above, in rechargeable batteries where ions can flow through the battery but current flows outside the battery through an external circuit, a separator or barrier layer is used to separate the negative and positive electrodes. Due to many factors, the separator can tear, which can cause a short circuit within the rechargeable battery. A short circuit leads to rapid discharge, and in some cases, overheating and thermal runaway. Below, we describe devices and methods related to internal current limiters that limit the rate of internal discharge of a rechargeable battery in the event of an internal short circuit.

[0058] The terms used herein are intended to describe only certain exemplary embodiments and are not intended to limit the disclosure. As used herein, singular nouns also include plural nouns unless the context clearly indicates otherwise. The terms “comprises” and / or “comprising,” as used herein, identify the presence of a given feature, integer, process, operation, and / or component, but do not exclude the presence or addition of one or more other features, integers, processes, operations, elements, components, and / or groups thereof.

[0059] In this specification, terms such as “first,” “second,” etc., are used to describe various members, elements, regions, layers, and / or parts, but these members, regions, layers, and / or parts should not be limited by these terms. These terms are used simply to distinguish one member, element, region, and / or part from other members, elements, regions, layers, and / or parts. Thus, for example, the first member, element, region, layer, and / or part described below may be referred to as the second member, element, region, layer, and / or part without departing from the teachings of this disclosure.

[0060] Figures 1A-1G are schematic diagrams illustrating an exemplary configuration of a film-type lithium-ion battery having one or more resistive layers (6 in Figures 4A-4D) that function as current limiters. These layers protect the battery from overheating in the event of an internal short circuit and, in combination with a current interrupter 8 that is thermally activated by rising temperatures, irreversibly interrupt the self-discharge process if the battery overheats or reaches a dangerous temperature. Figures 1A and 1C show a battery configuration having a cathode current collector 101, a cathode energy layer 102, a separator 103, an anode energy layer 104, a resistive limiter and thermal interruption layer 105, and an anode current collector 106. The configuration shown in Figure 1B has a cathode current collector 101, a cathode energy layer 102, a separator 103, a first anode energy layer 107, a resistive limiter and thermal interruption layer 105, a second anode energy layer 108, and an anode current collector 106. Figure 1D shows a configuration comprising a cathode current collector 101, a first cathode energy layer 109, a separator 103, a second cathode energy layer 110, a resistance limiter and thermal insulation layer 105, an anode energy layer 104, and an anode current collector 106. Figure 1E-1G shows a battery configuration comprising a cathode current collector 101, a cathode energy layer 102, a separator 103, an anode energy layer 104, a first resistance limiter and thermal insulation layer 111, a second resistance limiter and thermal insulation layer 112, an anode energy layer 104, and an anode current collector 106.

[0061] Figures 2A and 2B are schematic diagrams illustrating exemplary configurations of film-type lithium-ion batteries having one or more layers that function as a combined current limiter 6 and current interrupter 8. These layers protect the battery from overheating in the event of an internal short circuit and, in combination with the current interrupter 8 which is voltage-activated by an increase in voltage, irreversibly interrupt the self-discharge process if the battery overheats. Figure 2A shows a battery configuration having an anode current collector 201, an anode energy layer 202, a separator 203, a cathode energy layer 204, a resistance limiter and thermal interruption layer 205, and a cathode current collector 206. The configuration shown in Figure 2B has an anode current collector 201, an anode energy layer 202, a separator 203, a first cathode energy layer 207, a resistance limiter and thermal interruption layer 205, a second cathode energy layer 208, and a cathode current collector 206.

[0062] Figures 3A and 3B are schematic diagrams illustrating an exemplary configuration of a film-type lithium-ion battery having one or more resistive layers that function as current limiters 6. These layers protect the battery from overheating in the event of an internal short circuit and, in combination with a current interrupter 8 that is thermally activated by rising temperatures, irreversibly interrupt the self-discharge process if the battery overheats or reaches a dangerous temperature. Furthermore, in combination with a current interrupter 8 that is activated by increasing voltage, irreversibly interrupts the self-discharge process if the battery is overcharged. Figure 3A shows the configuration of a battery having an anode current collector 301, an anode energy layer 302, a separator 303, a cathode energy layer 304, a resistive limiter, a thermal and voltage interruption layer 305, and a cathode current collector 306. The configuration shown in Figure 3B includes an anode current collector 301, an anode energy layer 302, a separator 303, a first cathode energy layer 307, a resistance limiter, a thermal and voltage blocking layer 305, a second cathode energy layer 308, and a cathode current collector 306.

[0063] Figures 4C and 4D show the film-type lithium-ion battery of Figure 1A, 2A, or 3A. More specifically, Figures 4A-4D show the current flowing through a film-type lithium-ion battery that is discharged to supply power to a load (L). Figures 4A and 4C show the current flow in a film-type lithium-ion battery with an undamaged, fully functional separator 2 (no short circuit). Figures 4B and 4D show the current flow in a film-type lithium-ion battery with a resistive layer that functions as a current limiter 6, where the separator 2 is short-circuited by a conductive dendrite 10. In Figures 4B and 4D, the separator 2 is subjected to internal discharge by the dendrite 10 penetrating it. Note that in a device with a separator 2 without a short circuit (Figures 4A and 4C) and a conventional device with a short-circuited separator 2 (Figure 4B), current flows from one current collector 4 to the other current collector. However, in the exemplary apparatus of this disclosure having a short-circuited separator 2 and a resistive layer 6 (Figure 4D), the current is diverted away from the current collector 4 and significantly reduced. In Figure 4D, the interrupter 8 is not triggered.

[0064] Figures 5C and 5D show the film-type lithium-ion battery of Figure 1A, 2A, or 3A. More specifically, Figures 5A-5D show the current flow through the film-type lithium-ion battery when being charged by a smart power supply (PS), which stops charging when an abnormal charging voltage is detected. Figures 5A and 5C show the current flow in a film-type lithium-ion battery with an undamaged, fully functional separator 2 (no short circuit). Figures 5B and 5D show the current flow in a film-type lithium-ion battery with a separator 2 short-circuited by a conductive dendrite 10. Note that in the device with a separator 2 without a short circuit (Figures 5A and 5C) and the conventional device with a short-circuited separator 2 (Figure 5B), current flows from one current collector 4 to the other. However, in the exemplary device of this disclosure having a short-circuited separator 2 and a resistive layer 6 (Figure 5D), the current is diverted away from the current collector 4 and significantly reduced. In Figure 5D, the interrupter 8 is not triggered.

[0065] Figures 6C and 6D show the film-type lithium-ion battery of Figure 1A, 2A, or 3A after the interrupter 8 has been triggered by excessive temperature or voltage. More specifically, Figures 6A-6D show the current flowing through a film-type lithium-ion battery being discharged to supply power to a load (L). Figures 6A and 6C show the current flow in a film-type lithium-ion battery with an undamaged, fully functional separator 2 (no short circuit). Figures 6B and 6D show the current flow in a film-type lithium-ion battery that is short-circuited by a conductive dendrite 10 penetrating the separator 2. Note that in the device with a separator 2 without a short circuit (Figures 6A and 6C) and the conventional device with a short-circuited separator 2 (Figure 6B), current flows from one current collector 4 to the other current collector. However, in an exemplary apparatus of this disclosure (Figure 6D) having both a short-circuited separator 2 and a resistive layer (current limiter 6) and a current interrupter 8, the current is diverted from the current collector 4 and significantly reduced. In Figure 6D, the interrupter 8 is triggered.

[0066] Figures 7C and 7D show the film-type lithium-ion battery of Figure 1A, 2A, or 3A after the interrupter 8 has been triggered by excessive temperature or voltage. More specifically, Figure 7 shows the current flow through the film-type lithium-ion battery when being charged by a smart power supply (PS), and charging stops when an abnormal charging voltage is detected. Figures 7A and 7C show the current flow of a film-type lithium-ion battery with an undamaged, fully functional separator 2 (no short circuit). Figures 7B and 7D show the current flow of a film-type lithium-ion battery with a short circuit caused by a separator 2 short-circuited by a conductive dendrite 10. Note that in a device with a separator 2 without a short circuit (Figures 7A and 7C) and a conventional device with a short-circuited separator 2 (Figure 7B), current flows from one current collector 4 to the other current collector. However, in an exemplary apparatus of the present disclosure (Figure 7D) having a short-circuited separator 2 and a resistive layer (current limiter 6), the current is diverted from the current collector 4 and significantly reduced. In Figure 7D, the interrupter 8 is triggered.

[0067] Figures 8C and 8D show film-type lithium-ion batteries of Figures 1A, 2A, or 3A. More specifically, Figures 8A-8D show the current flowing through a film-type lithium-ion battery that is discharged to supply power to a load (L). Figures 8A and 8C show the current flow in a film-type lithium-ion battery with an undamaged, fully functional separator 2 (no short circuit). Figures 8B and 8D show the current flow in a film-type lithium-ion battery with a resistive layer that functions as a current limiter 6, where the separator 2 is short-circuited due to damage 16. In Figures 8B and 8D, the cell is undergoing internal discharge through a tear 16 that penetrates the separator 2. Note that in a device with an unshort-circuited separator 2 (Figures 8A and 8C) and a conventional device with a short-circuited separator 2 (Figure 8B), current flows from one current collector 4 to the other current collector. However, in an exemplary apparatus of this disclosure (Figure 8D) having a short-circuited separator 2 and a resistive layer 6, the current is diverted away from the current collector 4 and significantly reduced. In Figure 8D, the interrupter 8 is not triggered.

[0068] Figures 9C and 9D show the film-type lithium-ion battery of Figure 1A, 2A, or 3A. More specifically, Figures 9A-9D show the current flow through the film-type lithium-ion battery when being charged by a smart power supply (PS), and charging stops when an abnormal charging voltage is detected. Figures 9A and 9C show the current flow in a film-type lithium-ion battery with an undamaged, fully functional separator 2 (no short circuit). Figures 9B and 9D show the current flow in a film-type lithium-ion battery with a separator 2 that is short-circuited by a damaged portion 16. Note that in the device with a separator 2 that is not short-circuited (Figures 9A and 9C) and the conventional device with a short-circuited separator 2 (Figure 9B), current flows from one current collector 4 to the other current collector. However, in the exemplary device of this disclosure having a short-circuited separator 2 and a resistive layer 6 (Figure 9D), the current is diverted away from the current collector 4 and significantly reduced. In Figure 9D, the interrupter 8 is not triggered.

[0069] Figures 10C and 10D show the film-type lithium-ion battery of Figure 1A, 2A, or 3A after the interrupter 8 has been triggered by excessive temperature or voltage. More specifically, Figures 10A-10D show the current flowing through a film-type lithium-ion battery being discharged to supply power to a load (L). Figures 10A and 10C show the current flow in a film-type lithium-ion battery with an undamaged, fully functional separator 2 (no short circuit). Figures 10B and 10D show the current flow in a film-type lithium-ion battery with a short circuit due to a damaged portion 16. Note that in a device with an unshort-circuited separator 2 (Figures 10A and 10C) and a conventional device with a short-circuited separator 2 (Figure 10B), current flows from one current collector 4 to the other current collector. However, in an exemplary apparatus of this disclosure (Figure 10D) having both a short-circuited separator 2 and a resistive layer (current limiter 6) and a current interrupter 8, the current is diverted from the current collector 4 and significantly reduced. In Figure 10D, the interrupter 8 is triggered.

[0070] Figures 11C and 11D show the film-type lithium-ion battery of Figure 1A, 2A, or 3A after the interrupter 8 has been triggered by excessive temperature or voltage. More specifically, Figures 11A-11D show the current flow through the film-type lithium-ion battery when being charged by a smart power supply (PS), and charging stops when an abnormal charging voltage is detected. Figures 11A and 11C show the current flow of a film-type lithium-ion battery with an undamaged, fully functional separator 2 (no short circuit). Figures 11B and 11D show the current flow of a film-type lithium-ion battery with a separator 2 that has been short-circuited by a damaged portion 16. Note that in a device with a separator 2 that is not short-circuited (Figures 11A and 11C) and a conventional device with a short-circuited separator 2 (Figure 11B), current flows from one current collector 4 to the other current collector. However, in an exemplary apparatus of this disclosure (Figure 11D) having a short-circuited separator 2 and a resistive layer (current limiter 6), the current is diverted from the current collector 4 and significantly reduced. In Figure 11D, the interrupter 8 is triggered.

[0071] Figure 12A shows a resistance layer 6 with a high proportion of binder-coated ceramic particles. The intervening voids between the coated ceramic particles make the resistance layer 6 porous. Figure 12B shows a resistance layer 6 with a high proportion of ceramic particles bound together by binder particles. The intervening voids between the coated ceramic particles make the resistance layer 6 porous. Figure 12C shows a resistance layer 6 with an intermediate proportion (less than 80%) of ceramic particles held together with the binder. The resistance layer 6 lacks intervening voids between the coated ceramic particles and is non-porous.

[0072] Current limiter A first aspect of this disclosure relates to an improved high-energy-density HEDR battery, the type comprising an anode energy layer 12, a cathode energy layer 14, a separator 2 disposed between the anode energy layer 12 and the cathode energy layer 14 to prevent internal discharge, and at least one current collector that exchanges electrons with either the anode energy layer or the cathode energy layer. The anode energy layer and the cathode energy layer each have an internal resistivity. The HEDR battery has a preferred temperature range for discharging current and an upper temperature safety limit. If the separator fails, improvements can be used to limit the rate of internal discharge through the failed separator and the resulting generation of Joule heat. More specifically, the improvements include a resistive layer 6 interposed between the separator and one of the current collectors 4 to limit the rate of internal discharge through the failed separator if the separator fails. The resistive layer 6 has a constant resistivity at temperatures between the preferred temperature range and the upper temperature safety limit. The constant resistivity of the resistive layer 6 is greater than the internal resistivity of any of the energy layers. The resistive layer 6 helps prevent the battery from exceeding its upper temperature safety limit in the event of separator failure.

[0073] Some embodiments of this disclosure include the following types of improved high-energy-density rechargeable batteries: 1. The two electrodes (12 and 14) of opposite polarity are characterized by resistivity, safe operating temperature range, and safe charging voltage, and the two electrodes are exposed to the risk of overcharging above the safe charging voltage and resulting short circuit formation, and the two electrodes are exposed to the risk of thermal runaway above the safe operating temperature range. 2. A separator 2 that separates two electrodes and prevents internal discharge between them, wherein the separator is exposed to the risk of forming a short circuit, which would potentially allow a rapid internal discharge between the two electrodes, which would potentially allow a rapid generation of Joule heat from them, which would potentially allow a thermal runaway. 3. At least one electrode using a current collector 4 for electron transfer. 4. A current limiter 6 that forms an electrical coupling between one of the electrodes and the corresponding current collector, the current limiter having a resistivity that resistively blocks the current, and when the separator forms a short circuit, it diverts the current from the coupled electrode current collector and reduces the rate of internal discharge between the two electrodes. 5. A current interrupter 8 having an engaging configuration, a non-engaging configuration, and a gas generating element that transitions the current interrupter from the engaging configuration to the non-engaging configuration, wherein the gas generating element has a trigger that generates gas, the trigger is selected from the group consisting of a temperature trigger and a voltage trigger, the temperature trigger operates at a temperature exceeding the safe operating temperature range, and the voltage trigger operates at a voltage exceeding the safe charging voltage, and in the engaging configuration, the current interrupter electrically connects one of the electrodes to the corresponding current collector by lamination coupling, while in the non-engaging configuration, the lamination coupling As the bond separates, the current interrupter forms a non-conductive gap that interrupts the electrical coupling between the electrode and the corresponding current collector, and the current interrupter transitions from the engaged configuration to the disengaged configuration by initiating the operation of the gas generating element in response to a trigger, and the generated gas separates the laminated bond in order to interrupt the electrical coupling between the electrode and the corresponding current collector, thereby reducing the risk of thermal runaway caused by short circuits of the separator, overcharging of the electrodes, and overheating of the electrodes when used in combination with the current limiter.

[0074] In some embodiments, the current interrupter starts operating based on temperature.

[0075] In some embodiments, the current interrupter has a layer containing a single gas generating element that is activated by temperature.

[0076] In some embodiments, the current interrupter is initiated by voltage.

[0077] In some embodiments, the current interrupter has a layer containing a single gas generating element that is activated by voltage.

[0078] In some embodiments, the current interrupter is activated by temperature and voltage.

[0079] In some embodiments, the current interrupter has a layer containing a single gas generating element that is activated by temperature and voltage.

[0080] In some embodiments, the current interrupter has two gas generating elements, one of which is activated by temperature and the other by voltage.

[0081] In some embodiments, the current interrupter has a layer containing one or more inorganic gas-generating compounds that generate gas at a specific temperature or voltage.

[0082] In some embodiments, the inorganic gas-generating compound is selected from the group consisting of CaCO3, La2(CO3)3, Na2SO3, ZnCO3Zn(OH)2, CuCO3Cu(OH)2, and Cu(NO3)2, as disclosed in Figure 32.

[0083] In some embodiments, the current interrupter has a layer containing one or more organic gas-generating compounds that generate gas at a specific temperature or voltage.

[0084] In some embodiments, the organic gas generating compound is selected from the group consisting of Carbopol, Tolon, AI-50, CMC, and PVDF, as disclosed in Figure 34.

[0085] In some embodiments, the current interrupter has a layer containing inorganic and organic gas-generating compounds that generate gas at a specific temperature or voltage.

[0086] In some embodiments of the improved high-energy-density rechargeable battery, as disclosed in Figures 1A, 1C, and 2A, the current limiter and current interrupter are simultaneously incorporated within a protective layer interposed by lamination between the same electrode and current collector.

[0087] In some embodiments of the improved high-energy-density rechargeable battery, as disclosed in Figure 3A, a current limiter and a current interrupter that initiates operation on both temperature and voltage are simultaneously incorporated within a protective layer interposed between the same electrode and current collector by lamination.

[0088] In some embodiments, the improved high-energy-density rechargeable battery is of a type that includes two current collectors, a first current collector and a second current collector, and two electrodes, a first electrode and a second electrode, and the improvement includes the following features: As disclosed in Figure 1E, The current limiter and current interrupter are simultaneously incorporated into a first protective layer interposed between the first electrode and the first current collector by lamination, and The current limiter and current interrupter are simultaneously incorporated into a second protective layer that is laminated between the second electrode and the second current collector.

[0089] In some embodiments, the improved high-energy-density rechargeable battery is of a type that includes two current collectors, a first current collector and a second current collector, and two electrodes, a first electrode and a second electrode, and the improvement includes the following features: As disclosed in Figure 1F, The current limiter and current interrupter are simultaneously incorporated into a first protective layer interposed between the first electrode and the first current collector by lamination, and The current limiter and current interrupter are simultaneously incorporated into a second protective layer that is interposed between the second electrode and the separator by lamination.

[0090] In some embodiments, the improved high-energy-density rechargeable battery is of a type that includes two current collectors, a first current collector and a second current collector, and two electrodes, a first electrode and a second electrode, and the improvement includes the following features: As disclosed in Figure 1G, The current limiter and current interrupter are simultaneously incorporated into a first protective layer interposed between the first electrode and the separator by lamination, and The current limiter and current interrupter are simultaneously incorporated into a second protective layer that is laminated between the second electrode and the second current collector.

[0091] In some embodiments, the improved high-energy-density rechargeable battery includes two current collectors, a first current collector and a second current collector, and two electrodes, a first electrode and a second electrode, wherein the first electrode includes a first portion and a second portion, and the second portion of the first electrode is interposed between the first portion of the first electrode and the first current collector, and the improvement includes the following features: 1. The current limiter is stacked between the first portion of the first electrode and the second portion of the first electrode; and 2. The current interrupter is stacked between the second portion of the first electrode and the first current collector.

[0092] In some embodiments, the improved high-energy-density rechargeable battery includes two current collectors, a first current collector and a second current collector, and two electrodes, a first electrode and a second electrode, wherein the first electrode includes a first portion and a second portion, and the second portion of the first electrode is interposed between the first portion of the first electrode and the first current collector. The improvement further includes the following features: as disclosed in Figures 1B and 2B, a current limiter and a current interrupter are simultaneously incorporated in a protective layer interposed by lamination between the first portion and the second portion of the first electrode.

[0093] In some embodiments, the improved high-energy-density rechargeable battery is of a type that includes two current collectors, a first current collector and a second current collector, and two electrodes, a first electrode and a second electrode, wherein the first electrode includes a first portion and a second portion, and the second portion of the first electrode is interposed between the first portion of the first electrode and the first current collector. The improvement further includes the following features: as disclosed in Figure 3B, a current limiter and a current interrupter that is activated by both temperature and voltage are simultaneously incorporated in a protective layer interposed by lamination between the first portion and the second portion of the first electrode.

[0094] In some embodiments, the improved high-energy-density rechargeable battery includes two current collectors, a first current collector and a second current collector, and two electrodes, a first electrode and a second electrode, wherein the second electrode includes a first portion and a second portion, and the first portion of the second electrode is interposed between the second portion of the second electrode and the second current collector, and the improvement includes the following features: 1. The current limiter is stacked between the first portion of the second electrode and the second portion of the second electrode; and 2. The current interrupter is stacked between the second portion of the second electrode and the second current collector.

[0095] In some embodiments, the improved high-energy-density rechargeable battery includes two current collectors, a first current collector and a second current collector, and two electrodes, a first electrode and a second electrode, wherein the second electrode includes a first portion and a second portion, and the first portion of the second electrode is interposed between the second portion of the second electrode and the second current collector, and the improvement includes the following features: 1. The current limiter is stacked between the first portion of the second electrode and the second portion of the second electrode; and 2. The current interrupter is stacked between the second portion of the second electrode and the second current collector.

[0096] In some embodiments, the improved high-energy-density rechargeable battery includes two current collectors, a first current collector and a second current collector, and two electrodes, a first electrode and a second electrode, wherein the first electrode includes a first portion and a second portion, and the first portion of the second electrode is interposed between the second portion of the second electrode and the second current collector. The improvement further includes the following features: as disclosed in Figure 1D, a current limiter and a current interrupter are simultaneously incorporated in a protective layer interposed by lamination between the first and second portions of the second electrode.

[0097] In some embodiments, the improved high-energy-density rechargeable battery includes two current collectors, a first current collector and a second current collector, and two electrodes, a first electrode and a second electrode, wherein the first electrode includes a first portion and a second portion, and the second portion of the first electrode is interposed between the first portion of the first electrode and the first current collector, and the improvement further includes the following features: 1. The current limiter is stacked between the second portion of the first electrode and the first current collector; and 2. The current interrupter is stacked between the first portion of the first electrode and the second portion of the first electrode.

[0098] In some embodiments, the improved high-energy-density rechargeable battery is of a type that includes two current collectors, a first current collector and a second current collector, and two electrodes, a first electrode and a second electrode, and the improvement further includes the following features: 1. The current limiter is stacked between the first electrode and the first current collector; and 2. The current interrupter is stacked between the second electrode and the second current collector.

[0099] In some embodiments, the improved high-energy-density rechargeable battery is of a type in which each electrode has a temperature range for safe operation and an internal resistivity, and the improvement further includes the following features: within the temperature range for safe operation, the current limiter has a resistivity greater than the internal resistivity of the electrodes with which the current limiter is stacked.

[0100] In some embodiments, the improved high-energy-density rechargeable battery further includes the following improvements: the current limiter is absent at temperatures within a temperature range for safe operation, and the resistivity transition switch is absent.

[0101] In some embodiments, the improved high-energy-density rechargeable battery is of a type in which each electrode has a temperature range for standard operation, and the improvement further includes the following features: the current limiter has a resistivity lower than the internal resistivity of the electrode within the temperature range for standard operation, and a resistivity higher than the internal resistivity of the electrode at temperatures above the temperature range for standard operation.

[0102] In some embodiments, the improved high-energy-density rechargeable battery is of a type in which each electrode has a temperature range for standard operation, and the improvement further includes the following features: the current interrupter operates at temperatures above the temperature range for standard operation.

[0103] In some embodiments, the improved high-energy-density rechargeable battery is of a type in which each electrode has a temperature range for standard operation, and the improvement further includes the following features: the current interrupter operates at temperatures above the temperature range for standard operation but within the temperature range for safe operation.

[0104] In some embodiments, the improved high-energy-density rechargeable battery is of a type in which each electrode has an internal resistivity within a temperature range for safe operation, and the improvement further includes the following features: the current limiter has a resistivity greater than the internal resistivity of the electrodes stacked with the current limiter, within a temperature range for safe operation.

[0105] In some embodiments of the improved high-energy-density rechargeable battery, the improvements further include the following features: the current limiter and current interrupter are simultaneously incorporated within a protective layer interposed by lamination between the same electrode and current collector.

[0106] In some embodiments, the improved high-energy-density rechargeable battery is of a type in which each electrode has a voltage range for safe operation, and the improvement further includes the following features: the current interrupter operates at a voltage exceeding the voltage range for standard operation.

[0107] In some embodiments, the improved high-energy-density rechargeable battery is of a type in which each electrode has a voltage range for standard operation and a voltage range for safe operation, and the improvement further includes the following features: the current interrupter operates at a voltage that is above the voltage range for standard operation but within the voltage range for safe operation.

[0108] In some embodiments of the improved high-energy-density rechargeable battery, the improvements further include the following features: the current limiter and current interrupter are simultaneously incorporated within a protective layer interposed by lamination between the same electrode and current collector.

[0109] Another embodiment of the present disclosure includes an improved high-energy-density rechargeable (HEDR) battery, the rechargeable battery comprising two electrodes of opposite polarity, a separator separating the two electrodes, and at least one current collector electrically coupled to one of the electrodes, wherein the separator prevents internal discharge between the two electrodes, and damage to the separator potentially results in internal discharge between the two electrodes (as shown in Figures 6A-6B and 7A-7B), the internal discharge resulting in the generation of Joule heat as a potential hazard, and the improvements include: 1. A thermally operated current interrupter and a voltage-operated current interrupter, wherein the thermally operated current interrupter can be laminated between one of the current collectors and one of the electrodes by a lamination method, and when not operating, the thermally operated current interrupter electrically couples the current collector to the electrode laminated with the current collector, while when operating, it forms a non-conductive gap to detach the current collector from the electrode laminated with the current collector (as shown in Figures 6C-6D and 7C-7D), and the electrical isolation slows down the rate of internal discharge between the two electrodes if the separator is damaged; 2. A voltage-operated current interrupter can be laminated between one of the current collectors and one of the electrodes by a lamination method. When the voltage-operated current interrupter is not operating, it electrically couples the current collector to the electrode laminated with the current collector. When operating, it forms a non-conductive gap to detach the current collector from the electrode laminated with the current collector, thereby electrically separating the current collector from the electrode. This electrical separation slows down the rate of internal discharge between the two electrodes if the separator is damaged (as shown in Figures 6C-6D and 7C-7D). This allows for the slowing down of Joule heating in the event of separator failure, by activating either a thermally actuated or voltage-actuated current interrupter, thereby reducing the potential hazard.

[0110] Some embodiments of the present disclosure include a method for avoiding thermal runaway inside a high-energy-density rechargeable battery that is subjected to internal discharge due to separator failure, the method including separating the electrodes inside the battery from the current collector by generating a gas from a thermosensitive gas generating material in a barrier layer interposed between the electrodes and the current collector, the separation electrically separating the electrodes from the current collector to slow the rate of internal discharge.

[0111] Some embodiments of the present disclosure include a method for avoiding thermal runaway inside a high-energy-density rechargeable battery that is at risk of separator damage due to voltage overcharging (shown in Figures 7A-7B), the method including separating the electrodes inside the battery from the current collector by generating a gas from a voltage-sensitive gas-generating material in a barrier layer interposed between the electrodes and the current collector, the separation electrically separating the electrodes from the current collector to interrupt voltage overcharging (shown in Figures 7C-7D).

[0112] The following abbreviations have the following meanings: Carbopol (registered trademark)-934 = Cross-linked polyacrylate polymer supplied by Lubrizol Advanced Materials, Inc. CMC = Carboxymethylcellulose CMC-DN-800H = CMC in which the sodium salt of the carboxymethyl group is substituted with ammonium (supplied by Daicel Fine Chemicals). MCMB = Mesocarbon Microbeads NMC = Nickel, Manganese, and Cobalt NMP = N-methylpyrrolidone PTC = positive temperature coefficient PVDF = Polyvinylidene Fluoride SBR = Styrene-butadiene rubber Super (registered trademark) P = conductive carbon black supplied by Timcal Corporation. Torlon (registered trademark) AI-50 = Water-soluble derivative of Torlon 4000TF Torlon (registered trademark) 4000TF = Pure resin polyamide-imide (PAI) powder

[0113] The methods for fabricating the resistive layer and the electrode active layer are described below, along with the assembly of the battery cell.

[0114] The general fabrication process for the resistive layer (first layer) is shown below: i. Dissolve the binder in a suitable solvent. ii. Add conductive additives and ceramic powder to the binder solution. iii. The slurry prepared in step ii is applied to the surface of the metal foil and then dried to form a resistive layer on the surface of the metal foil.

[0115] The general procedure for electrode fabrication (on the upper surface of the first layer) is as follows: i. Dissolve the binder in a suitable solvent. ii. Add conductive additives and ceramic powder to the binder solution. iii. Add the cathode material or anode material to the slurry prepared in step v and mix to form a slurry for electrode coating. iv. The electrode slurry prepared in step vi is applied to the surface of the layer obtained in step iii. v. Compress the electrode to the desired thickness.

[0116] The general process for assembling cells is as follows: i. Dry the positive electrode at 125°C for 10 hours and the negative electrode at 140°C for 10 hours. ii. Punch out electrodes into the individual pieces that have electrode tabs. iii. The positive and negative electrodes are stacked together with a separator acting as an intermediate layer. iv. Place the jelly roll prepared in step xi into an aluminum composite bag.

[0117] The general procedure for performing an impact test on the battery cells described in this specification, as shown in Figure 21, is described below. i. Charge the cell at 2A, 4.2V for 3 hours. ii. Place the cell on a hard, flat surface such as concrete. iii. Attach the thermocouple to the surface of the cell using high-temperature tape, and connect the positive and negative tabs to the voltmeter. iv. Place a steel rod (diameter 15.8mm ± 0.1mm, length approximately 70mm) so that its side crosses the center of the cell. A 9.1±0.46Kg steel block (75mm in diameter, 290mm in height) is suspended at a height of 610±25mm above the v. cell. vi. Protect the steel block using a containment tube (8 cm inner diameter), release the steel block inside the tube, and let it freefall onto a steel rod lying on the surface of the cell, damaging the separator while recording the temperature. vii. Leave the steel rods and steel blocks on the surface of the cell to allow the cell temperature to stabilize at near room temperature. viii. Exam finished.

[0118] The general procedure for performing an overcharge test is as follows: i. Charge the cell at 2A, 4.2V for 3 hours. ii. Place the charged cells in a room temperature oven. iii. Connect the cell to a power supply (Hewlett-Packard). iv. Set the power supply voltage and current to 12V and 2A. v. Turn on the power switch and perform an overcharge test while recording the temperature and voltage. vi. The test is terminated when the cell temperature decreases and stabilizes near room temperature.

[0119] The general procedure for performing a resistance measurement test is as follows: i. Place a 1 square copper foil (4.2 × 2.8 cm) with tabs on a metal plate (~12 × ~8 cm). Next, cut the thermal tape into small pieces and carefully cover the 1 square copper foil. ii. Cut the electrodes into small pieces so that they are slightly larger than the copper foil. Place the electrodes on top of the copper foil. iii. Place another copper foil (4.2 × 2.8 cm) with tabs on the surface of the electrode and repeat steps i-ii using it. iv. At this point, gather them together, cover with heat-resistant tape, and remove any air bubbles. v. Cut out V-shaped pieces of metal from both tabs. vi. Attach the metal clamp to the completed strip and tighten it with screws. Ensure the screws are tightly fastened. vii. Attach the tab to the connector of the Battery HiTester (manufactured by HIOKI USA) and measure the resistance to confirm that a good sample for measurement has been prepared. viii. Place the metal clamp inside the oven, connect the V-shaped tabs to the connector, and tighten the screws. Secure the thermocouple to the metal clamp with tape. ix. Connect the wiring from the oven to the battery high tester. Make sure you don't mix up the positive and negative terminals. x. Close the oven and raise the temperature to 200°C at a rate of 4°C / min to begin the test. Record data every 15 seconds. xi. Stop recording data when the temperature of the metal clamp and oven slightly exceeds 200°C. xii. Turn off the oven and the battery high tester. xiii. Exam ends.

[0120] The general steps for performing cycle life testing are as follows: i. Pause for 5 minutes. ii. Discharge to 2.8V at 1A. iii. Take a 20-minute break. Charge at 0.7A until it reaches 4.2V for 270 minutes. v. Pause for 10 minutes. Discharge to 2.8V with vi.0.7A. vii. Pause for 10 minutes. viii. Repeat steps iii to vii 100 times. ix. Exam ends.

[0121] The general procedure for discharge testing at 1A, 3A, 6A, and 10A for battery cells with a resistive layer is as follows: i. Pause for 5 minutes. ii. Discharge to 2.8V at 1A. iii. Take a 20-minute break. Charge at 0.7A until it reaches 4.2V for 270 minutes. v. Pause for 10 minutes. Discharge to 2.8V with 1A. vii. Pause for 10 minutes. viii. Charge at 0.7A until it reaches 4.2V in 270 minutes. ix. Take a 10-minute break. Discharge to 2.8V at x.3A. Charge at xi.0.7A until it reaches 4.2V in 270 minutes. xii. Pause for 10 minutes. Discharge to 2.8V at xiii.6A. Charge to 4.2V for 270 minutes at xiv.0.7A. Pause for 10 minutes. Discharge to 2.8V with xvi.10A. xvii. Pause for 10 minutes. xviii. Exam finished.

[0122] definition Unless otherwise specified, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the field to which this disclosure pertains. If there are multiple definitions of a term herein, the definitions in this section shall prevail unless otherwise specified.

[0123] As used herein, “high energy density rechargeable (HEDR) battery” means a battery capable of storing a relatively large amount of electrical energy on the order of approximately 50 W-hr / kg or more per unit weight, and is designed for reuse and can be recharged after repeated use. Examples of HEDRs, not limited to HEDRs, include metal-ion batteries and metal batteries.

[0124] As used herein, “metal-ion battery” refers to any type of rechargeable battery in which metal ions move from the negative electrode to the positive electrode during discharge and in the reverse direction during charge. Examples of metal-ion batteries, not limited to those containing lithium ions, aluminum ions, potassium ions, sodium ions, magnesium ions, and others.

[0125] As used herein, the "metal ion battery" means any type of rechargeable battery in which the anode is a metal or metal alloy. The anode may be solid or liquid. During discharge, metal ions move from the negative electrode to the positive electrode, and during charging, they move in the opposite direction. Non-limiting examples of metal batteries include M-S, M-NiCl2, M-V2O5, M-Ag2VP2O8, M-TiS2, M-TiO2, M-MnO2, M-Mo3S4, M-MoS6Se2, M-MoS2, M-MgCoSiO4, M-Mg 1.03 Mn 0.97 SiO4, and others, where M = Li, Na, K, Mg, Al or Zn.

[0126] As used herein, the "lithium ion battery" means any type of rechargeable battery in which lithium ions move from the negative electrode to the positive electrode during discharge and in the opposite direction during charging. Non-limiting examples of lithium ion batteries include lithium cobalt oxide (LiCoO2), lithium iron phosphate (LiFeO4), lithium cobalt phosphate (LiCoPO4), lithium-excess layered oxides such as (LiMnO3)x(LiMO2) (M = Ni, Co, Mn), olivine, LiMSiO4 (M = iron, cobalt, nickel and vanadium), lithium manganese oxide (LiMn2O4), lithium nickel oxide (LiNiO2), lithium nickel manganese cobalt oxide (LiNiMnCoO2), lithium nickel cobalt aluminum oxide (LiNiCoAlO2), lithium titanate (Li4Ti5O 12Lithium-ion batteries may also include lithium dititanate, lithium / graphene, lithium / graphene oxide-coated sulfur, lithium-sulfur, lithium-purpurine, and others. Lithium-ion batteries may also have various anodes, including silicon-carbon nanocomposite anodes. Lithium-ion batteries can take various forms, including small cylindrical (solid without terminals), large cylindrical (solid with large screw terminals), prismatic (semi-rigid plastic case with large screw terminals), and pouches (soft flat bodies). Lithium-ion batteries may be placed in soft packaging or pouches. The electrolytes in these batteries may be liquid electrolytes (carbonate-based or ionic, etc.), solid electrolytes, polymer-based electrolytes, or mixtures of these electrolytes.

[0127] As used herein, “aluminum-ion battery” refers to any type of rechargeable battery in which aluminum ions move from the negative electrode to the positive electrode during discharge and in the reverse direction during charge. Examples of aluminum-ion batteries, not limited to Al n M2(XO4)3, where X = Si, P, S, Mo, As, etc., and M = Fe, Ca, Mg, V, Cr, etc., and Al x (V4O8), Al x NiS2,Al x FeS2,Al x VS2,Al x Aluminum transition metal oxides such as WS2 (Al x MO2, where M = Fe, Mn, Ni, Mo, Co, Cr, Ti, V, etc.

[0128] As used herein, “potassium-ion battery” refers to any type of rechargeable battery in which potassium ions move from the negative electrode to the positive electrode during discharge and in the reverse direction during charge. Examples of potassium-ion batteries, not limited to K n M2(XO4)3, where X = Si, P, S, Mo, As, etc., and M = Fe, Ca, Mg, V, Cr, etc., and also includes potassium transition metal oxides (KMO2, where M = Fe, Mn, Ni, Mo, Co, Cr, Ti, V, etc.).

[0129] As used herein, “sodium-ion battery” refers to any type of rechargeable battery in which sodium ions move from the negative electrode to the positive electrode during discharge and in the reverse direction during charge. Examples of sodium-ion batteries, not limited to Na n M2(XO4)3, where X = Si, P, S, Mo, As, etc., and M = Fe, Ca, Mg, V, Cr, etc.; NaV 1-x Cr x PO4F, NaVPO4F, Na4Fe3(PO4)2(P2O7), Na2FePO4F, Na2FeP2O7, Na 2 / 3 [Fe 1 / 2 Mn 1 / 2 ]O2, Na(Ni 1 / 3 Fe 1 / 3 Mn 1 / 3 )O2, NaTiS2, NaFeF3;Na 2 / 3 [Fe 1 / 2 Mn 1 / 2 ]O2, Na(Ni 1 / 3 Fe 1 / 3 Mn 1 / 3 )O2, Na x Mo2O4, NaFeO2, Na 0.7 CoO2, NaCrO2, NaMnO2, N a0.44 MnO2, Na 0.7 MnO2, Na 0.7 MnO 2.25 kaNa 2 / 3 Mn 2 / 3 Ni 1 / 3 O2, Na 0.61 Ti 0.48 Mn 0.52 Sodium transition metal oxides such as O2 (NaMO2, where M = Fe, Mn, Ni, Mo, Co, Cr, Ti, V, etc.); Na 1+x V3O8, Na x V2O5, and Na x It contains vanadium oxides such as VO2 (x=0.7,1).

[0130] As used herein, “magnesium-ion battery” refers to any type of rechargeable battery in which magnesium ions move from the negative electrode to the positive electrode during discharge and in the reverse direction during charge. An example of a magnesium-ion battery, not limited to Mg n M2(XO4)3, where X = Si, P, S, Mo, As, etc., and M = Fe, Ca, Mg, V, Cr, etc.; includes magnesium transition metal oxides (MgMO2, where M = Fe, Mn, Ni, Mo, Co, Cr, Ti, V, etc.).

[0131] As used herein, “silicon-ion battery” refers to any type of rechargeable battery in which silicon ions move from the negative electrode to the positive electrode during discharge and in the reverse direction during charge. Examples of silicon-ion batteries, not limited to Si, include n M2(XO4)3, where X = Si, P, S, Mo, As, etc., and M = Fe, Ca, Mg, V, Cr, etc.; includes silicon transition metal oxides (SiMO2, where M = Fe, Mn, Ni, Mo, Co, Cr, Ti, V, etc.).

[0132] As used herein, “binder” means any material that provides mechanical adhesion and unlimited tolerance to large volume changes. Examples of binders, not limited to these, include styrene-butadiene rubber (SBR) binders, polyvinylidene fluoride (PVDF) binders, carboxymethylcellulose (CMC) binders, polyacrylic acid (PAA) binders, polyvinyl acid (PVA) binders, and poly(vinylpyrrolidone) (PVP) binders.

[0133] As used herein, “conductive additives” means any material that increases the conductivity of a material. Examples of conductive additives, not limited to these, include carbon black additives, graphite non-aqueous ultrafine carbon (UFC) suspensions, carbon nanotube composite (CNT) additives (monolayer and multilayer), carbon nanoonion (CNO) additives, graphene-based additives, reduced graphene oxide (rGO), conductive acetylene black (AB), conductive poly(3-methylthiophene) (PMT), fibrous nickel powder additives, aluminum powder, and electrochemically active oxides such as lithium nickel manganese cobalt oxide.

[0134] As used herein, “metal foil” refers to any metal foil that is stable under high voltage. Examples of metal foil, though not limited to these, include aluminum foil, copper foil, titanium foil, steel foil, nanocarbon paper, graphene paper, and carbon fiber sheets.

[0135] As used herein, “ceramic powder” means any unfired electrical insulator or conductor. Examples of ceramic powders, not limited to these, include barium titanate (BaTiO3), barium zirconium titanate, strontium titanate (SrTiO3), calcium titanate (CaTiO3), magnesium titanate (MgTiO3), calcium magnesium titanate, zinc titanate (ZnTiO3), lanthanum titanate (LaTiO3), neodymium titanate (Nd2Ti2O7), barium zirconate (BaZrO3), and calcium zirconate (CaZrO3). This includes magnesium lead niobate, zinc lead niobate, lithium niobate (LiNbO3), barium stannate (BaSnO3), calcium stannate (CaSnO3), aluminum magnesium silicate, sodium silicate (NaSiO3), magnesium silicate (MaSiO3), barium tantalate (BaTa2O6), niobium oxide, zirconium tin titanate, silicon dioxide (SiO2), aluminum oxide (Al2O3), titanium dioxide (TiO2), etc.

[0136] As used herein, “gas-generating material” refers to any material that decomposes to generate gas at high temperature or high voltage, and which either directly generates gas or indirectly generates gas through the reaction of decomposition products produced by the reaction of the gas-generating material with other materials contained in the battery (e.g., electrolyte and electrodes). Examples of gas-generating materials that are not limited to M n (CO3) m M n (SO3) m M n (NO3) m , 1 M n 2 M n (CO3)m, NaSiO3 * Inorganic carbonates such as H2O, CuCO3Cu(OH)2, and polymethacrylates [-CH2-C(CH3)(COOM)-] p or polyacrylates [-CH2-CH(COOM)-] p It contains organic carbonates such as M, 1 M, 2 M is independently selected from the group consisting of Ba, Ca, Cd, Co, Cu, Fe, K, Li, Mg, Mn, Na, Ni, Pb, Sr, and Zn, where n is 1 to 3 and m is 1 to 4. In some embodiments, M is independently selected from the group consisting of ammonium ions, pyridinium ions, and quaternary ammonium ions. In some embodiments, the gas-generating material may decompose to produce a liquid (e.g., water). The liquid reacts with another material contained in the cell to form a gas, which detaches the electrodes (for example, water reacts with the electrolyte [LiFP6] to form gaseous HF and lithium at the negative electrode, generating hydrogen gas (H2). If the cell temperature exceeds the vaporization temperature of the liquid, the liquid may undergo a phase change to form a gas, which also detaches the electrodes).

[0137] A layer was applied to the metal foil using an automated coating machine (compact coater, model No. 3R250W-2D) manufactured by Sank Metal. Next, the layer was compressed to the desired thickness using a calendering machine (model No. X15-300-1-DZ) manufactured by Beijing Sevenstar Huachuang Electronics. [Examples]

[0138] The present disclosure will be described in more detail using the following embodiments, but the present disclosure is not limited to the embodiments shown below.

[0139] Example 1 The following describes the fabrication of the reference electrode, positive electrode, and negative electrode, as well as the preparation of completed cell No. 1, which will be used for resistance measurement, discharge capacity testing at 50°C, shock testing, and cycle life evaluation.

[0140] A) Fabrication of POS1A as an example of cathode fabrication i) PVDF (21.6g) was dissolved in NMP (250g); ii) Add carbon black (18g) and mix at 6500rpm for 15 minutes; iii) LiNi 0.5 Mn 0.3 Co 0.2 O2(NMC) (560.4g) was added to the slurry prepared in step ii, and the mixture was heated at 6500 rpm for 30 minutes to produce a fluid slurry. iv) Some NMP was added to adjust the viscosity; v) Using an automated coating apparatus equipped with a first heating region set to approximately 80°C and a second heating region set to approximately 130°C, the slurry was applied onto a 15 μm thick aluminum foil, and the NMP was evaporated. The final solid load was approximately 15.55 mg / cm³. 2 Next, the positive electrode layer was compressed to a thickness of approximately 117 μm. The fabricated electrode was treated as having zero voltage relative to a standard graphite electrode and used for impedance measurement at 0V to investigate its relationship with temperature, and then dried for cell assembly.

[0141] B) Fabrication of NEG2A as an example of negative electrode fabrication i) CMC (5.2g) was dissolved in deionized water (~300g); ii) Add carbon black (8.4g) and mix at 6500rpm for 15 minutes; iii) Activated graphite for the negative electrode (JFE Chemical Co., Ltd., graphitized mesophase carbon microbead (MCMB) and synthetic graphite (TIMCAL)) (378.4 g in total) was added to the slurry prepared in step ii, and mixed at 6500 rpm for 30 minutes to prepare a fluid slurry; iv) SBR (50% solids, aqueous suspension) (16.8 g) was added to the slurry prepared in step ii and mixed at 6500 rpm for 5 minutes; v) The viscosity was adjusted for smooth application; vi) Using an automated coating apparatus equipped with a first heating region set to approximately 70°C and a second heating region set to approximately 100°C, this slurry was applied onto a 9 μm thick copper foil, and the water was evaporated. The final solid load was approximately 9.14 mg / cm³. 2 Next, the negative electrode layer was compressed to a thickness of approximately 117 μm. The fabricated negative electrode was then dried for cell assembly.

[0142] C) Creation of cells for evaluation i) The electrodes were punched out to create individual pieces with electrode tabs; ii) The positive electrode was dried at 125°C for 10 hours, and the negative electrode was dried at 140°C for 10 hours; iii) The positive and negative electrodes were stacked with a separator as an intermediate layer; iv) The jelly rolls prepared in step iii were laid flat inside an aluminum composite bag; v) Dry the bags from step iv in a vacuum oven at 70°C; vi) The bag from step v was filled with an organic carbonate-based electrolyte containing LiPF6; vii) The bag from step vi was sealed; viii) Let it stand for 16 hours; ix) The cell was charged to 4.2V at a rate of C / 20 for 5 hours, then charged to 4.2V at a rate of 0.5C for 2 hours, then rested for 20 minutes, and then discharged to 2.8V at a rate of 0.5C. Under vacuum, the cell was punctured to release the gas, and then resealed. The fabricated cell was used for evaluation and other tests such as discharge capacity testing at 50°C, shock testing, and cycle life testing.

[0143] Figure 15 shows the change in resistance with temperature rise for the positive electrode recovered by autopsying a 3.6V cell. The resistance decreased by approximately 10 times. Figure 18 shows the discharge capacity at discharge currents of 1, 3, 6, and 10 A. Figure 20 shows the cell impedance at 1 kHz, the capacity at currents of 1 A, 3 A, 6 A, and 10 A, and the ratio of the capacity at 3, 6, and 10 A to the capacity at 1 A. Figure 22 shows the temperature profile of the cell during the shock test. Figure 23 shows the maximum temperature of the cell during the shock test. The cell ignited during the shock test. Figure 25 shows the voltage and temperature profile of the cell during an overcharge test at 12V / 2A. The cell ignited during the overcharge test (Figure 28).

[0144] Example 2 The following describes the preparation of the CaCO3-based gas generator, resistive layer, positive electrode, and negative electrode, as well as the preparation of completed cell No. 3, which will be used for resistance measurement, discharge capacity testing at 50°C, shock testing, and cycle life evaluation.

[0145] A) Positive electrode POS3B as an example of gas generating agent and resistance layer (first layer) fabrication. i) Toron® 4000TF (0.8g) was dissolved in NMP (10g); ii) PVDF (4.8g) was dissolved in NMP (~70g); iii) The solutions prepared in steps i and ii were mixed, then carbon black (0.32 g) was added and mixed at 6500 rpm for 10 minutes; iv) Nano CaCO3 powder (34.08 g) was added to the solution prepared in step iii, and mixed at 6500 rpm for 20 minutes to prepare a fluid slurry; v) Using an automated coating apparatus equipped with a first heating region set to approximately 135°C and a second heating region set to approximately 165°C, the slurry was applied onto a 15 μm thick aluminum foil, and the NMP was evaporated. The final solid load was approximately 1 mg / cm². 2 That was the case.

[0146] B) Fabrication of POS3A as an example of cathode fabrication (second layer) i) PVDF (21.6g) was dissolved in NMP (250g); ii) Add carbon black (18g) and mix at 6500rpm for 15 minutes; iii) LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2(NMC) (560.4g) was added to the slurry prepared in step ii, and the mixture was heated at 6500 rpm for 30 minutes to produce a fluid slurry. iv) Some NMP was added to adjust the viscosity; v) Using an automated coating apparatus equipped with a first heating region set to approximately 85°C and a second heating region set to approximately 135°C, this slurry was applied onto POS3B (Example 2A), and the NMP was evaporated. The final solid load was approximately 19.4 mg / cm³. 2 Next, the positive electrode layer was compressed to a thickness of approximately 153 μm. The fabricated electrode was treated as having zero voltage relative to a standard graphite electrode and used for impedance measurement at 0V to investigate its relationship with temperature.

[0147] C) Fabrication of NEG3A as an example of negative electrode fabrication i) Dissolve CMC (13g) in deionized water (~1000g); ii) Add carbon black (20g) and mix at 6500rpm for 15 minutes; iii) Activated graphite for the negative electrode (JFE Chemical Co., Ltd., graphitized mesophase carbon microbeads (MCMB) and synthetic graphite (TIMCAL)) (945.92 g in total) was added to the slurry prepared in step ii, and mixed at 6500 rpm for 30 minutes to prepare a fluid slurry; iv) SBR (50% solids, aqueous suspension) (42 g) was added to the slurry prepared in step ii and mixed at 6500 rpm for 5 minutes; v) The viscosity was adjusted for smooth application; vi) Using an automated coating apparatus equipped with a first heating region set to approximately 100°C and a second heating region set to approximately 130°C, the slurry was applied onto a 9 μm thick copper foil, and the water was evaporated. The final solid load was approximately 11.8 mg / cm³. 2 Next, the negative electrode layer was compressed to a thickness of approximately 159 μm. The fabricated negative electrode was then dried for cell assembly.

[0148] D) Creation of cells for evaluation i) The electrodes were punched out to create individual pieces with electrode tabs; ii) The positive electrode was dried at 125°C for 10 hours, and the negative electrode was dried at 140°C for 10 hours; iii) The positive and negative electrodes were stacked with a separator as an intermediate layer; iv) The jelly rolls prepared in step iii were laid flat inside an aluminum composite bag; v) Dry the bags from step iv in a vacuum oven at 70°C; vi) The bag from step v was filled with an organic carbonate-based electrolyte containing LiPF6; vii) The bag from step vi was sealed; viii) Let it stand for 16 hours; ix) The cell was charged to 4.2V at a rate of C / 50 for 8 hours, then charged to 4.2V at a rate of 0.5C for 2 hours, then left to rest for 20 minutes, and then discharged to 2.8V at a rate of 0.5C; x) Under vacuum, a hole was made in the cell to release the gas, and then it was resealed. The fabricated cell was used for evaluation and other tests such as discharge capacity testing at 50°C, shock testing, and cycle life testing.

[0149] Figure 16 shows the change in resistance with increasing temperature for positive electrodes recovered from disassembled 0, 3.6, and 4.09V cells. Resistance increased with increasing temperature, particularly in positive electrodes obtained from cells with voltages of 3.66V and 4V. Figure 19 shows the discharge capacity at 1, 3, and 6A at 50°C. Cell capacity decreased significantly with increasing current, indicating a strong influence from the resistive layer. Figure 20 shows the cell impedance at 1kHz, the capacity at currents of 1A, 3A, 6A, and 10A, and the ratio of capacity at 3, 6, and 10A to capacity at 1A. Figure 26 shows the overcharge profile during the overcharge test. Figure 28 shows the maximum cell temperature during the overcharge test and the residual current at the end of the overcharge test. Figure 29 shows the discharge capacity against the number of cycles. The cell lost approximately 1% of its capacity, which is approximately 100% better than that of the reference cell (2.5%). Figure 22 shows the cell temperature profile during the impact test. Figure 23 shows the maximum cell temperature during the impact test.

[0150] Example 3 The following describes the preparation of a gas generating agent containing 50% Al2O3 and 50% CaCO3, a resistive layer, a positive electrode, and a negative electrode, as well as the preparation of a completed cell No. 4 used for resistance measurement, discharge capacity testing at 50°C, shock testing, and cycle life evaluation.

[0151] A) Positive electrode POS4B as an example of gas generating agent and resistive layer (first layer) fabrication. i) Toron® 4000TF (0.8g) was dissolved in NMP (10g); ii) PVDF (4.8g) was dissolved in NMP (~70g); iii) The solutions prepared in steps i and ii were mixed, then carbon black (0.32 g) was added and mixed at 6500 rpm for 10 minutes; iv) Nano CaCO3 powder (17.04 g) and Al2O3 powder (17.04 g) were added to the solution prepared in step iii and mixed at 6500 rpm for 20 minutes to prepare a fluid slurry; v) Using an automated coating apparatus equipped with a first heating region set to approximately 135°C and a second heating region set to approximately 165°C, the slurry was applied onto a 15 μm thick aluminum foil, and the NMP was evaporated. The final solid load was approximately 1 mg / cm². 2 That was the case.

[0152] B) Fabrication of POS4A as an example of cathode fabrication (second layer) i) PVDF (21.6g) was dissolved in NMP (250g); ii) Add carbon black (18g) and mix at 6500rpm for 15 minutes; iii) LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2(NMC) (560.4g) was added to the slurry prepared in step ii, and the mixture was heated at 6500 rpm for 30 minutes to produce a fluid slurry. iv) Some NMP was added to adjust the viscosity; v) Using an automated coating apparatus equipped with a first heating region set to approximately 85°C and a second heating region set to approximately 135°C, this slurry was applied onto POS4B (Example 3A), and the NMP was evaporated. The final solid load was approximately 19.4 mg / cm³. 2 Next, the positive electrode layer was compressed to a thickness of approximately 153 μm. The fabricated electrode was treated as having zero voltage relative to a standard graphite electrode and used for impedance measurement at 0V to investigate its relationship with temperature.

[0153] C) Fabrication of NEG4A as an example of negative electrode fabrication i) Dissolve CMC (13g) in deionized water (~1000g); ii) Add carbon black (20g) and mix at 6500rpm for 15 minutes; iii) Activated graphite for the negative electrode (JFE Chemical Co., Ltd., graphitized mesophase carbon microbeads (MCMB) and synthetic graphite (TIMCAL)) (945.92 g in total) was added to the slurry prepared in step ii, and mixed at 6500 rpm for 30 minutes to prepare a fluid slurry; iv) SBR (50% solids, aqueous suspension) (42 g) was added to the slurry prepared in step ii and mixed at 6500 rpm for 5 minutes; v) The viscosity was adjusted for smooth application; vi) Using an automated coating apparatus equipped with a first heating region set to approximately 100°C and a second heating region set to approximately 130°C, the slurry was applied onto a 9 μm thick copper foil, and the water was evaporated. The final solid load was approximately 11.8 mg / cm³. 2 Next, the negative electrode layer was compressed to a thickness of approximately 159 μm. The fabricated negative electrode was then dried for cell assembly.

[0154] D) Creation of cells for evaluation i) The electrodes were punched out to create individual pieces with electrode tabs; ii) The positive electrode was dried at 125°C for 10 hours, and the negative electrode was dried at 140°C for 10 hours; iii) The positive and negative electrodes were stacked with a separator as an intermediate layer; iv) The jelly rolls prepared in step iii were laid flat inside an aluminum composite bag; v) Dry the bags from step iv in a vacuum oven at 70°C; vi) The bag from step v was filled with an organic carbonate-based electrolyte containing LiPF6; vii) The bag from step vi was sealed; viii) Let it stand for 16 hours; ix) The cell was charged to 4.2V at a rate of C / 50 for 8 hours, then charged to 4.2V at a rate of 0.5C for 2 hours, then left to rest for 20 minutes, and then discharged to 2.8V at a rate of 0.5C; x) Under vacuum, a hole was made in the cell to release the gas, and then it was resealed. The fabricated cell was used for evaluation and other tests such as discharge capacity testing at 50°C, shock testing, and cycle life testing.

[0155] Figure 20 shows the cell impedance at 1 kHz, the capacitance at currents of 1 A, 3 A, 6 A, and 10 A, and the ratios of the capacitances at 3 A, 6 A, and 10 A to the capacitance at 1 A. Figure 22 shows the temperature profile of the cell during the impact test. Figure 23 shows the maximum temperature of the cell in the impact test. Figure 26 shows the overcharge profile during the 12 V / 2 A overcharge test. Figure 28 shows the maximum temperature of the cell during the overcharge test.

[0156] Example 4 The preparation of a gas generating agent obtained by mixing Al2O3 and sodium silicate (NaSiO3), a resistance layer, a positive electrode, and a negative electrode, as well as resistance measurement, a discharge capacity test at 50 °C, an impact test, and the preparation of a completed cell No. 5 used for evaluating cycle life are described below.

[0157] A) Positive electrode POS5B as an example of the preparation of a gas generating agent and a resistance layer (first layer) i) Torlon® 4000TF (0.8 g) was dissolved in NMP (~10 g); ii) PVDF (4.8 g) was dissolved in NMP (60 g); iii) The solutions prepared in steps i and ii were mixed, and then carbon black (0.32 g) was added and mixed at 6500 rpm for 10 minutes; iv) Nano Al2O3 powder (17.04 g) and NaSiO3 (17.04 g) were added to the solution prepared in step iii and mixed at 6500 rpm for 20 minutes to prepare a fluid slurry; v) Using an automatic coating device equipped with a first heating region set at approximately 135 °C and a second heating region set at approximately 165 °C, this slurry was coated on an aluminum foil with a thickness of 15 μm, and NMP was evaporated. The final solid loading was approximately 0.7 mg / cm 2 was.

[0158] B) Preparation of POS5A (second layer) as an example of positive electrode preparation i) PVDF (21.6 g) was dissolved in NMP (270 g); ii) Carbon black (18 g) was added and mixed at 6500 rpm for 15 minutes; iii) LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2(NMC) (560.4g) was added to the slurry prepared in step ii, and the mixture was heated at 6500 rpm for 30 minutes to produce a fluid slurry. iv) Some NMP was added to adjust the viscosity; v) Using an automated coating apparatus equipped with a first heating region set to approximately 85°C and a second heating region set to approximately 135°C, this slurry was applied onto POS5B (Example 4A), and the NMP was evaporated. The final solid load was approximately 19.4 mg / cm³. 2 Next, the positive electrode layer was compressed to a thickness of approximately 153 μm. The fabricated electrode was treated as having zero voltage relative to a standard graphite electrode and used for impedance measurement at 0V to investigate its relationship with temperature.

[0159] C) Fabrication of NEG5A as an example of negative electrode fabrication i) Dissolve CMC (13g) in deionized water (~1000g); ii) Add carbon black (20g) and mix at 6500rpm for 15 minutes; iii) Activated graphite for the negative electrode (JFE Chemical Co., Ltd., graphitized mesophase carbon microbeads (MCMB) and synthetic graphite (TIMCAL)) (945.92 g in total) was added to the slurry prepared in step ii, and mixed at 6500 rpm for 30 minutes to prepare a fluid slurry; iv) SBR (50% solids, aqueous suspension) (42 g) was added to the slurry prepared in step ii and mixed at 6500 rpm for 5 minutes; v) The viscosity was adjusted for smooth application; vi) Using an automated coating apparatus equipped with a first heating region set to approximately 100°C and a second heating region set to approximately 130°C, the slurry was applied onto a 9 μm thick copper foil, and the water was evaporated. The final solid load was approximately 11.8 mg / cm³. 2 Next, the negative electrode layer was compressed to a thickness of approximately 159 μm. The fabricated negative electrode was then dried for cell assembly.

[0160] D) Creation of cells for evaluation i) The electrodes were punched out to create individual pieces with electrode tabs; ii) The positive electrode was dried at 125°C for 10 hours, and the negative electrode was dried at 140°C for 10 hours; iii) The positive and negative electrodes were stacked with a separator as an intermediate layer; iv) The jelly rolls prepared in step iii were laid flat inside an aluminum composite bag; v) Dry the bags from step iv in a vacuum oven at 70°C; vi) The bag from step v was filled with an organic carbonate-based electrolyte containing LiPF6; vii) The bag from step vi was sealed; viii) Let it stand for 16 hours; ix) The cell was charged to 4.2V at a rate of C / 50 for 8 hours, then charged to 4.2V at a rate of 0.5C for 2 hours, then left to rest for 20 minutes, and then discharged to 2.8V at a rate of 0.5C; x) Under vacuum, a hole was made in the cell to release the gas, and then it was resealed. The fabricated cell was used for evaluation and other tests such as discharge capacity testing at 50°C, shock testing, and cycle life testing.

[0161] Figure 20 shows the cell impedance at 1 kHz, the capacitance at currents of 1 A, 3 A, 6 A, and 10 A, and the ratio of capacitance at 3, 6, and 10 A to capacitance at 1 A. Figure 22 shows the cell temperature profile during the shock test. Figure 23 shows the maximum cell temperature during the shock test. Figure 28 shows the maximum cell temperature during the 12 V / 2 A overcharge test.

[0162] Example 5 The following describes the preparation of a gas generating agent containing 52% CaCO3 and 48% PVDF, a resistive layer, a positive electrode, and a negative electrode, as well as the preparation of a completed cell No. 6 used for resistance measurement, discharge capacity testing at 50°C, shock testing, and cycle life evaluation.

[0163] A) Positive electrode POS6B as an example of gas generating agent and resistive layer (first layer) fabrication. i) PVDF (23.25 g) was dissolved in NMP (~250 g); ii) The solutions prepared in step i were mixed, then carbon black (1.85 g) was added and mixed at 6500 rpm for 10 minutes; iv) Nano CaCo3 powder (24.9 g) was added to the solution prepared in step iii, and mixed at 6500 rpm for 20 minutes to prepare a fluid slurry; v) Using an automatic coating device equipped with a first heating zone set at about 135 °C and a second heating zone set at about 165 °C, this slurry was coated onto an aluminum foil with a thickness of 15 μm, and NMP was evaporated. The final solid loading was about 1 mg / cm 2 It was.

[0164] B) Preparation of POS6A as an example of positive electrode preparation (second layer) i) PVDF (24 g) was dissolved in NMP (300 g); ii) Carbon black (12 g) was added and mixed at 6500 rpm for 15 minutes; iii) LiNi 0.4 Co 0.3 Mn 0.4 Co 0.3 O2 (NMC) (558 g) was added to the slurry prepared in step ii and mixed at 6500 rpm for 30 minutes to prepare a fluid slurry; iv) Some NMP was added for viscosity adjustment; v) Using an automatic coating device equipped with a first heating zone set at about 85 °C and a second heating zone set at about 135 °C, this slurry was coated onto POS6B (Example 5A), and NMP was evaporated. The final solid loading was about 22 mg / cm 2 It was. Next, the positive electrode layer was compressed to a thickness of about 167 μm. The prepared electrode was regarded as having a zero voltage with respect to a standard graphite electrode, and was used for impedance measurement at 0 V to examine the relationship with temperature.

[0165] C) Preparation of NEG6A as an example of negative electrode preparation i) CMC (9 g) was dissolved in deionized water (~530 g); ii) Carbon black (12 g) was added and mixed at 6500 rpm for 15 minutes; iii) Active graphite for the negative electrode (JFE Chemical Co., Ltd., graphitized mesophase carbon microbeads (MCMB)) (564 g) was added to the slurry prepared in step ii, and mixed at 6500 rpm for 30 minutes to prepare a fluid slurry; iv) SBR (solid content 50%, water suspension) (30 g) was added to the slurry prepared in step ii and mixed at 6500 rpm for 5 minutes; v) For smooth coating, some water was added to adjust the viscosity; vi) Using an automatic coating device equipped with a first heating zone set at about 95 °C and a second heating zone set at about 125 °C, this slurry was coated on a copper foil with a thickness of 9 μm, and water was evaporated. The final solid loading was about 12 mg / cm 2 It was. Next, the negative electrode layer was compressed to a thickness of about 170 μm. The prepared negative electrode was dried for cell assembly.

[0166] D) Fabrication of cells for evaluation i) Electrodes were punched out to produce individual pieces with electrode tabs; ii) The positive electrode was dried at 125 °C for 10 hours, and the negative electrode was dried at 140 °C for 10 hours; iii) The positive electrode and the negative electrode were laminated with a separator as an intermediate layer; iv) The jelly roll prepared in step iii was laid flat in an aluminum composite bag; v) The bag from step iv was dried in a vacuum oven at 70 °C; vi) The bag from step v was filled with an organic carbonate-based electrolyte containing LiPF6; vii) The bag from step vi was sealed;[[ID=2*]] viii) It was left standing for 16 hours; ix) The cell was charged to 4.2 V at a rate of C / 50 for 8 hours, then charged to 4.2 V at a rate of 0.5 C for 2 hours, then rested for 20 minutes, and then discharged to 2.8 V at a rate of 0.5 C; x) Under vacuum, a hole was made in the cell to release the gas, and then it was resealed. The fabricated cell was used for evaluation and other tests such as discharge capacity testing at 50°C, shock testing, and cycle life testing.

[0167] Figure 20 shows the cell impedance at 1 kHz, the capacitance at currents of 1 A, 3 A, 6 A, and 10 A, and the ratio of capacitance at 3, 6, and 10 A to capacitance at 1 A. Figure 22 shows the cell temperature profile during the shock test. Figure 23 shows the maximum cell temperature during the shock test. Figure 28 shows the maximum cell temperature during the overcharge test.

[0168] Example 6 The following describes the preparation of a positive electrode for measuring chemical decomposition voltage.

[0169] POS7B was created using the following method: i) Deionized water (~300g) was mixed with Carbopol®-934 (19.64g); ii) Super P (registered trademark) (160 mg) and LiOH (200 mg) were added to the slurry prepared in step i, and the mixture was mixed at 5000 rpm for 30 minutes; iii) An appropriate amount of deionized water was added to prepare the slurry, forming a spreadable slurry; iv) Using an automated coating apparatus equipped with a first heating region set to approximately 135°C and a second heating region set to approximately 165°C, the slurry was applied onto 15 μm aluminum foil, and the NMP was evaporated. The final solid load was approximately 0.7 mg / cm³. 2 That was the case.

[0170] POS8B was fabricated using the following method: i) Deionized water (~100g) was mixed with AI-50 (19.85g); ii) Super P (registered trademark) (160 mg) was added to the slurry prepared in step i, and mixed at 5000 rpm for 30 minutes; iii) An appropriate amount of deionized water was added to prepare the slurry, forming a spreadable slurry; iv) Using an automatic coating device equipped with a first heating zone set at approximately 135 °C and a second heating zone set at approximately 165 °C, this slurry was applied onto a 15-μm aluminum foil, and NMP was evaporated. The final solid loading was approximately 0.7 mg / cm 2 It was.

[0171] POS9B was prepared based on the following method: i) Deionized water (~322 g) was mixed with 19.85 g of CMC-DN-800H; ii) Super P® (160 mg) was added to the slurry prepared in step i), and mixed at 5000 rpm for 30 minutes; iii) An appropriate amount of deionized water was added to adjust the slurry to form a coatable slurry; iv) Using an automatic coating device equipped with a first heating zone set at approximately 135 °C and a second heating zone set at approximately 165 °C, this slurry was applied onto a 15-μm aluminum foil, and NMP was evaporated. The final solid loading was approximately 0.7 mg / cm 2 It was.

[0172] POS13B was prepared based on the following method: i) Torlon® 4000TF (400 mg) was dissolved in NMP (4 g); ii) PVDF-A (2.4 g) was dissolved in NMP (30 g); iii) The above two solutions were mixed, and Super P® (160 mg) was added and mixed at 5000 rpm for 30 minutes; iv) Using an automatic coating device equipped with a first heating zone set at approximately 13 °C and a second heating zone set at approximately 16 °C, this slurry was applied onto a 15-μm aluminum foil, and NMP was evaporated. The final solid loading was approximately 0.7 mg / cm 2 It was.

[0173] Example 7 The electrochemical tests of the positive electrode coated with the gas generation layer are described below.

[0174] The decomposition voltage of all resistive layers was measured at room temperature using linear sweep voltammetry with a VMP2 multi-channel potentiostat apparatus, employing a three-electrode configuration (resistive layer as the working electrode, lithium metal as the reference electrode, and lithium metal as the counter electrode). One 0.3 cm × 2.0 m piece of the resistive layer served as the working electrode, and one 0.3 cm × 2.0 m piece of lithium served as the reference electrode and counter electrode. These electrodes were placed in a glass containing LiPF6 ethylene carbonate electrolyte (5 g). The sweep rate was 5 mV / sec within a voltage range of 0 to 6 V. Figures 31 and 33 show the decomposition voltage profiles of these compounds. Figures 32 and 34 show the peak current and peak voltage of each of the tested compounds.

[0175] Example 8 The following describes the preparation of the CaCO3-based gas generating agent, resistive layer, positive electrode, and negative electrode, as well as the preparation of completed cell No. 7 for resistance measurement, discharge capacity testing at 50°C, shock testing, and cycle life evaluation. The gas generating layer can function as a resistive layer if the content of conductive additives is within a specific range (at least 50%) such that the resistivity of the gas generating layer is greater than the resistivity of the energy layer or layer that provides the majority (>50%) of the battery's discharge energy. The content of the gas generating layer can be between 2% and 99%.

[0176] A) Cathode POS71A as an example of gas generation layer (first layer) fabrication. i) Toron® 4000TF (0.9g) was dissolved in NMP (10g); ii) PVDF (5.25 g) was dissolved in NMP (~68 g); iii) The solutions prepared in steps i and ii were mixed, then carbon black (1.8 g) was added and mixed at a speed of approximately 6500 rpm for 10 minutes; iv) Nano CaCO3 powder (7.11 g) and 134.94 g of LiNi 0.33 Al 0.33 Co 0.33 O2 was added to the solution prepared in step iii, and the mixture was stirred at 6500 rpm for 20 minutes to prepare a fluid slurry. v) Using an automated coating apparatus equipped with a first heating region set to approximately 90°C and a second heating region set to approximately 140°C, the slurry was applied onto a 15 μm thick aluminum foil, and the NMP was evaporated. The final solid load was approximately 4 mg / cm³. 2 That was the case.

[0177] B) Fabrication of POS071B as an example of cathode fabrication (second layer) i) PVDF (25.2g) was dissolved in NMP (327g); ii) Add carbon black (21g) and mix at 6500 rpm for 15 minutes; iii) LiNi 0.82 Al 0.03 Co 0.15 O2(NCA) (649g) was added to the slurry prepared in step ii, and the mixture was heated at 6500 rpm for 30 minutes to produce a fluid slurry. iv) Some NMP was added to adjust the viscosity; v) Using an automated coating apparatus equipped with a first heating region set to approximately 85°C and a second heating region set to approximately 135°C, the slurry was applied onto POS71A, and the NMP was evaporated. The final solid load was approximately 20.4 mg / cm³. 2 Next, the positive electrode layer was compressed to a thickness of approximately 155 μm.

[0178] C) Fabrication of NEG015B as an example of negative electrode fabrication i) CMC (15g) was dissolved in deionized water (~951g); ii) Add carbon black (15g) and mix at 6500rpm for 15 minutes; iii) Activated graphite for the negative electrode (JFE Chemical Co., Ltd., graphitized mesophase carbon microbead (MCMB)) (945g) was added to the slurry prepared in step ii, and mixed at 6500 rpm for 30 minutes to prepare a fluid slurry; iv) SBR (50% solids, aqueous suspension) (50 g) was added to the slurry prepared in step ii and mixed at 6500 rpm for 5 minutes; v) To ensure a smooth application, some water was added to adjust the viscosity; vi) Using an automated coating apparatus equipped with a first heating region set to approximately 100°C and a second heating region set to approximately 130°C, the slurry was applied onto a 9 μm thick copper foil, and the water was evaporated. The final solid load was approximately 11 mg / cm³. 2 Next, the negative electrode layer was compressed to a thickness of approximately 155 μm. The fabricated negative electrode was then dried for cell assembly.

[0179] D) Creation of cells for evaluation i) The electrodes were punched out to create individual pieces with electrode tabs; ii) The positive electrode was dried at ~125°C for 10 hours, and the negative electrode was dried at ~140°C for 10 hours; iii) The positive and negative electrodes were stacked with a separator as an intermediate layer; iv) The jelly rolls prepared in step iii were laid flat inside an aluminum composite bag; v) Dry the bags from step iv in a vacuum oven at 70°C; vi) The bag from step v was filled with a carbonate-based electrolyte; vii) The bag from step vi was sealed; viii) Let it stand for 16 hours; ix) The cells were charged to 4.2V at a rate of C / 50 for 8 hours, then charged to 4.2V at a rate of 0.5C for 2 hours, then rested for 20 minutes, and then discharged to 2.8V at a rate of 0.5C. The fabricated cells were used for evaluation and other tests such as overcharge testing.

[0180] Figure 35 shows the overcharge voltage, cell temperature, and oven chamber temperature during overcharge tests (2A and 12V). The maximum cell temperature during the overcharge test was approximately 83°C, and the cell passed the overcharge test. The embodiments described herein are not limited to but may include products (e.g., apparatus, systems, etc.), manufacturing methods or methods of use, material compositions, etc., that are consistent with the descriptions herein.

[0181] Example 9 The following describes the preparation of the Al2O3-based gas generator, resistance layer, positive electrode, and negative electrode, as well as the preparation of the completed cell 3 used for resistance measurement, discharge capacity testing at 50°C, shock testing, and cycle life evaluation.

[0182] A) Positive electrode POS3B as an example of resistive layer (first layer) fabrication. i) Toron® 4000TF (1g) was dissolved in NMP (10g); ii) PVDF (6g) was dissolved in NMP (70g); iii) The solutions prepared in steps i and ii were mixed, then carbon black (0.4 g) was added and mixed at a speed of approximately 6500 rpm for 10 minutes; iv) Nano Al2O3 powder (42 g) was added to the solution prepared in step iii, and the mixture was heated at 6500 rpm for 20 minutes to prepare a fluid slurry; v) Using an automated coating apparatus equipped with a first heating region set to approximately 130°C and a second heating region set to approximately 160°C, the slurry was applied onto a 15 μm thick aluminum foil, and the NMP was evaporated. The final solid load was approximately 1 mg / cm². 2 That was the case.

[0183] B) Fabrication of POS071B as an example of cathode fabrication (second layer) i) PVDF (21.6g) was dissolved in NMP (250g); ii) Add carbon black (18g) and mix at 6500rpm for 15 minutes; iii) LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2(NMC) (560.4g) was added to the slurry prepared in step ii, and the mixture was heated at 6500 rpm for 30 minutes to produce a fluid slurry. iv) Some NMP was added to adjust the viscosity; v) Using an automated coating apparatus equipped with a first heating region set to approximately 85°C and a second heating region set to approximately 135°C, the slurry was applied onto POS3B and the NMP was evaporated. The final solid load was approximately 19.4 mg / cm³. 2Next, the positive electrode layer was compressed to a thickness of approximately 153 μm. The fabricated electrode was treated as having zero voltage relative to a standard graphite electrode and used for impedance measurement at 0V to investigate its relationship with temperature.

[0184] C) Fabrication of NEG3A as an example of negative electrode fabrication i) Dissolve CMC (13g) in deionized water (~1000g); ii) Add carbon black (20g) and mix at 6500rpm for 15 minutes; iii) Activated graphite for the negative electrode (JFE Chemical Co., Ltd., graphitized mesophase carbon microbeads (MCMB) and synthetic graphite (TIMCAL)) (945.92 g in total) was added to the slurry prepared in step ii, and mixed at 6500 rpm for 30 minutes to prepare a fluid slurry; iv) SBR (50% solids, aqueous suspension) (42 g) was added to the slurry prepared in step ii and mixed at 6500 rpm for 5 minutes; v) To ensure a smooth application, some water was added to adjust the viscosity; vi) Using an automated coating apparatus equipped with a first heating region set to approximately 100°C and a second heating region set to approximately 130°C, the slurry was applied onto a 9 μm thick copper foil, and the water was evaporated. The final solid load was approximately 11.8 mg / cm³. 2 Next, the negative electrode layer was compressed to a thickness of approximately 159 μm. The fabricated negative electrode was then dried for cell assembly.

[0185] D) Creation of cells for evaluation i) The electrodes were punched out to create individual pieces with electrode tabs; ii) The positive electrode was dried at 125°C for 10 hours, and the negative electrode was dried at 140°C for 10 hours; iii) The positive and negative electrodes were stacked with a separator as an intermediate layer; iv) The jelly rolls prepared in step iii were laid flat inside an aluminum composite bag; v) Dry the bags from step iv in a vacuum oven at 70°C; vi) The bag from step v was filled with an organic carbonate-based electrolyte containing LiPF6; vii) The bag from step vi was sealed; viii) Let it stand for 16 hours; ix) The cell was charged to 4.2V at a rate of C / 50 for 8 hours, then charged to 4.2V at a rate of 0.5C for 2 hours, then rested for 20 minutes, and then discharged to 2.8V at a rate of 0.5C. Under vacuum, the cell was punctured to release the gas, and then resealed. The fabricated cell was used for evaluation and other tests such as discharge capacity testing at 50°C, shock testing, and cycle life testing.

[0186] Figure 38 shows the change in resistance with respect to temperature rise for the positive electrode recovered from a disassembled 4.09V cell. The change in resistance is small compared to that of the reference cell (Figure 37). Figure 42 shows the relationship between the number of cycles and the discharge capacity. The cell lost approximately 2% of its capacity, which is similar to that of the reference cell (2.5%). Figure 36 shows the cell impedance at 1kHz, the capacity at currents of 1A, 3A, 6A, and 10A, and the ratio of the capacity at 3, 6, and 10A to the capacity at 1A. Figure 40 shows the cell temperature profile during the shock test. Figure 41 shows the maximum cell temperature during the shock test.

[0187] Example 10 The following describes the fabrication of a resistive layer, positive electrode, and negative electrode containing 50% polyacrylic latex and 50% barium titanate (BaTiO2), as well as the fabrication of a completed cell 4 used for resistance measurement, discharge capacity testing at 50°C, shock testing, and cycle life evaluation.

[0188] A) Positive electrode POS4B as an example of resistive layer (first layer) fabrication. i) CMC (0.375g) was dissolved in deionized water (~30g); ii) The solutions prepared in step i were mixed, then carbon black (1.75 g) was added and mixed for several minutes; iii) Nano BaTiO2 powder (25 g) was added to the slurry prepared in step ii, and mixed at 6500 rpm for 20 minutes to prepare a fluid slurry; v) Using an automated coating apparatus equipped with a first heating region set to approximately 90°C and a second heating region set to approximately 140°C, the slurry was applied onto a 15 μm thick aluminum foil, and the water was evaporated. The final solid load was approximately 0.7 mg / cm³. 2 That was the case.

[0189] B) Fabrication of POS4A as an example of cathode fabrication (second layer) i) PVDF (14.4g) was dissolved in NMP (~160g); ii) Add carbon black (12g) and mix at 6500rpm for 15 minutes; iii) LiNi 0.5 Mn 0.3 Co 0.2 O2(NMC) (373.6g) was added to the slurry prepared in step ii, and the mixture was heated at 6500 rpm for 30 minutes to produce a fluid slurry. iv) Some NMP was added to adjust the viscosity; v) Using an automated coating apparatus equipped with a first heating region set to approximately 80°C and a second heating region set to approximately 130°C, this slurry was applied onto POS4B (Example 2A), and the NMP was evaporated. The final solid load was approximately 15.2 mg / cm³. 2 Next, the positive electrode layer was compressed to a thickness of approximately 113 μm. The fabricated electrode was treated as having zero voltage relative to a standard graphite electrode and used for impedance measurement at 0V to investigate its relationship with temperature.

[0190] C) Fabrication of NEG3A as an example of negative electrode fabrication i) CMC (7.8g) was dissolved in deionized water (~800g); ii) Add carbon black (12g) and mix at 6500rpm for 15 minutes; iii) Activated graphite for the negative electrode (JFE Chemical Co., Ltd., graphitized mesophase carbon microbeads (MCMB) and synthetic graphite (TIMCAL)) (568.6 g in total) was added to the slurry prepared in step ii, and mixed at 6500 rpm for 30 minutes to prepare a fluid slurry; iv) SBR (50% solids, aqueous suspension) (25.2 g) was added to the slurry prepared in step ii and mixed at 6500 rpm for 5 minutes; v) To ensure a smooth application, some water was added to adjust the viscosity; vi) Using an automated coating apparatus equipped with a first heating region set to approximately 70°C and a second heating region set to approximately 100°C, this slurry was applied onto a 9 μm thick copper foil, and the water was evaporated. The final solid load was approximately 8.99 mg / cm³. 2 Next, the negative electrode layer was compressed to a thickness of approximately 123 μm. The fabricated negative electrode was then dried for cell assembly.

[0191] D) Creation of cells for evaluation i) The electrodes were punched out to create individual pieces with electrode tabs; ii) The positive electrode was dried at 125°C for 10 hours, and the negative electrode was dried at 140°C for 10 hours; iii) The positive and negative electrodes were stacked with a separator as an intermediate layer; iv) The jelly rolls prepared in step iii were laid flat inside an aluminum composite bag; v) Dry the bags from step iv in a vacuum oven at 70°C; vi) The bag from step v was filled with an organic carbonate-based electrolyte containing LiPF6; vii) The bag from step vi was sealed; viii) Let it stand for 16 hours; ix) The cell was charged to 4.2V at a rate of C / 50 for 8 hours, then charged to 4.2V at a rate of 0.5C for 2 hours, then rested for 20 minutes, and then discharged to 2.8V at a rate of 0.5C. Under vacuum, the cell was punctured to release the gas, and then resealed. The fabricated cell was used for evaluation and other tests such as discharge capacity testing at 50°C, shock testing, and cycle life testing.

[0192] Figure 39 shows the discharge capacity at 50°C with currents of 1A, 3A, and 6A. The cell capacity decreases sharply with increasing current, indicating a strong influence of the resistive layer. Figure 36 shows the cell impedance at 1kHz, the capacity at currents of 1A, 3A, 6A, and 10A, and the ratio of the capacity at 3A, 6A, and 10A to the capacity at 1A. Figure 40 shows the cell temperature profile during the shock test. Figure 41 shows the maximum cell temperature during the shock test.

[0193] Example 11 The following describes the fabrication of the resistive layer in the negative electrode, the positive electrode and the negative electrode, as well as the fabrication of the completed cell 5 used for resistance measurement, discharge capacity testing at 50°C, shock testing, and cycle life evaluation.

[0194] A) Fabrication of POS5A as an example of cathode fabrication i) PVDF (31.5g) was dissolved in NMP (~340g); ii) Add carbon black (13.5 g) and mix at 6500 rpm for 15 minutes; iii) LiNi 0.33 Mn 0.33 Co 0.33 O2(NMC) (855g) was added to the slurry prepared in step ii, and the mixture was heated at 6500 rpm for 30 minutes to produce a fluid slurry. iv) Some NMP was added to adjust the viscosity; v) Using an automated coating apparatus equipped with a first heating region set to approximately 80°C and a second heating region set to approximately 130°C, the slurry was applied onto 15 μm aluminum foil, and the NMP was evaporated. The final solid load was approximately 14.8 mg / cm³. 2 Next, the positive electrode layer was compressed to a thickness of approximately 113 μm. The fabricated electrode was treated as having zero voltage relative to a standard graphite electrode and used for impedance measurement at 0V to investigate its relationship with temperature, and then dried for cell assembly.

[0195] B) Fabrication of NEG5B as an example of negative electrode fabrication (first layer) i) CMC (0.375g) was dissolved in deionized water (~90g); ii) Add carbon black (1.75 g) and mix at 6500 rpm for 15 minutes; iii) BaTiO2 (25 g in total) was added to the slurry prepared in step ii, and mixed at 6500 rpm for 30 minutes to prepare a fluid slurry; iv) SBR (50% solids, aqueous suspension) (45.6 g) was added to the slurry prepared in step iii and mixed at 6500 rpm for 5 minutes; v) The viscosity was adjusted for smooth application; vi) Using an automated coating apparatus equipped with a first heating region set to approximately 90°C and a second heating region set to approximately 140°C, the slurry was applied onto a copper foil with a thickness of 9 μm, and the water was evaporated.

[0196] C) Fabrication of NEG5A as an example of negative electrode fabrication (second layer) i) CMC (3.9g) was dissolved in deionized water (~350g); ii) Add carbon black (6g) and mix at 6500 rpm for 15 minutes; iii) Activated graphite for the negative electrode (JFE Chemical Co., Ltd., graphitized mesophase carbon microbead (MCMB) and synthetic graphite (TIMCAL)) (283.8 g in total) was added to the slurry prepared in step ii, and mixed at 6500 rpm for 30 minutes to prepare a fluid slurry; iv) SBR (50% solids, aqueous suspension) (25.2 g) was added to the slurry prepared in step ii and mixed at 6500 rpm for 5 minutes; v) The viscosity was adjusted for smooth application; vi) Using an automated coating apparatus equipped with a first heating region set to approximately 70°C and a second heating region set to approximately 100°C, the slurry was applied onto NEG5B and the water was evaporated. The final solid load was approximately 9.8 mg / cm³. 2 Next, the negative electrode layer was compressed to a thickness of approximately 114 μm. The fabricated negative electrode was then dried for cell assembly.

[0197] D) Creation of cells for evaluation i) The electrodes were punched out to create individual pieces with electrode tabs; ii) The positive electrode was dried at 125°C for 10 hours, and the negative electrode was dried at 140°C for 10 hours; iii) The positive and negative electrodes were stacked with a separator as an intermediate layer; iv) The jelly rolls prepared in step iii were laid flat inside an aluminum composite bag; v) Dry the bags from step iv in a vacuum oven at 70°C; vi) The bag from step v was filled with an organic carbonate-based electrolyte containing LiPF6; vii) The bag from step vi was sealed; viii) Let it stand for 16 hours; ix) The cell was charged to 4.2V at a rate of C / 20 for 5 hours, then charged to 4.2V at a rate of 0.5C for 2 hours, then rested for 20 minutes, and then discharged to 2.8V at a rate of 0.5C. Under vacuum, the cell was punctured to release the gas, and then resealed. The fabricated cell was used for evaluation and other tests such as discharge capacity testing at 50°C, shock testing, and cycle life testing.

[0198] Figure 36 shows the cell impedance at 1 kHz, the capacitance at currents of 1 A, 3 A, 6 A, and 10 A, and the ratio of the capacitance at 3, 6, and 10 A to the capacitance at 1 A. Figure 40 shows the cell temperature profile during the shock test. Figure 41 shows the maximum cell temperature during the shock test.

[0199] Example 12 The following describes the preparation of the resistive layer, positive electrode, and negative electrode made by mixing Al2O3 and sodium silicate (NaSiO3), as well as the preparation of the completed cell 6 used for resistance measurement, discharge capacity testing at 50°C, shock testing, and cycle life evaluation.

[0200] A) Positive electrode POS6B as an example of resistive layer (first layer) fabrication. i) Toron® 4000TF (0.8g) was dissolved in NMP (~10g); ii) PVDF (4.8g) was dissolved in NMP (60g); iii) The solutions prepared in steps i and ii were mixed, then carbon black (0.32 g) was added and mixed at a speed of approximately 6500 rpm for 10 minutes; iv) Nano Al2O3 powder (17.04 g) and NaSiO3 (17.04 g) were added to the solution prepared in step iii, and mixed at 6500 rpm for 20 minutes to prepare a fluid slurry; v) Using an automated coating apparatus equipped with a first heating region set to approximately 135°C and a second heating region set to approximately 165°C, the slurry was applied onto a 15 μm thick aluminum foil, and the NMP was evaporated. The final solid load was approximately 0.7 mg / cm². 2 That was the case.

[0201] B) Fabrication of POS6A as an example of cathode fabrication (second layer) i) PVDF (21.6 g) was dissolved in NMP (270 g); ii) Add carbon black (18g) and mix at 6500rpm for 15 minutes; iii) LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2(NMC) (560.4g) was added to the slurry prepared in step ii, and the mixture was heated at 6500 rpm for 30 minutes to produce a fluid slurry. iv) Some NMP was added to adjust the viscosity; v) Using an automated coating apparatus equipped with a first heating region set to approximately 85°C and a second heating region set to approximately 135°C, this slurry was applied onto POS6B (Example 1A), and the NMP was evaporated. The final solid load was approximately 19.4 mg / cm³. 2 Next, the positive electrode layer was compressed to a thickness of approximately 153 μm. The fabricated electrode was treated as having zero voltage relative to a standard graphite electrode and used for impedance measurement at 0V to investigate its relationship with temperature.

[0202] C) Fabrication of NEG6A as an example of negative electrode fabrication i) Dissolve CMC (13g) in deionized water (~1000g); ii) Add carbon black (20g) and mix at 6500rpm for 15 minutes; iii) Activated graphite for the negative electrode (JFE Chemical Co., Ltd., graphitized mesophase carbon microbeads (MCMB) and synthetic graphite (TIMCAL)) (945.92 g in total) was added to the slurry prepared in step ii, and mixed at 6500 rpm for 30 minutes to prepare a fluid slurry; iv) SBR (50% solids, aqueous suspension) (42 g) was added to the slurry prepared in step ii and mixed at 6500 rpm for 5 minutes; v) The viscosity was adjusted for smooth application; vi) Using an automated coating apparatus equipped with a first heating region set to approximately 100°C and a second heating region set to approximately 130°C, the slurry was applied onto a 9 μm thick copper foil, and the water was evaporated. The final solid load was approximately 11.8 mg / cm³. 2 Next, the negative electrode layer was compressed to a thickness of approximately 159 μm. The fabricated negative electrode was then dried for cell assembly.

[0203] D) Creation of cells for evaluation i) The electrodes were punched out to create individual pieces with electrode tabs; ii) The positive electrode was dried at 125°C for 10 hours, and the negative electrode was dried at 140°C for 10 hours; iii) The positive and negative electrodes were stacked with a separator as an intermediate layer; iv) The jelly rolls prepared in step iii were laid flat inside an aluminum composite bag; v) Dry the bags from step iv in a vacuum oven at 70°C; vi) The bag from step v was filled with an organic carbonate-based electrolyte containing LiPF6; vii) The bag from step vi was sealed; viii) Let it stand for 16 hours; ix) The cell was charged to 4.2V at a rate of C / 20 for 8 hours, then charged to 4.2V at a rate of 0.5C for 2 hours, then rested for 20 minutes, and then discharged to 2.8V at a rate of 0.5C. Under vacuum, the cell was punctured to release the gas, and then resealed. The fabricated cell was used for evaluation and other tests such as discharge capacity testing at 50°C, shock testing, and cycle life testing.

[0204] Figure 36 shows the cell impedance at 1 kHz, the capacitance at currents of 1 A, 3 A, 6 A, and 10 A, and the ratio of the capacitance at 3, 6, and 10 A to the capacitance at 1 A. Figure 40 shows the cell temperature profile during the shock test. Figure 41 shows the maximum cell temperature during the shock test.

[0205] In the above description and claims, phrases such as “at least one” or “one or more” may be followed by a concatenated description of an element or feature. The term “and / or” may appear in descriptions of two or more elements or features. Unless implicitly or explicitly contradicted by the context in which they are used, these phrases are intended to mean one of the described elements or features, or a combination of any of the other described elements or features. For example, the phrases “at least one of A and B,” “one or more of A and B,” and “A and / or B” are intended to mean “A only, B only, or both A and B,” respectively. The same interpretation is intended for descriptions containing three or more items. For example, the phrases “at least one of A, B, and C,” and “A, B, and / or C” are intended to mean “A only, B only, C only, both A and B, both A and C, both B and C, or all of A, B, and C,” respectively. The use of the term “based on” in the above description and claims is intended to mean “based on at least part of” so that features or elements not described may be permitted.

[0206] The subject matter described herein can be embodied in systems, apparatus, methods, and / or articles, depending on the desired configuration. The embodiments described above do not represent all embodiments consistent with the subject matter described herein. Rather, they are merely some examples consistent with aspects relating to the subject matter described herein. While a few variations are described in detail above, other modifications or additions are possible. In particular, it is possible to provide further features and / or variations in addition to those described herein. For example, the embodiments described above can be directed to various combinations and partial combinations of the disclosed features, and / or combinations and partial combinations of several further disclosed features. In addition, the logical flows shown in the accompanying drawings and described herein do not necessarily require a specific order or sequence to achieve the desired result. Other embodiments are within the scope of the following claims.

Claims

1. An improved high-energy-density rechargeable battery, A first electrode having a first part and a second part, A first current collector for transmitting electrons, A second electrode having polarity opposite to that of the first electrode, A separator for separating the first electrode and the second electrode, wherein the separator is configured to prevent internal discharge between the first electrode and the second electrode that occurs due to damage to the separator, The second portion of the first electrode interposed between the first portion of the first electrode and the first current collector, and A current interrupter interposed between the first portion and the second portion of the first electrode, The current interrupter includes a thermosensitive material configured to be activated by a temperature trigger or voltage trigger to generate a gas that causes the formation of a nonconductive gap between the first and second portions of the first electrode, the nonconductive gap delaminating the lamination between the first and second portions of the first electrode, and the formation of the nonconductive gap electrically isolates the second portion from the first portion of the first electrode. The current interrupter has a layer containing an inorganic gas generating compound and an organic gas generating compound. The rechargeable battery.

2. The rechargeable battery according to claim 1, further comprising a current limiter.

3. The rechargeable battery according to claim 1 or 2, further comprising a second current collector.

4. The second electrode consists of a first portion and a second portion of the second electrode, The rechargeable battery according to claim 2, wherein the current limiter is interposed between the first portion and the second portion of the second electrode.

5. The rechargeable battery according to any one of claims 2 or 4, wherein the current limiter and the current interrupter are simultaneously incorporated in a single protective layer interposed between the first portion and the second portion of the first electrode by lamination.

6. The rechargeable battery according to any one of claims 2, 4, and 5, wherein the resistivity of the current limiter is greater than the internal resistivity of the first electrode at temperatures exceeding the temperature range for standard operation.

7. The rechargeable battery according to any one of claims 2, 4, and 5, wherein the resistivity of the current limiter does not shift at temperatures within the temperature range for standard operation.

8. The rechargeable battery according to any one of claims 2, 4, and 5, wherein the resistivity of the current limiter is less than the internal resistivity of the first electrode at temperatures within the temperature range for standard operation.

9. The rechargeable battery according to any one of claims 1 to 8, wherein the temperature trigger activates when the temperature exceeds the temperature range for standard operation.

10. The rechargeable battery according to any one of claims 1 to 9, wherein the voltage trigger is activated when the voltage exceeds the voltage range for standard operation.

11. The rechargeable battery according to any one of claims 1 to 10, wherein the first portion and the second portion of the first electrode are electrically coupled via a stacked connection provided by the current interrupter when the current interrupter is in an engagement configuration, and the formation of the nonconductive gap decouples the stacked connection between the first portion and the second portion of the first electrode.

12. The rechargeable battery according to any one of claims 1 to 11, wherein the heat-sensitive material forms the non-conductive gap by generating at least a liquid that vaporizes and forms a gas when the temperature trigger is activated.

13. The rechargeable battery according to any one of claims 1 to 12, wherein the heat-sensitive material, when the temperature trigger is activated, generates at least one liquid that reacts with the first electrode, the first current collector, the separator, and the electrolyte contained in the battery to form a gas, thereby forming the non-conductive gap.

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