Toxic gas inhibitor for secondary-battery fire, toxic gas inhibiting member for secondary-battery fire, and secondary battery

Abstract

A toxic gas inhibitor for a fire, according to an embodiment of the present invention, comprises: at least one first material having decomposition onset temperatures; and a second material mixed with the first material to bind the first material, wherein the first material is decomposed, when reaching the decomposition onset temperatures, thereby detoxifying toxic materials generated during a secondary-battery fire.

Description

Secondary battery fire toxic gas suppression agent, secondary battery fire toxic gas suppression agent, and secondary battery

[0001] The present invention relates to a secondary battery fire toxic gas suppressor, a secondary battery fire toxic gas suppressor, and a secondary battery, and more particularly, to a secondary battery fire toxic gas suppressor, a secondary battery fire toxic gas suppressor, and a secondary battery capable of effectively suppressing fire toxic gases of a secondary battery.

[0002] Secondary batteries with high electrical energy density can be vulnerable to shock.

[0003] Secondary batteries can cause a thermal runaway in a short period of time by instantly releasing high energy accumulated due to internal defects or external impact, which can lead to fire, making it very difficult to respond to accidents.

[0004] If a fire breaks out in a secondary battery, the normal response is to try to extinguish it.

[0005] However, these conventional countermeasures are ineffective against thermal runaway and the rapid spread of fire caused by it, and in particular, it is difficult to effectively deal with the lethal toxic gas contained in the thermal runaway gas that causes secondary battery fires using conventional fire suppression methods.

[0006] Secondary batteries utilize a variety of organic compounds as anodes, cathodes, and electrolytes. Consequently, thermal runaway, a characteristic phenomenon in secondary battery fires, can occur when a high-temperature environment is created inside the battery due to physical or thermal shock or an electrical short circuit inside or outside the battery. High-temperature flammable gases are emitted from the cells inside the battery, which then combine with oxygen inside and outside the pack, resulting in rapid ignition and flames. Furthermore, when these flammable gases are emitted, toxic gases that are lethal to the human body, such as HCl (hydrogen chloride), HF (hydrogen fluoride), and CO (carbon monoxide), are also generated. This can cause secondary damage due to extremely toxic gases in addition to fires caused by thermal runaway.

[0007] [Prior Art Literature]

[0008] [Patent Document]

[0009] (Patent Document 0001) Republic of Korea Patent Publication No. 10-2022-0125085

[0010] In order to solve the technical problem to be achieved by the present invention, the purpose is to provide a fire toxic gas suppressant capable of effectively suppressing fire toxic gases of a secondary battery and a fire toxic gas suppressant sheet including the same.

[0011] The technical problems to be solved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by a person having ordinary skill in the technical field to which the present invention belongs from the description below.

[0012] A fire toxic gas suppressant according to one embodiment of the present invention comprises: at least one first material having a decomposition initiation temperature; and a second material mixed with the first material and binding the first material; wherein the first material decomposes when the decomposition initiation temperature is reached, thereby detoxifying toxic substances that may be generated in the event of a secondary battery fire.

[0013] The above first material is decomposed to include a reactive decomposition gas capable of detoxifying toxic substances generated in a secondary battery fire during decomposition, thereby detoxifying toxic substances generated in a secondary battery fire.

[0014] The first material comprises two or more materials, and the two or more materials have two or more decomposition initiation temperatures and can be decomposed in stages to detoxify the toxic material.

[0015] The first material may include one or more of carbonate, chloride, hydroxide, and phosphate.

[0016] The above carbonate may include one or more of sodium carbonate (Na2CO3), sodium bicarbonate (NaHCO3), potassium carbonate (K2CO3), potassium bicarbonate (KHCO3), ammonium carbonate ((NH4)2CO3), and ammonium bicarbonate (NH4HCO3).

[0017] The above chloride may include one or more of ammonium chloride (NH4Cl), potassium chloride (KCl), aluminum chloride (AlCl3), and sodium chloride (NaCl).

[0018] The above hydroxide salt may include one or more of sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH)2), and magnesium hydroxide (Mg(OH)2).

[0019] The above phosphate may include one or more of ammonium phosphate ((NH4)3PO4), sodium phosphate (Na3PO4), and potassium phosphate (K3PO4).

[0020] The above fire toxic gas suppressant can be prepared in one or more of a paste, liquid, and gaseous form.

[0021] The second material may include one or more of an organic adhesive and an elastomer.

[0022] According to another embodiment of the present invention, a fire toxic gas suppression member comprises a pair of fiber members; and at least one fire extinguishing material provided between the pair of fiber members, which has a decomposition initiation temperature and can decompose to decompose a combustible organic compound when the decomposition initiation temperature is reached; and an organic binder mixed with the fire extinguishing material, thereby capable of detoxifying toxic substances that may be generated in the event of a secondary battery fire.

[0023] According to another embodiment of the present invention, a secondary battery comprises: at least one first material having a decomposition initiation temperature; and a second material mixed with the first material to bind the first material; wherein the first material decomposes when the decomposition initiation temperature is reached, thereby detoxifying toxic substances that may be generated in the event of a secondary battery fire.

[0024] According to one embodiment of the present invention, a fire toxic gas suppressant capable of effectively suppressing fire toxic gases of a secondary battery, a fire toxic gas suppressant sheet including the same, and a secondary battery including the same can be provided.

[0025] FIG. 1 is an exemplary diagram of a secondary battery fire toxic gas suppressant according to one embodiment of the present invention.

[0026] FIG. 2 is a graph of a Fourier transform infrared analysis (FRIT) experiment on hydrogen chloride and hydrogen fluoride, which are toxic gases generated during thermal runaway of a secondary battery, conducted when a sheet impregnated with a secondary battery fire toxic gas suppressant according to one embodiment of the present invention was attached and when it was not attached.

[0027] Figure 3 is a photograph showing a paste-like form of a secondary battery fire toxic gas suppressant according to one embodiment of the present invention.

[0028] FIG. 4 is a photograph showing a secondary battery fire toxic gas suppression sheet according to one embodiment of the present invention.

[0029] FIG. 5 is an exemplary diagram illustrating an example of use of a secondary battery fire toxic gas suppression sheet according to one embodiment of the present invention.

[0030] Hereinafter, the present invention will be described with reference to the attached drawings.

[0031] However, the present invention may be implemented in various different forms and is therefore not limited to the embodiments described herein. In order to clearly explain the present invention in the drawings, parts irrelevant to the description have been omitted, and similar parts have been designated with similar reference numerals throughout the specification.

[0032] Throughout the specification, when it is said that a part is “connected” (connected, contacted, coupled) to another part, this includes not only cases where it is “directly connected” but also cases where it is “indirectly connected” with another part in between. In addition, when it is said that a part “includes” a certain component, this does not mean that other components are excluded, but that other components can be included, unless otherwise specifically stated.

[0033] The terminology used herein is for the purpose of describing specific embodiments only and is not intended to limit the present invention. The singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, it should be understood that the terms "comprise" or "have" specify the presence of a feature, number, step, operation, component, part or combination thereof described in the specification, but do not exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts or combinations thereof.

[0034] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings.

[0035] As shown in Fig. 1, the secondary battery toxic gas suppressant (100) is intended to suppress toxic gases generated in the event of a fire in a secondary battery, and may include a first material and a second material. The first material is a material having a decomposition initiation temperature and having extinguishing and non-toxic properties, and may be referred to as one of a extinguishing agent, a extinguishing agent, a extinguishing powder, a non-toxicizing agent, a non-toxicizing material, or a non-toxicizing powder when describing embodiments of the present invention hereinafter. In addition, the second material is a material that is mixed with the first material and binds the first material, and may be referred to as an organic binder (120) when describing embodiments of the present invention hereinafter.

[0036] A secondary battery fire toxic gas suppressant (100) according to an embodiment of the present invention may include a first material (110) having extinguishing and non-toxic properties and a second material including an organic binder (120).

[0037] Hereinafter, the extinguishing properties of the first material (110) will be described. When describing in relation to extinguishing properties, the first material (110) may be referred to as a extinguishing material, a extinguishing agent, a extinguishing powder, etc. Meanwhile, when describing the detoxification properties of the first material (110) included in the secondary battery fire toxic gas suppressant according to an embodiment of the present invention, the first material (110) may be referred to as a detoxification material, a detoxification agent, a detoxification powder, etc.

[0038]

[0039] The digestive substance (110) refers to a composition having digestive properties that can function in a liquid, gaseous, solid, or powdery state, and is hereinafter sometimes described as a digestive substance (100) or digestive powder (100), but this is for the purpose of describing a representative example and is not to be interpreted as being limited to a specific state or form.

[0040] The extinguishing agent (110) may be a carbonate ion that has reactivity with lithium and may be combined with a monovalent or divalent cation, which may cause asphyxiation in the fire by blocking contact with oxygen.

[0041] The digestible substance (110) may be an inorganic salt, for example, an inorganic salt powder. In addition, the inorganic salt preparation may include alkali metals, alkaline earth metals, and ammonium-based substances on the periodic table that have strong oxygen radical absorption capabilities.

[0042] The alkali metal series may include one or more of sodium carbonate (Na2C03), sodium bicarbonate (NaHCO3), potassium carbonate (K2CO3), and potassium bicarbonate (KHC03).

[0043] And, as alkaline earth metals, one or more of magnesium hydrogen carbonate (Mg(HC03)2), magnesium carbonate (MgC03), calcium carbonate (CaC03), and calcium bicarbonate (Ca(HC03)2) may be included.

[0044] Additionally, the ammonium-based substance may include at least one of ammonium carbonate ((NH4)2C03) and ammonium bicarbonate (NH4HC03).

[0045] The digestible substance (110) may specifically be an inorganic carbonate.

[0046] When carbonates are decomposed by heat, reactive decomposition gases and cationic metal ions can be automatically emitted.

[0047] When secondary batteries are damaged by internal or external factors, such as separator damage or external pressure, the resulting short circuit between the anode and cathode increases resistance. This, in addition to the resulting resistive heat, triggers a rapid exothermic reaction that causes thermal decomposition of the electrolyte and the release of flammable and toxic gases. This, in turn, causes a rapid increase in the temperature and internal pressure of the secondary battery, as shown in Table 1 below.

[0048]

[0049] Pressure (atmospheric pressure)0.000010.00010.0010.010.11Temperature ( o C)52461272287110641337

[0050] Here, when a carbonate included in a secondary battery fire toxic gas suppressant according to an embodiment of the present invention, for example, a carbonate included in a lithium battery, is exposed to such heat, it may react and decompose as shown in the reaction formula below.

[0051] This phenomenon is influenced by organic substances inside the battery cell, but the biggest factor is that lithium ions gain electrons to become lithium metal and vaporize themselves, or combine with nitrogen in the air to form lithium nitride, as shown in [Chemical Formula 1] and [Chemical Formula 2] below.

[0052]

[0053] [Chemical Formula 1]

[0054] Li + + e - → Li

[0055] [Chemical Formula 2]

[0056] 6Li + N2→ 2Li3N

[0057]

[0058] And, as seen in [Chemical Formula 3] to [Chemical Formula 5] below, lithium or lithium nitride reacts rapidly with water vapor or oxygen, generating strong heat and burning into lithium peroxide or lithium oxide.

[0059]

[0060] [Chemical Formula 3]

[0061] 4Li + O2→ 2Li2O

[0062] [Chemical Formula 4]

[0063] 4Li + 2H2O + O2→ 4LiOH

[0064] [Chemical Formula 5]

[0065] 2Li + H2O → Li2O + H2

[0066]

[0067] Meanwhile, in such a high-temperature environment, the carbonate according to the embodiment of the present invention may decompose to generate reactive decomposition gas and cationic metal ions.

[0068] The reactive decomposition gas generated can decompose the flammable gas (lithium gas) emitted from the secondary battery. The reactive decomposition gas emitted when carbonate is decomposed by heat may be carbon dioxide (C02).

[0069] Additionally, cationic metal ions can absorb radicals generated from electrical sparks or flames, thereby preventing chain reactions of combustion.

[0070] As shown in Chemical Formulas 6 and 7 below, if a fire occurs in a secondary battery, the generated heat can decompose the carbonate, releasing carbon dioxide. The vaporized lithium then reacts with carbon dioxide and oxygen to convert into carbonate, rendering it non-flammable.

[0071] In this way, as the carbonate decomposes, carbon dioxide is released, and when the carbon dioxide blocks oxygen access due to the suffocating effect, combustion caused by a secondary battery fire can be effectively mitigated or effectively extinguished.

[0072]

[0073] [Chemical Formula 6]

[0074] 4Li + 2CO2+ O2→ 2Li2CO3

[0075] [Chemical Formula 7]

[0076] 2Li + 2CO2+ H2O + 1 / 2O2→ 2LiHCO3

[0077]

[0078] Meanwhile, in situations where the temperature and internal pressure of a secondary battery rapidly increase due to various causes, sparks generated inside the secondary battery may cause ignition of the secondary battery by generating radical ions.

[0079] When the carbonate included in the digestible material (110) according to an embodiment of the present invention is decomposed by heat, cationic metal ions (e.g., alkali metals or alkaline earth metals) may be generated.

[0080] Here, radical ions can be absorbed by cationic metal ions. This can suppress spark generation in the secondary battery and prevent ignition of the secondary battery. In other words, this anti-catalytic effect can suppress the chain reaction of combustion in the secondary battery. Therefore, fires in secondary batteries containing the secondary battery fire toxic gas suppressant according to an embodiment of the present invention can be prevented, and the spread of any fires that occur can be suppressed.

[0081]

[0082] Here, the carbonate that may be included in the extinguishing material (110) according to the embodiment of the present invention may be one or more of sodium carbonate (Na2CO3), sodium bicarbonate (NaHCO3), potassium carbonate (K2CO3), potassium bicarbonate (KHCO3), magnesium hydrogen carbonate (Mg(HCO3)2), magnesium carbonate (MgCO3), calcium carbonate (CaCO3), calcium bicarbonate (Ca(HCO3)2), ammonium carbonate ((NH4)2CO3), and ammonium bicarbonate (NH4HCO3). Here, depending on the decomposition initiation temperature of each carbonate as shown in Table 2 below, one carbonate may be included, or two or more of these may be combined and included.

[0083]

[0084] Classification Chemical formula Molecular weight Decomposition onset temperature ( oC) Ammonium bicarbonate NH4HCO3 79.0641-45 Ammonium carbonate (NH4)2CO3 96.0960 Sodium bicarbonate NaHCO3 84.80 Sodium carbonate Na2CO3 105.99100 Potassium bicarbonate KHCO3 100.1100-200 Potassium carbonate K2CO3 138.2850 Magnesium carbonate MgCO3 84.3350 (anhydrous bone) 165 (trihydrate)

[0085] Here, the decomposition initiation temperature may be the temperature at which the carbonate begins to decompose. As described in Table 2, each carbonate may have a unique decomposition initiation temperature. The carbonate may be selected based on user needs, such as the temperature at which the desired carbonate decomposes to exhibit fire suppression and fire toxic gas suppression functions, weight adjustments based on differences in reactivity with organic substances that may be included in secondary batteries, or other requirements, and may be included in secondary battery fire toxic gas suppression agents.

[0086]

[0087] In addition, as shown in Table 3 below, two or more carbonates may be combined and included in the secondary battery fire toxic gas suppressant. This combination is intended to achieve gradual detoxification, and has the effect of further ensuring the effect of fire suppression. Here, since the carbonate begins to decompose at the decomposition initiation temperature at which the carbonate decomposes as described in Table 2, thereby achieving the fire suppression function, the secondary battery fire toxic gas suppressant according to an embodiment of the present invention may include 50% or more of a carbonate having a decomposition initiation temperature closest to the dangerous temperature of fire occurrence. In addition, the carbonate having a decomposition initiation temperature closest to the dangerous temperature of fire occurrence while being equal to or lower than the dangerous temperature may be included 50% or more.

[0088]

[0089] Decomposition onset temperature 60 o C100 o C150 oC Ammonium carbonate 55 wt% 10 wt% Potassium bicarbonate 20 wt% 60 wt% 10 wt% Magnesium carbonate 5 wt% 10 wt% 70 wt%

[0090] Here, the decomposition initiation temperature at which the decomposition of the carbonate begins to suppress the fire can be selected. This selection can be based on the settings of the manufacturer of the lithium-ion secondary battery or the manufacturer of the product in which the lithium-ion secondary battery is mounted. The temperature determined as a dangerous temperature may vary depending on the production and usage environments of the secondary battery user. For example, a lithium-ion secondary battery may be determined to have a fire risk or a fire may have occurred at temperatures above 60°C. This is because, depending on the situation, a lithium-ion secondary battery may be determined to have a fire risk or a fire may have occurred at temperatures above 100°C. Therefore, a specific temperature range considering the usage temperature range of the secondary battery is determined to be a dangerous temperature range, and a carbonate may be included so as to have a decomposition initiation temperature that falls within the dangerous temperature range, or a carbonate that does not fall within the dangerous temperature range but has a decomposition initiation temperature lower or higher than the dangerous temperature may be additionally selected and mixed.

[0091] For example, as shown in Table 3, if the user determines that the hazardous temperature range is 60°C or higher, the carbonate may include 55 wt% ammonium carbonate, 20 wt% potassium bicarbonate, and 5 wt% magnesium carbonate. The carbonate may be formed by mixing these. In this case, ammonium carbonate, which accounts for the largest wt%, may be decomposed first at the hazardous temperature of 60°C, and the primary digestion process may proceed. However, if the primary digestion process does not proceed and the temperature further increases to 100-120°C, potassium bicarbonate, which accounts for the next largest wt%, may be decomposed, and the secondary digestion process may proceed. Nevertheless, if the temperature further increases to the decomposition initiation temperature of magnesium carbonate, a tertiary digestion process by magnesium carbonate may proceed. That is, as the temperature increases, the digestion process may proceed in stages.

[0092] If the carbonate is composed solely of substances with a decomposition onset temperature within the hazardous temperature range, decomposition of all substances will occur at that temperature, and the extinguishing process will begin. However, if complete extinguishment is not achieved despite this extinguishing process, the rapid increase in the fire temperature will not be prevented, preventing the onset of thermal runaway. This will not provide the driver with time to evacuate the vehicle.

[0093] However, as in the embodiment of the present invention, when two or more carbonates are combined and the carbonates have a decomposition initiation temperature equal to or lower than the lower limit of the dangerous temperature range while not falling within the dangerous temperature range, and the extinguishing process is carried out in stages, a rapid increase in the fire temperature can be prevented and the occurrence of thermal runaway can be delayed. This has the effect of providing time for the driver of the vehicle to evacuate.

[0094]

[0095] Secondary batteries contain a variety of organic compounds as anodes, cathodes, and electrolytes. A characteristic phenomenon of secondary battery fires is thermal runaway, which occurs when high-temperature flammable gases are emitted from the cells within the battery, combining with oxygen inside and outside the pack, resulting in an electrical short or high-temperature ignition. This can lead to thermal runaway and flame generation. Toxic substances can be generated during this process.

[0096] Table 4 below shows the main gases generated during thermal runaway of an exemplary secondary battery.

[0097]

[0098] Combustible Gas Volume Content (%) Hydrogen 30.6% Carbon Dioxide 29.9% Carbon Monoxide 21.3% Methane 7.2% Ethylene 5.6% Propane or Propylene 2.0% Ethane 1.8% Other 1.6%

[0099] FIG. 2 is a graph for examining gases generated during thermal runaway and fire in a secondary battery including a secondary battery fire toxic gas suppressant according to one embodiment of the present invention.

[0100] Fire suppressants can be included in secondary batteries in various forms. FIG. 2 is a Fourier transform infrared analysis (FRIT) experimental graph of hydrogen chloride and hydrogen fluoride gases generated during thermal runaway and fire of a secondary battery in the case where a member impregnated with a secondary battery fire toxic gas suppressant according to an embodiment of the present invention is attached ('CO ppm absent' and 'C2H6ppm absent') and not attached ('CO ppm' and 'C2H6ppm').

[0101] As illustrated in FIG. 2, it can be confirmed that the secondary battery including the secondary battery fire toxic gas suppressant (100) effectively suppresses hydrogen chloride (HCl) and hydrogen fluoride (HF), which are toxic gases generated in the event of a secondary battery fire, compared to the case where the secondary battery is not attached. In this way, the secondary battery fire toxic gas suppressant (100) according to one embodiment of the present invention can effectively suppress or neutralize toxic gases generated in the event of secondary battery thermal runaway and fire.

[0102] This suppression or neutralization can be explained by adsorption and conversion reactions. The secondary battery fire toxic gas suppressant may be a combination of one (1) or two (2) or more of carbonate ions, chloride ions, hydroxide ions, and phosphate ions that cause adsorption and conversion reactions in response to fires that occur during thermal runaway of secondary batteries, and one (1) or two (2) or more of monovalent, divalent, and trivalent cations.

[0103] According to one embodiment of the present invention, a secondary battery fire toxic gas suppressant may be provided in one (1) or two (2) or more of a paste, a liquid, and a gaseous state. The secondary battery fire toxic gas suppressant provided in this manner may be positioned in a separately partitioned area inside the secondary battery. In addition, the secondary battery fire toxic gas suppressant may not be positioned in a separately partitioned area, but may be positioned inside the secondary battery in a state of being impregnated into a sheet or the like. In this case, the sheet impregnated with the secondary battery fire toxic gas suppressant may be positioned on the outer surface, the inner surface, or the inner surface as an intermediate layer of a pouch forming each cell of the secondary battery, and may be included not only on the entire surface of the pouch but also on a portion of the surface of the pouch.

[0104] In addition, a sheet impregnated with a secondary battery fire toxic gas suppressant may be applied or attached to the inner surface of a battery pack case that accommodates a secondary battery, or may be sprayed and included inside or outside the battery pack.

[0105] When the secondary battery fire toxic gas suppressant is decomposed by heat due to thermal runaway of the secondary battery according to an embodiment of the present invention, reactive decomposition gases and cationic metal ions may be generated and emitted.

[0106] The reactive decomposition gas emitted can suppress a fire and at the same time detoxify toxic gases emitted from a secondary battery. The reactive decomposition gas emitted by the secondary battery fire toxic gas suppressant according to an embodiment of the present invention, which is prepared by including one (1) or two (2) or more of carbonate, chloride, hydroxide, or phosphate, decomposes by heat, may be a mixture of one (1) or two (2) or more of carbon dioxide (CO2), chlorine gas, hydroxyl radical, and phosphoric acid gas.

[0107] In addition, cationic metal ions can absorb radicals generated from electrical sparks or flames, thereby preventing a chain reaction of combustion reactions and thus suppressing the chain reaction of fire.

[0108] The carbonate included in the secondary battery fire toxic gas suppressant according to an embodiment of the present invention may be a secondary battery fire toxic gas suppressant including at least one of sodium carbonate (Na2CO3), sodium bicarbonate (NaHCO3), potassium carbonate (K2CO3), potassium bicarbonate (KHCO3), ammonium carbonate ((NH4)2CO3), and ammonium bicarbonate (NH4HCO3).

[0109] The chloride salt that may be included in the secondary battery fire toxic gas suppressant according to an embodiment of the present invention may be a fire toxic gas suppressant including one (1) or a combination of two (2) or more of ammonium chloride (NH4Cl), potassium chloride (KCl), aluminum chloride (AlCl3), and sodium chloride (NaCl).

[0110] The hydroxide salt that may be included in the secondary battery fire toxic gas suppressant according to an embodiment of the present invention may be a fire toxic gas suppressant including one (1) or a combination of two (2) or more of sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH)2), and magnesium hydroxide (Mg(OH)2).

[0111] The phosphate that may be included in the secondary battery fire toxic gas suppressant according to an embodiment of the present invention may be a fire toxic gas suppressant including one (1) or two (2) or more of ammonium phosphate ((NH4)3PO4), sodium phosphate (Na3PO4), and potassium phosphate (K3PO4).

[0112]

[0113] An example of mixing carbonate substances among secondary battery fire toxic gas suppressants can be implemented as shown in Table 5 above.

[0114]

[0115] Combustible gas COC2H 23 CH4 Sodium Carbonate 55 wt% 10 wt% 10 wt% Potassium Bicarbonate 20 wt% 60 wt% 10 wt% Magnesium Carbonate 5 wt% 10 wt% 70 wt%

[0116] An example of mixing chloride substances among secondary battery fire toxic gas suppressants can be implemented as in Table 6 above.

[0117]

[0118] Combustible gas COC2H 23 CH4 Ammonium Chloride 30 wt% 20 wt% 20 wt% Potassium Chloride 20 wt% 40 wt% 30 wt% Aluminum Chloride 10 wt% 10 wt% 20 wt%

[0119] An example of mixing hydroxide salts among secondary battery fire toxic gas suppressants can be implemented as shown in Table 7.

[0120]

[0121] Combustible gas COC2H 23CH4 Sodium hydroxide 40 wt% 40 wt% 30 wt% Calcium hydroxide 20 wt% 20 wt% 20 wt% Magnesium hydroxide 10 wt% 10 wt% 20 wt%

[0122] An example of mixing phosphate materials among secondary battery fire toxic gas suppressants can be implemented as shown in Table 8.

[0123]

[0124] Combustible gas COC2H 23 CH4 Ammonium Phosphate 20 wt% 40 wt% 30 wt% Potassium Phosphate 20 wt% 10 wt% 20 wt% Calcium Phosphate 10 wt% 10 wt% 10 wt% Magnesium Phosphate 10 wt% 10 wt% 10 wt%

[0125]

[0126] Here, the carbonate included in the secondary battery fire toxic gas suppression agent according to an embodiment of the present invention may be selected taking into account combustible gases. The carbonate may be selected by the secondary battery manufacturer or user taking into account the usage environment (operating temperature, etc.) of the secondary battery containing the secondary battery fire toxic gas suppression agent according to an embodiment of the present invention or the type of gas determined to be a hazardous combustible gas.

[0127] In other words, depending on the usage or operating environment, the flammable gases that are deemed to be at risk of causing a dangerous fire when using secondary batteries may vary. For example, CO may be considered a gas that can cause a dangerous fire in secondary batteries. In this case, some carbonates may be appropriately selected and used alone or in combination, depending on the flammable gas that could cause a dangerous fire.

[0128] For example, if the combustible gas that can cause a dangerous fire is carbon monoxide (CO), it may contain 55 wt% sodium carbonate, 20 wt% sodium bicarbonate, and 5 wt% magnesium carbonate. The carbonate may be formed by a combination thereof. It may also contain 30 wt% ammonium chloride, 20 wt% potassium chloride, and 10 wt% aluminum chloride. The chloride salt may be formed by a combination thereof. It may also contain 40 wt% sodium hydroxide, 20 wt% calcium hydroxide, and 10 wt% magnesium hydroxide. The hydroxide salt powder may be formed by a combination thereof. It may also contain 20 wt% ammonium phosphate, 20 wt% potassium phosphate, 10 wt% calcium phosphate, and 10 wt% magnesium phosphate. The phosphate may be formed by a combination thereof. Additionally, one or more of the above carbonates, chlorides, hydroxides, or phosphates may be blended.

[0129] Meanwhile, the organic binder (120) can be mixed with a carbonate (121).

[0130] In addition, the organic binder (120) may include one or more of an organic adhesive and an elastomer. Through this, the secondary battery fire toxic gas suppressant (100) may have any shape.

[0131] Figure 3 is a photograph showing the paste state of a secondary battery fire toxic gas suppressant according to one embodiment of the present invention.

[0132] As shown in Fig. 3, the secondary battery fire toxic gas suppressant can be formed into a paste state by mixing with an organic binder (120) including at least one of an organic adhesive and a rubber.

[0133] As a specific example, the secondary battery fire toxic gas suppressant of FIG. 3 is a mixture of 80 wt% carbonate and 20 wt% soft polyurethane with an organic binder (120).

[0134] A secondary battery fire toxic gas suppressant in the form of a paste like this can be applied or coated on the inner surface of a case that accommodates a secondary battery (corresponding to a battery pack cover (20) when referring to FIG. 5).

[0135] If a fire occurs in a secondary battery and the temperature increases to a temperature range deemed dangerous, each carbonate may sequentially decompose according to its decomposition initiation temperature, releasing carbon dioxide and cationic metal ions.

[0136] This can block oxygen access to combustible gases generated from secondary batteries through the suffocating effect of carbon dioxide. Furthermore, lithium, which can cause ignition, is converted to lithium carbonate, rendering it non-flammable. Furthermore, the spread of fire can be suppressed by absorbing radicals generated by sparks.

[0137] The secondary battery fire toxic gas suppressant may be provided in the form of an elastic pad.

[0138] In a case where a plurality of secondary batteries are provided, a secondary battery fire toxic gas suppression pad according to an embodiment of the present invention provided in the form of a pad may be provided positioned between at least one of the plurality of secondary batteries.

[0139] If a fire occurs in a secondary battery, generating heat and reaching a temperature range deemed hazardous, each carbonate in the secondary battery fire toxic gas suppression pad will sequentially decompose according to its decomposition initiation temperature, releasing carbon dioxide and cationic metal ions. This can suppress or extinguish the fire.

[0140] Meanwhile, if necessary, the secondary battery fire toxic gas suppressant (100) may further include solid powder.

[0141] FIG. 4 is a photograph showing a secondary battery fire toxic gas suppression member according to one embodiment of the present invention, and FIG. 5 is an exploded view between layers of a secondary battery fire toxic gas suppression member according to one embodiment of the present invention.

[0142] As shown in FIGS. 4 and 5, the secondary battery fire toxic gas suppression member (1000) may include a pair of fiber members (210, 220) and a secondary battery fire toxic gas suppression member (100).

[0143] A pair of fiber members (210, 220) may be non-combustible fiber members. In addition, a secondary battery fire toxic gas suppressant (100) may be provided between the pair of fiber members (210, 220).

[0144] In this embodiment, the secondary battery fire toxic gas suppression member (1000) may be formed by first applying a paste-type secondary battery fire toxic gas suppression member (100) to one fiber member (220), and then covering the top with another fiber member (210). A coater may be used to coat the paste-type secondary battery fire toxic gas suppression member (100).

[0145] Alternatively, the secondary battery fire toxic gas suppression member (1000) may be formed by first forming the secondary battery fire toxic gas suppression member (100) into a pad shape, and then attaching a pair of fiber members (210, 220) to both sides of the secondary battery fire toxic gas suppression pad formed into a pad shape.

[0146] A secondary battery fire toxic gas suppression member (1000) may be provided to cover at least a portion of a secondary battery. Referring to FIG. 4, the secondary battery fire toxic gas suppression member (1000) may be provided to cover the battery pack (10) from the inside of the battery pack cover (20).

[0147] Since the secondary battery fire toxic gas suppression member (1000) can be formed to correspond to the shape of the battery pack (10), it can stably cover the entire battery pack (10).

[0148] When a fire occurs in a secondary battery and the temperature increases to reach a temperature range deemed dangerous, the carbonate of the secondary battery fire toxic gas suppression member (1000) sequentially decomposes according to the decomposition initiation temperature, and carbon dioxide and cationic metal ions may be emitted. Through this, the spread of the fire can be suppressed or extinguished.

[0149] As shown in FIG. 5, the secondary battery fire toxic gas suppression member (1000) may include a pair of fiber members (210, 220), a secondary battery fire toxic gas suppression member (100), a heating wire (300), and a switch (400).

[0150] A pair of fiber members (210, 220) and a secondary battery fire toxic gas suppressant (100) may be the same as those described in FIGS. 4 and 5.

[0151] The heating wire (300) can be placed on one of the fiber members (220) among a pair of fiber members (210, 220). The heating wire (300) can be in direct contact with the secondary battery fire toxic gas suppressant (100). In addition, the heating wire (300) can be connected to the secondary battery (11).

[0152] And, the switch (400) can be connected to the heating wire (3W). In one embodiment, the switch (400) can be connected to the heating wire (300) on the outside of the fiber member (220).

[0153] When the detected temperature exceeds a preset allowable temperature, the switch (400) can cause the current of the secondary battery (11) to be applied to the heating wire (300) arranged in the fiber member (220), and the heating wire (300) can be heated. The heating wire (300) can be heated by Joules. Here, the allowable temperature can be a dangerous temperature requested by the user.

[0154] Therefore, when a fire occurs and the temperature exceeds a dangerous temperature, the current of the secondary battery (11) is applied to the heating wire (300), which may heat the heating wire (300). And, the carbonate may be decomposed by the heat of the heating wire (300).

[0155] At this time, the heating wire (300) can be heated to correspond to the lowest decomposition initiation temperature among the powders included in the extinguishing material, thereby allowing the powder with the lowest decomposition initiation temperature to be decomposed primarily. If the fire is not extinguished through the primary extinguishing process, the temperature will rise, and secondary and tertiary extinguishing processes can then be performed.

[0156] The switch (400) can be configured to allow the allowable temperature to be set according to the dangerous temperature required by the user. Through this, the extinguishing process initiation temperature of the secondary battery fire toxic gas suppression member (1000) can be easily and accurately set according to the dangerous temperature required by each user.

[0157] For example, the switch (400) may be configured to include a bimetal that can automatically implement a switching operation depending on temperature.

[0158] In addition, the secondary battery fire toxic gas suppression member (1000) may further include a temperature sensor unit (500) for temperature detection. In this case, the switch (400) may be configured to perform a switching operation based on the temperature detected by the temperature sensor unit (500).

[0159] Meanwhile, the secondary battery fire toxic gas suppression member (1000) is not limited to detecting temperature, and may also detect other objects. For example, the secondary battery fire toxic gas suppression member (1000) may detect pressure.

[0160] In case of detecting pressure as a target, the secondary battery fire toxic gas suppression member (1000) may further include a pressure sensor unit (not shown).

[0161] The pressure sensor unit can detect the internal pressure of the secondary battery (11).

[0162] When a fire occurs and the internal pressure of the secondary battery (11) increases and the detected pressure exceeds a preset allowable pressure, the switch (400) can cause the current of the secondary battery (11) to be applied to the heating wire (300) arranged in the fiber member (220), and the heating wire (300) can be heated.

[0163] The foregoing description of the present invention is for illustrative purposes only, and those skilled in the art will readily appreciate that the present invention can be readily modified into other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single entity may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined manner.

[0164] The scope of the present invention is indicated by the claims set forth below, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

[0165]

[0166] [Explanation of symbols]

[0167] 10: Battery pack 11: Secondary battery

[0168] 20: Battery pack cover 100: Secondary battery fire toxic gas suppressant

[0169] 110: Digestible powder 120: Organic binder

[0170] 210,220: Fiber sheet 300: Heating wire

[0171] 400: Switch 500: Temperature sensor section

[0172] 1000: Secondary battery fire toxic gas suppression sheet

Claims

1. One or more first substances having an initiation temperature of decomposition: and A second material mixed with the first material and binding the first material; The above first material is a fire toxic gas suppressant that decomposes when the decomposition initiation temperature is reached and can detoxify toxic substances generated in a secondary battery fire.

2. In paragraph 1, The above first material is a fire toxic gas suppressant that is decomposed to include a reactive decomposition gas capable of detoxifying toxic substances generated in a secondary battery fire during the decomposition process, thereby detoxifying toxic substances generated in a secondary battery fire.

3. In paragraph 1, The above first material comprises two or more materials, The above two or more substances have two or more decomposition initiation temperatures and are a fire toxic gas suppressant that can detoxify toxic substances generated in a secondary battery fire by gradually decomposing them.

4. In paragraph 1, The above first material is a fire toxic gas suppressant that contains at least one of carbonate, chloride, hydroxide, and phosphate and can detoxify toxic substances generated in a secondary battery fire.

5. In paragraph 4, The above carbonate contains at least one of sodium carbonate (Na2CO3), sodium bicarbonate (NaHCO3), potassium carbonate (K2CO3), potassium bicarbonate (KHCO3), ammonium carbonate ((NH4)2CO3), and ammonium bicarbonate (NH4HCO3), and is a fire toxic gas suppressant capable of detoxifying toxic substances generated in a secondary battery fire.

6. In paragraph 4, The above chloride salt contains at least one of ammonium chloride (NH4Cl), potassium chloride (KCl), aluminum chloride (AlCl3), and sodium chloride (NaCl), and is a fire toxic gas suppressant capable of detoxifying toxic substances generated in a secondary battery fire.

7. In paragraph 4, The above hydroxide salt contains at least one of sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH)2), and magnesium hydroxide (Mg(OH)2), and is a fire toxic gas suppressant capable of detoxifying toxic substances generated in a secondary battery fire.

8. In paragraph 4, The above phosphate comprises at least one of ammonium phosphate ((NH4)3PO4), sodium phosphate (Na3PO4), and potassium phosphate (K3PO4), and is a fire toxic gas suppressant capable of detoxifying toxic substances generated in a secondary battery fire.

9. In paragraph 2, The above fire toxic gas suppressant is provided in at least one of a paste state, a liquid state, and a gas state, and is a fire toxic gas suppressant capable of detoxifying toxic substances generated in the event of a secondary battery fire.

10. In paragraph 1, The above second material is a fire toxic gas suppressant capable of detoxifying toxic substances generated in a secondary battery fire, including at least one of an organic adhesive and an elastomer.

11. A pair of fiber members; and One or more detoxifying substances provided between a pair of said fiber members, said detoxifying substances having a decomposition initiation temperature and capable of decomposing and detoxifying a toxic substance when said decomposition initiation temperature is reached: and A fire toxic gas suppression member comprising a fire toxic gas suppression agent comprising an organic binder mixed with the above-mentioned non-toxic substance.

12. One or more non-toxic substances having an onset temperature of decomposition: and An organic binder mixed with the above-mentioned non-toxic substance; A secondary battery, wherein the above-mentioned non-toxic substance comprises a fire toxic gas suppressant that can decompose when the decomposition initiation temperature is reached and detoxify toxic substances that may be generated in the event of a secondary battery fire.

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