Secondary battery fire suppression agent, secondary battery fire suppression member, secondary battery, and method for producing fire suppression agent

Abstract

According to one embodiment of the present invention, a liquid or paste-phase secondary battery fire suppression agent and a method for producing same may be provided, the fire suppression agent comprising: a fire-extinguishing material that decomposes and spurts out at a decomposition initiation temperature; and a solvent that dissolves and converts the fire-extinguishing material to a liquid phase. The fire-extinguishing material includes: a first material including an ionic material that causes adsorption and conversion reactions of a flammable organic compound gas; and a second material including at least one selected from an alkali metal, an alkaline earth metal, a trivalent metal, and an ammonium-based material, and absorbing oxygen radicals, and thus prevents combustion reactions.

Description

Secondary battery fire suppressant, secondary battery fire suppressant member, secondary battery and method for manufacturing fire suppressant

[0001] The present invention relates to a secondary battery fire suppressant, a secondary battery fire suppressant member, a secondary battery, and a method for manufacturing a fire suppressant.

[0002] Secondary batteries, which possess a high electrical energy density, are vulnerable to shock. Internal defects or external impacts can cause a rapid release of stored energy, triggering thermal runaway within a short period of time, potentially leading to fire. This makes responding to accidents extremely difficult.

[0003] If a fire breaks out in a secondary battery, the normal response is to try to extinguish it.

[0004] Lithium in secondary batteries liquefies at its melting point of 108.5°C and rapidly vaporizes above 500°C. When a secondary battery experiences thermal runaway, a white gas is generated, the primary component of which is vaporized lithium. As the lithium vaporizes, the pressure within the battery cell rises, completely vaporizing at 1337°C. If the battery cell cannot withstand this pressure increase and explodes, the lithium gas reacts rapidly with oxygen, generating flames and heat, and causing thermal runaway.

[0005] Conventional methods of dealing with secondary battery fires generally use powder-type fire extinguishing agents or foam-type fire extinguishing agents, but these agents have limitations as effective response methods for extinguishing secondary battery fires. Powder-type fire extinguishing agents have the disadvantage of having difficulty responding to the pressure of thermal runaway gas due to the low density of the powder, and they have the disadvantage of not being easy to continuously block oxygen and cool the battery. In addition, foam-type fire extinguishing agents also have difficulty responding to the pressure of thermal runaway gas due to the low density of the foam, and despite the large specific surface area of ​​the foam, the amount of reactive fire extinguishing agent involved in extinguishing is extremely limited, making them an effective means of responding to battery fires.

[0006] Therefore, in the event of a fire in a secondary battery, an inhibitor is required that can be sprayed at a pressure higher than a certain level, sufficiently apply a reactive extinguishing agent involved in extinguishing the fire, and remain on the battery surface at a certain viscosity.

[0007] [Prior Art Literature]

[0008] [Patent Document]

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

[0010]

[0011] The present invention has been devised to solve the above-mentioned technical problem, and its purpose is to provide a secondary battery fire suppressant, a secondary battery fire suppressant member, a secondary battery, and a method for manufacturing a fire suppressant capable of effectively suppressing a fire in a secondary battery.

[0012] The tasks of the present invention are not limited to the tasks mentioned above, and other tasks not mentioned will be clearly understood by those skilled in the art from the description below.

[0013] A fire suppressant according to one embodiment of the present invention is:

[0014] Extinguishing substances which are included to decompose and eject at the decomposition initiation temperature: and

[0015] A solvent that dissolves the above-mentioned digestive substance and converts it into a liquid phase;

[0016] The above digestive substances are,

[0017] A first material comprising an ionic material that causes an adsorption and conversion reaction for a combustible organic compound gas; and

[0018] A second material including at least one of an alkali metal, an alkaline earth metal, a trivalent metal, and an ammonium-based material that absorbs oxygen radicals; capable of blocking a combustion reaction.

[0019] According to one embodiment of the present invention,

[0020] The above first material is,

[0021] It can be formed by combining at least one of carbonate ions, chloride ions, hydroxide ions, phosphate ions, and monovalent, divalent, or trivalent cations.

[0022] According to one embodiment of the present invention,

[0023] The above alkali metals are,

[0024] It may contain one or more of sodium carbonate (Na2CO3), sodium bicarbonate (NaHCO3), potassium carbonate (K2CO3), and potassium bicarbonate (KHCO3), sodium chloride (NaCl), potassium chloride (KCl), sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium phosphate (Na3PO4), and potassium phosphate (K3PO4).

[0025] According to one embodiment of the present invention,

[0026] The above alkaline earth metals are

[0027] It may include one or more of magnesium bicarbonate (Mg(HCO3)2), magnesium carbonate (MgCO3), calcium carbonate (CaCO3), calcium bicarbonate (Ca(HCO3)2), calcium hydroxide (Ca(OH)2), magnesium hydroxide (Mg(OH)2), calcium phosphate (Ca3(PO4)2), and magnesium phosphate (Mg3(PO4)2).

[0028] According to one embodiment of the present invention,

[0029] The above ammonium-based substance

[0030] It may contain at least one of ammonium carbonate ((NH4)2CO3), ammonium bicarbonate (NH4HCO3), and ammonium phosphate ((NH4)3PO4).

[0031] According to one embodiment of the present invention,

[0032] The above three metallic substances are,

[0033] It may contain one or more of aluminum chloride (AlCl3), aluminum hydroxide (Al(OH)3), aluminum phosphate (AlPO4), and iron phosphate (FePO4).

[0034] According to one embodiment of the present invention,

[0035] The above first material is,

[0036] It is decomposed and ejected by the above decomposition initiation temperature,

[0037] The reactive decomposition gas emitted when the first material is decomposed by heat may include one or more of carbon dioxide (CO2), chlorine gas, hydroxyl radicals, and phosphoric acid gas.

[0038] According to one embodiment of the present invention,

[0039] The above solvent is

[0040] It may contain water, ethanol, and one of the organic solvents benzene, acetone, phenol, and ether.

[0041] According to one embodiment of the present invention,

[0042] The above digestive substances are,

[0043] It can be formed by adding one or more of cationic, anionic and amphoteric surfactants.

[0044] According to one embodiment of the present invention,

[0045] The above digestive substances are,

[0046] Viscosity and adhesive strength can be further enhanced by adding an additive containing one or more of glycerin, corn syrup, CMC (carboxymethyl cellulose), and guar gum.

[0047] According to one embodiment of the present invention,

[0048] The above fire retardant may be prepared in one or more of a paste form and a liquid form.

[0049] A method for manufacturing a fire suppressant according to one embodiment of the present invention

[0050] A manufacturing step for manufacturing a fire extinguishing material comprising a first material that causes an adsorption and conversion reaction for a combustible organic compound gas and a second material that absorbs oxygen radicals;

[0051] A mixing step of mixing the above-mentioned digestible substance and solvent; and

[0052] It may include a viscosity control step of mixing an additive into the digestible material mixed in the above solvent.

[0053] A fire suppression member according to one embodiment of the present invention is:

[0054] A pair of fiber members;

[0055] Extinguishing substances which are included to decompose and eject at the decomposition initiation temperature: and

[0056] A solvent that dissolves the above-mentioned digestive substance and converts it into a liquid phase;

[0057] The above digestive substances are,

[0058] A first material comprising an ionic material that causes an adsorption and conversion reaction for a combustible organic compound gas; and

[0059] A second material including at least one of an alkali metal, an alkaline earth metal, a trivalent metal, and an ammonium-based material that absorbs oxygen radicals; capable of blocking a combustion reaction.

[0060] A secondary battery including a topical inhibitor according to one embodiment of the present invention,

[0061] Extinguishing substances which are included to decompose and eject at the decomposition initiation temperature: and

[0062] A solvent that dissolves the above-mentioned digestive substance and converts it into a liquid phase;

[0063] The above digestive substances are,

[0064] A first material comprising an ionic material that causes an adsorption and conversion reaction for a combustible organic compound gas; and

[0065] A second material including at least one of an alkali metal, an alkaline earth metal, a trivalent metal, and an ammonium-based material that absorbs oxygen radicals; capable of blocking a combustion reaction.

[0066] According to one embodiment of the present invention, a fire suppressant capable of effectively suppressing a fire in a secondary battery can be provided.

[0067] According to one embodiment of the present invention, a method for manufacturing a fire suppressant capable of effectively suppressing a fire in a secondary battery can be provided.

[0068] Figure 1 shows a fire extinguisher including a secondary battery fire suppressant according to an embodiment of the present invention, sprayed on a secondary battery in which thermal runaway and fire have occurred, and 100 minutes after the start of thermal runaway. o This is a graph showing the cooling time to C.

[0069] Figure 2 shows a fire extinguisher containing a powdered fire extinguishing agent sprayed on a secondary battery in which thermal runaway and fire occurred, and 100 minutes after the start of thermal runaway.o This is a graph showing the cooling time to C.

[0070] Figure 3 shows a case where a fire extinguisher containing a foam-type extinguishing agent is sprayed on a secondary battery in which thermal runaway and fire have occurred, and the fire is extinguished 100 times after the start of thermal runaway. o This is a graph showing the cooling time to C.

[0071] Figure 4 is a photograph showing a paste-like form of a fire extinguishing material of a secondary battery fire suppressant according to one embodiment of the present invention.

[0072] FIG. 5 is a photograph showing a liquid inhibitor for secondary battery fire according to one embodiment of the present invention.

[0073] Figure 6 is a flow chart of a method for manufacturing a secondary battery fire suppressant according to one embodiment of the present invention.

[0074] FIG. 7 is a photograph showing a fire extinguishing vessel including a liquid inhibitor for secondary battery fire according to one embodiment of the present invention.

[0075] Figure 8 is a fire suppression member including a liquid and paste-type suppressant for secondary battery fire according to one embodiment of the present invention.

[0076] FIG. 9 is an exploded view of layers of a secondary battery fire suppression member according to one embodiment of the present invention.

[0077] Hereinafter, an embodiment of a secondary battery fire suppressant, a secondary battery fire suppressant member, a secondary battery, and a method for manufacturing a fire suppressant according to the present invention will be described in detail with reference to the attached drawings.

[0078] When assigning reference numerals to components in each drawing, it should be noted that identical components are assigned the same numerals whenever possible, even if they appear on different drawings. Furthermore, when describing embodiments of the present invention, if a detailed description of a related known configuration or function is deemed to hinder understanding of the embodiments of the present invention, the detailed description will be omitted.

[0079] In describing the components of the embodiments of the present invention, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are only intended to distinguish the components from other components, and the nature, order, or sequence of the components are not limited by the terms. In addition, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as generally understood by a person of ordinary skill in the art to which the present invention pertains. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning they have in the context of the relevant technology, and shall not be interpreted in an idealized or overly formal sense unless explicitly defined in this application.

[0080]

[0081] Figure 1 shows a fire extinguisher including a secondary battery fire suppressant according to an embodiment of the present invention, sprayed on a secondary battery in which thermal runaway and fire have occurred, and 100 minutes after the start of thermal runaway. o This is a graph showing the cooling time to C, and Figure 2 shows the time taken to cool down to 100°C after the start of thermal runaway by spraying a fire extinguisher containing a powdered fire extinguishing agent on a secondary battery in which thermal runaway and fire occurred. o This is a graph showing the cooling time to C, and Figure 3 shows the time taken to cool down to 100°C after the start of thermal runaway by spraying a fire extinguisher containing a foam-type fire extinguishing agent on a secondary battery in which thermal runaway and fire occurred. oThis is a graph showing the cooling time to C, and FIG. 4 is a photograph showing a paste-like fire extinguishing material of a secondary battery fire suppressant according to an embodiment of the present invention, and FIG. 5 is a photograph showing a liquid-like fire suppressant for a secondary battery according to an embodiment of the present invention.

[0082]

[0083] The fire suppressant according to FIGS. 1 to 5 may include an extinguishing agent that is decomposed and emitted at a decomposition initiation temperature. Here, the extinguishing agent may include a first substance that causes an adsorption and conversion reaction for a combustible organic compound gas and a second substance that absorbs oxygen radicals, and the extinguishing agent may be decomposed and emitted at the decomposition initiation temperature to block a combustion reaction. Here, the extinguishing agent is a substance that has a decomposition initiation temperature and extinguishing properties, and may be referred to as one of a extinguishing agent, a extinguishing agent, and a extinguishing powder when describing embodiments of the present invention hereinafter.

[0084]

[0085] A secondary battery fire suppressant according to one embodiment of the invention may include a fire extinguishing agent. A fire extinguishing agent refers to a composition capable of extinguishing in liquid, gaseous, solid, or powdered states. While the term "fire extinguishing agent" is sometimes used herein, it is intended to illustrate representative examples and is not intended to be construed as being limited to a specific state or form.

[0086]

[0087] The extinguishing agent may include at least one of a first substance that causes an adsorption and conversion reaction for a combustible organic compound gas and a second substance that absorbs oxygen radicals.

[0088]

[0089] The extinguishing agent may include a first substance capable of blocking contact with oxygen and causing asphyxiation in response to fire, and having reactivity with lithium. The extinguishing agent may include a first substance capable of adsorbing and converting flammable organic compound gases generated during thermal runaway of a secondary battery, and the first substance may include one or more of carbonate ions, chloride ions, hydroxide ions, phosphate ions, and monovalent, divalent, or trivalent cations.

[0090]

[0091] The digestible material may include a second material, for example, an inorganic salt powder. The inorganic salt preparation may include alkali metals, alkaline earth metals, and ammonium compounds of the periodic table with strong oxygen radical absorbing properties.

[0092] Alkali metals may include, but are not limited to, one or more of sodium carbonate (Na2CO3), sodium bicarbonate (NaHCO3), potassium carbonate (K2CO3), and potassium bicarbonate (KHCO3), sodium chloride (NaCl), potassium chloride (KCl), sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium phosphate (Na3PO4), and potassium phosphate (K3PO4).

[0093] Alkaline earth metals may include, but are not limited to, one or more of magnesium bicarbonate (Mg(HCO3)2), magnesium carbonate (MgCO3), calcium carbonate (CaCO3), calcium bicarbonate (Ca(HCO3)2), calcium hydroxide (Ca(OH)2), magnesium hydroxide (Mg(OH)2), calcium phosphate (Ca3(PO4)2), and magnesium phosphate (Mg3(PO4)2).

[0094] Ammonium-based substances may include, but are not limited to, one or more of ammonium carbonate ((NH4)2CO3), ammonium bicarbonate (NH4HCO3), and ammonium phosphate ((NH4)3PO4).

[0095] The above trivalent metallic substance may include, but is not limited to, one or more of aluminum chloride (AlCl3), aluminum hydroxide (Al(OH)3), aluminum phosphate (AlPO4), and iron phosphate (FePO4).

[0096]

[0097] A fire suppressant according to one embodiment of the present invention may be decomposed by heat when it reaches a predetermined decomposition initiation temperature, thereby releasing reactive decomposition gases and cationic metal ions.

[0098] The cationic metal ions released when the decomposition initiation temperature is reached can absorb radicals generated from an electric spark or flame, thereby blocking a chain reaction of combustion.

[0099] The reactive decomposition gas emitted upon reaching the decomposition initiation temperature can decompose the flammable organic compound gas emitted from the secondary battery. The reactive decomposition gas emitted upon reaching the predetermined decomposition initiation temperature by the inhibitor containing at least one of carbonate, chloride, hydroxide, and phosphate may be carbon dioxide (CO2), chlorine gas, hydroxyl radical, or phosphoric acid gas.

[0100]

[0101] 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 resistance heat, can also trigger a rapid exothermic reaction, leading to thermal decomposition of the electrolyte and the release of flammable and toxic gases, potentially increasing the temperature and internal pressure of the secondary battery.

[0102] Here, when an inorganic salt included in a secondary battery fire 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.

[0103] 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.

[0104] [Chemical Formula 1]

[0105] Li + + e - → Li

[0106] [Chemical Formula 2]

[0107] 6Li + N2→ 2Li3N

[0108]

[0109] 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.

[0110]

[0111] [Chemical Formula 3]

[0112] 4Li + O2→ 2Li2O

[0113] [Chemical Formula 4]

[0114] 4Li + 2H2O + O2→ 4LiOH

[0115] [Chemical Formula 5]

[0116] 2Li + H2O → Li2O + H2

[0117]

[0118] 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.

[0119] 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).

[0120] Additionally, cationic metal ions can absorb radicals generated from electrical sparks or flames, thereby preventing chain reactions of combustion.

[0121] 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.

[0122] In this way, as the carbonate decomposes, it releases carbon dioxide, and when the carbon dioxide blocks oxygen access due to the suffocating effect, combustion resulting from a secondary battery fire can be effectively contained or effectively extinguished.

[0123]

[0124] [Chemical Formula 6]

[0125] 4Li + 2CO2+ O2→ 2Li2CO3

[0126] [Chemical Formula 7]

[0127] 2Li + 2CO2+ H2O + 1 / 2O2→ 2LiHCO3

[0128]

[0129] 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.

[0130] When the carbonate included in the digestible material 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.

[0131] Here, radical ions can be absorbed by cationic metal ions. This suppresses spark generation in the secondary battery and prevents ignition of the secondary battery. In other words, this anti-catalytic effect suppresses the chain reaction of combustion in the secondary battery. Therefore, fires in secondary batteries containing the secondary battery fire suppressant according to an embodiment of the present invention can be prevented, and the spread of any fires that occur can be suppressed.

[0132]

[0133] A fire suppressant according to one embodiment of the present invention may be comprised of a first substance dissolved in a solvent. The solvent may include, but is not limited to, water, ethanol, and organic solvents such as benzene, acetone, phenol, and ether.

[0134] The fire retardant formed by dissolving in the vein may further contain one or more additives to provide viscosity and adhesiveness. Examples of such additives include glycerin, corn syrup, carboxymethyl cellulose (CMC), and guar gum.

[0135] The extinguishing agent can be dissolved in a solvent to form a liquid fire retardant, and additives can be added to provide additional viscosity and adhesive strength.

[0136]

[0137] According to one embodiment of the present invention, the combination of extinguishing substances can be applied differently depending on the gas to be suppressed.

[0138] The inorganic salt included in the secondary battery fire suppressant according to an embodiment of the present invention may be selected based on the combustible gas emitted. The selection may be made by the secondary battery manufacturer or user, taking into account the usage environment (operating temperature, etc.) of the secondary battery including the secondary battery fire suppressant according to an embodiment of the present invention, or the type of gas determined to be a hazardous combustible gas.

[0139] In other words, depending on the usage or operating environment, the flammable gases 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 inorganic salts may be appropriately selected and used alone or in combination, depending on the flammable gas that could cause a dangerous fire.

[0140]

[0141] The combination ratio of fire suppressants based on carbonate substances among multiple inorganic salts for the suppression target gas is as follows.

[0142] When the gas to be suppressed is carbon monoxide (CO), a fire suppressant can be formed by mixing 15 wt% ammonium carbonate, 10 wt% potassium bicarbonate, 5 wt% magnesium carbonate, 60 wt% water, 5 wt% ethanol, 2 wt% surfactant, 2 wt% glycerin, and 1 wt% carboxymethyl cellulose.

[0143] When the gas to be suppressed is acetylene (C2H2), a fire suppressant can be formed by mixing 10 wt% ammonium carbonate, 10 wt% potassium bicarbonate, 10 wt% magnesium carbonate, 50 wt% water, 12 wt% ethanol, 3 wt% surfactant, 3 wt% glycerin, and 2 wt% carboxymethyl cellulose.

[0144] When the gas to be suppressed is methane (CH4), a fire suppressant can be formed by mixing 15 wt% ammonium carbonate, 5 wt% potassium bicarbonate, 5 wt% magnesium carbonate, 60 wt% water, 10 wt% ethanol, 1 wt% surfactant, 2 wt% glycerin, and 2 wt% carboxymethyl cellulose.

[0145]

[0146] The combination ratio of fire suppressants based on chloride substances among multiple inorganic salts for the target gas is as follows.

[0147] When the gas to be suppressed is propane (C3H8), a fire suppressant can be formed by mixing 25 wt% ammonium chloride, 20 wt% potassium chloride, 10 wt% calcium chloride, 40 wt% water, 1 wt% ethanol, 2 wt% surfactant, and 2 wt% guar gum.

[0148] When the gas to be suppressed is acetylene (C2H2), a fire suppressant can be formed by mixing 20 wt% ammonium chloride, 20 wt% potassium chloride, 10 wt% calcium chloride, 40 wt% water, 5 wt% ethanol, 3 wt% surfactant, and 2 wt% guar gum.

[0149] When the gas to be suppressed is methane (CH4), a fire suppressant can be formed by mixing 25 wt% ammonium chloride, 20 wt% potassium chloride, 10 wt% calcium chloride, 40 wt% water, 1 wt% ethanol, 2 wt% surfactant, and 2 wt% guar gum.

[0150]

[0151] The combination ratio of fire suppressants based on hydroxide substances among multiple inorganic salts for the target gas is as follows.

[0152] When the gas to be suppressed is carbon monoxide (CO), a fire suppressant can be formed by mixing 25 wt% potassium hydroxide, 20 wt% calcium hydroxide, 10 wt% magnesium hydroxide, 40 wt% water, 5 wt% ethanol, 2 wt% surfactant, and 3 wt% guar gum.

[0153] When the gas to be suppressed is acetylene (C2H2), a fire suppressant can be formed by mixing 25 wt% potassium hydroxide, 15 wt% calcium hydroxide, 10 wt% magnesium hydroxide, 40 wt% water, 5 wt% ethanol, 3 wt% surfactant, and 2 wt% guar gum.

[0154] When the gas to be suppressed is methane (CH4), a fire suppressant can be formed by mixing 30 wt% potassium hydroxide, 10 wt% calcium hydroxide, 10 wt% magnesium hydroxide, 40 wt% water, 3 wt% ethanol, 2 wt% surfactant, and 5 wt% guar gum.

[0155]

[0156] The combination ratio of fire suppressants based on phosphate substances among multiple inorganic salts for the target gas is as follows.

[0157] When the gas to be suppressed is carbon monoxide (CO), a fire suppressant can be formed by mixing 15 wt% ammonium phosphate, 15 wt% potassium phosphate, 10 wt% calcium phosphate, 10 wt% magnesium phosphate, 40 wt% water, 5 wt% ethanol, 2 wt% surfactant, and 3 wt% guar gum.

[0158] When the gas to be suppressed is acetylene (C2H2), a fire suppressant can be formed by mixing 10 wt% ammonium phosphate, 10 wt% potassium phosphate, 10 wt% calcium phosphate, 10 wt% magnesium phosphate, 50 wt% water, 5 wt% ethanol, 3 wt% surfactant, and 2 wt% guar gum.

[0159] When the gas to be suppressed is methane (CH4), a fire suppressant can be formed by mixing 20 wt% ammonium phosphate, 15 wt% potassium phosphate, 10 wt% calcium phosphate, 5 wt% magnesium phosphate, 40 wt% water, 3 wt% ethanol, 2 wt% surfactant, and 5 wt% guar gum.

[0160]

[0161] The secondary battery fire suppressant according to the embodiment of the present invention can be selected by the secondary battery manufacturer or user according to the above-described combination in consideration of the usage environment (operating temperature, etc.) of the secondary battery or the type of gas determined to be a dangerous flammable gas.

[0162] When a fire occurs in a secondary battery and the temperature increases to reach a temperature range deemed dangerous, each extinguishing agent may sequentially decompose according to its decomposition initiation temperature, releasing reactive decomposition gases and cationic metal ions.

[0163] This can block oxygen from accessing flammable gases generated from secondary batteries. Furthermore, lithium, which could be a source of ignition, can be rendered non-flammable, and radicals generated by sparks can be absorbed, thereby suppressing the spread of fire.

[0164]

[0165] FIG. 1 is a graph showing the temperature and time required for a secondary battery module to cool to 100 degrees Celsius after thermal runaway occurs by spraying a fire extinguishing container containing a liquid secondary battery fire suppressant according to an embodiment of the present invention onto a secondary battery module in which thermal runaway and fire have occurred.

[0166] As shown in Fig. 1, a liquid secondary battery fire suppressant according to an embodiment of the present invention was sprayed on a secondary battery module in which thermal runaway and fire occurred, and the thermal runaway and flame were effectively suppressed, and the time required for cooling to 100°C was 3 minutes and 20 seconds.

[0167] Figure 2 is a graph showing the temperature and time required for a secondary battery module to cool to 100°C after thermal runaway using a powder fire extinguisher for metal fires. While the powder fire extinguisher for metal fires suppressed thermal runaway and flames, it took 720 minutes to cool to 100°C after thermal runaway.

[0168] Figure 3 is a graph showing the temperature and time required for a secondary battery module to cool to 100°C after thermal runaway using a foam extinguishing agent. Furthermore, although spraying with foam extinguishing agent suppressed thermal runaway and flames, it took 120 minutes for the module to cool to 100°C after thermal runaway.

[0169]

[0170] The liquid and paste-type fire suppressants for secondary battery fires according to one embodiment of the present invention were able to suppress thermal runaway and flames more effectively than powder fire extinguishing agents or foam fire extinguishing agents for metal fires.

[0171]

[0172] The liquid and paste-type fire suppressant (10) for secondary battery fire according to one embodiment of the present invention has a high surface area according to the nanometer-sized particle size dissolved in the liquid, and at the same time, can be sprayed at a certain pressure or higher, can sufficiently apply a reactive fire extinguishing agent involved in fire extinguishing, and can remain on the battery surface with a certain viscosity to contribute to the cooling action of the battery surface, thereby enabling a rapid and effective response to thermal runaway and flames compared to powder fire extinguishing agents and foam-type fire extinguishing agents.

[0173] Liquid and paste-type fire suppressants for secondary battery fires according to one embodiment of the present invention can effectively suppress typical flammable gases generated during a secondary battery fire. The inclusion of a fire extinguishing agent according to one embodiment of the present invention can effectively neutralize flammable organic compounds generated during battery thermal runaway.

[0174]

[0175] Figure 6 is a flow chart of a method for manufacturing a secondary battery fire suppressant according to one embodiment of the present invention.

[0176] A method for manufacturing a fire suppressant according to FIG. 6 may include a manufacturing step (S100) of manufacturing a fire extinguishing material including a first material that causes an adsorption and conversion reaction for a combustible organic compound gas and a second material that absorbs oxygen radicals, a mixing step (S200) of forming a liquid fire extinguishing material by mixing the fire extinguishing material and a solvent, and a viscosity control step (S300) of mixing an additive into the fire extinguishing material mixed in the solvent.

[0177] A method for manufacturing a fire suppressant may include a manufacturing step (S100) of manufacturing a fire extinguishing material. The fire extinguishing material may include at least one of a first material that causes an adsorption and conversion reaction for a combustible organic compound gas and a second material that absorbs oxygen radicals. The first material may include at least one of carbonate ions, chloride ions, hydroxide ions, phosphate ions, and monovalent, divalent, or trivalent cations. The fire extinguishing material may include a second material, for example, an inorganic salt powder. In addition, the inorganic salt formulation may include an alkali metal, an alkaline earth metal, and an ammonium-based material on the periodic table that have strong oxygen radical absorption capabilities.

[0178] When the above-mentioned digestive substance is prepared in the manufacturing step (S200), a mixing step (S200) may be performed to mix the digestive substance with a solvent to form a liquid digestive substance. Here, the solvent may be one of water, ethanol, and organic solvents such as benzene, acetone, phenol, and ether, but is not limited thereto. The digestive substance may be converted into a liquid phase by mixing it with the solvent.

[0179] The liquid fire retardant may undergo a viscosity adjustment step (S300) to adjust its viscosity by adding additives. Additives may be added to the liquid fire retardant, and the viscosity and adhesive strength of the liquid fire retardant may be adjusted by the additives. The additives may include, but are not limited to, one or more of glycerin, corn syrup, CMC (carboxymethyl cellulose), and guar gum.

[0180] Liquid and paste fire suppressants for secondary battery fires can be manufactured by combining extinguishing substances in predetermined amounts according to the target gas to be suppressed and mixing solvents and additives.

[0181]

[0182] FIG. 7 is a photograph showing a fire extinguishing vessel including a liquid suppressant for secondary battery fire according to one embodiment of the present invention, FIG. 8 is a fire suppression member including liquid and paste-type suppressants for secondary battery fire according to one embodiment of the present invention, and FIG. 9 is an exploded view between layers of a secondary battery fire suppression member according to one embodiment of the present invention.

[0183]

[0184] In this embodiment, the secondary battery fire suppression member (1000) may be formed by first applying a paste-type secondary battery fire 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 suppression member (100).

[0185] Alternatively, the secondary battery fire suppression member (1000) may be formed by first forming the secondary battery fire 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 suppression member pad formed into a pad shape.

[0186] A secondary battery fire suppression member (1000) may be provided to cover at least a portion of a secondary battery. The secondary battery fire suppression member (1000) may be provided to cover the battery pack (10) from the inside of the battery pack cover (20).

[0187] Since the secondary battery fire 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).

[0188] When a fire occurs in a secondary battery and the temperature increases to a temperature range deemed dangerous, the inorganic salt of the secondary battery fire 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.

[0189]

[0190] As shown in FIG. 9, the secondary battery fire suppression member (1000) may include a pair of fiber members (210, 220), a secondary battery fire suppression member (100), a heating wire (300), and a switch (400).

[0191] A pair of fiber members (210, 220) and a secondary battery fire suppressant (100) may be the same as those described in FIG. 7.

[0192] The heating wire (300) may be placed on one of the fiber members (220) among a pair of fiber members (210, 220). The heating wire (300) may be in direct contact with the secondary battery fire suppressant (100). In addition, the heating wire (300) may be connected to the secondary battery (11).

[0193] 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).

[0194] 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.

[0195] 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).

[0196] 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.

[0197] The switch (400) can be configured to allow a permissible temperature to be set according to the dangerous temperature required by the user. This allows the extinguishing process initiation temperature of the secondary battery fire suppression member (1000) to be easily and accurately set according to the dangerous temperature required by each user.

[0198] For example, the switch (400) may be configured to include a bimetal that can automatically implement a switching operation depending on temperature.

[0199] In addition, the secondary battery fire 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).

[0200] Meanwhile, the secondary battery fire suppression member (1000) is not limited to detecting temperature, and may detect other things. For example, the secondary battery fire suppression member (1000) may detect pressure.

[0201] When pressure is the target of detection, the secondary battery fire suppression member (1000) may further include a pressure sensor unit (not shown). The pressure sensor unit may detect the internal pressure of the secondary battery (11).

[0202] 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.

[0203]

[0204] It should be understood that the embodiments of the present invention are not necessarily limited to the above-described embodiments, and that those skilled in the art will readily appreciate the possibility of various modifications and implementations within an equivalent scope. Therefore, the true scope of the present invention is defined by the claims set forth below.

[0205]

[0206] [Explanation of symbols]

[0207] 10: Battery pack 11: Secondary battery

[0208] 20: Battery pack cover 100: Secondary battery fire suppressant

[0209] 110: Digestible substances 120: Organic binders

[0210] 210, 220: Fiber member 300: Heating wire

[0211] 400: Switch 500: Temperature sensor part

[0212] 1000: Absence of secondary battery fire suppression

Claims

1. Extinguishing substances that are included to be decomposed and ejected at the decomposition initiation temperature: and A solvent that dissolves the above-mentioned digestive substance and converts it into a liquid phase; The above digestive substances are, A first material comprising an ionic material that causes an adsorption and conversion reaction for a combustible organic compound gas; and A fire suppressant that blocks a combustion reaction, comprising a second material comprising at least one of an alkali metal, an alkaline earth metal, a trivalent metal, and an ammonium-based material that absorbs oxygen radicals.

2. In paragraph 1, The above ionic substance is, A fire retardant formed by combining at least one of carbonate ions, chloride ions, hydroxide ions, and phosphate ions with monovalent cations, divalent cations, and trivalent cations.

3. In paragraph 1, The above alkali metals are, A fire retardant comprising at least one of sodium carbonate (Na2CO3), sodium bicarbonate (NaHCO3), potassium carbonate (K2CO3), and potassium bicarbonate (KHCO3), sodium chloride (NaCl), potassium chloride (KCl), sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium phosphate (Na3PO4), and potassium phosphate (K3PO4).

4. In paragraph 1, The above alkaline earth metals are A fire retardant comprising at least one of magnesium bicarbonate (Mg(HCO3)2), magnesium carbonate (MgCO3), calcium carbonate (CaCO3), calcium bicarbonate (Ca(HCO3)2), calcium hydroxide (Ca(OH)2), magnesium hydroxide (Mg(OH)2), calcium phosphate (Ca3(PO4)2), and magnesium phosphate (Mg3(PO4)2).

5. In paragraph 1, The above ammonium-based substance A fire suppressant comprising at least one of ammonium carbonate ((NH4)2CO3), ammonium bicarbonate (NH4HCO3), and ammonium phosphate ((NH4)3PO4).

6. In paragraph 1, The above three metallic substances are, A fire retardant comprising at least one of aluminum chloride (AlCl3), aluminum hydroxide (Al(OH)3), aluminum phosphate (AlPO4), and iron phosphate (FePO4).

7. In paragraph 1, The above first material is, It is decomposed and ejected by the above decomposition initiation temperature, A fire suppressant, wherein the reactive decomposition gas emitted when the first material is decomposed by heat includes at least one of carbon dioxide (CO2), chlorine gas, hydroxyl radicals, and phosphoric acid gas.

8. In paragraph 1, The above solvent is, A fire retardant containing water, ethanol, and one of the organic solvents benzene, acetone, phenol, or ether.

9. In paragraph 1, The above digestive substances are, A fire retardant formed by adding one or more of cationic, anionic and amphoteric surfactants.

10. In paragraph 1, The above digestive substances are, A fire retardant that provides viscosity and adhesion by adding an additive containing one or more of glycerin, corn syrup, CMC (carboxymethyl cellulose), and guar gum.

11. In paragraph 1, A fire suppressant, wherein the fire suppressant is provided in one or more of a paste form and a liquid form.

12. A manufacturing step for manufacturing a fire extinguishing material comprising a first material that causes an adsorption and conversion reaction for a combustible organic compound gas and a second material that absorbs oxygen radicals; A mixing step of mixing the above-mentioned digestible substance and solvent; and A method for manufacturing a fire retardant, comprising a viscosity control step of mixing an additive into a extinguishing material mixed in the solvent.

13. A pair of fiber members; and Extinguishing substances which are included to decompose and eject at the decomposition initiation temperature: and A solvent that dissolves the above-mentioned digestive substance and converts it into a liquid phase; The above digestive substances are, A first material comprising an ionic material that causes an adsorption and conversion reaction for a combustible organic compound gas; and A fire suppression member that blocks a combustion reaction, including a second material comprising at least one of an alkali metal, an alkaline earth metal, a trivalent metal, and an ammonium-based material that absorbs oxygen radicals.

14. Extinguishing substances that are included to decompose and eject at the decomposition initiation temperature: and A solvent that dissolves the above-mentioned digestive substance and converts it into a liquid phase; The above digestive substances are, A first material comprising an ionic material that causes an adsorption and conversion reaction for a combustible organic compound gas; and A secondary battery comprising a second material including at least one of an alkali metal, an alkaline earth metal, a trivalent metal, and an ammonium-based material that absorbs oxygen radicals; which blocks a combustion reaction.

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