High-temperature thermal release, its manufacturing process and use

Abstract

A high-temperature thermal release device, its manufacturing process, and its application are described. A slurry is produced from raw materials such as oxidizing agents, reducing agents, and binders. This slurry is then applied to an ignition wire and dried to form a core. Finally, a wire sheath is wound around the core, and a moisture-resistant curing adhesive is applied. The end product is a high-temperature thermal release device with an induction temperature of 350 °C ± 50 °C. This high-temperature thermal release device is suitable for scenarios with gradual temperature increases and elevated ignition thresholds, such as in energy storage power plants. It enables immediate activation of the fire suppression system after a fire breaks out, facilitating fire suppression and ensuring optimal fire suppression performance.This prevents premature activation of the fire extinguishing device, which could cause the extinguishing agent to settle or disperse, impairing the fire extinguishing effect and thus causing serious disasters.

Description

TECHNICAL AREA

[0001] The present invention belongs to the field of fire fighting technology and in particular relates to a high-temperature thermal trigger, its manufacturing process and use. STATE OF THE ART

[0002] Given the enormous scale of pumped-storage hydroelectric power plant construction projects, battery pack energy storage has become increasingly important in these plants as battery storage technology has advanced. Currently, energy storage technologies are widely used in numerous areas, including new energy vehicles, isolated microgrids, factory and grid-side, consumer-side, and grid-level applications. However, with the construction and commissioning of energy storage power plant projects, their fire hazards have gradually become apparent. In recent years, the number of fires and explosions at energy storage power plants has increased significantly. According to incomplete statistics, more than 30 major fires and explosions have occurred at large-capacity energy storage power plants worldwide in the last decade.Most of these incidents involved lithium-ion batteries; two further accidents involved lead-acid and sodium-sulfur batteries, resulting in numerous casualties and significant property damage. It goes without saying that ensuring fire safety in energy storage power plants is of paramount importance.

[0003] The fire hazards of energy storage power plants primarily encompass two aspects: the fire risks emanating from lithium batteries and the fire hazards associated with electrical systems. The fire risks emanating from lithium batteries arise primarily from their design and are directly related to the battery's material composition. Improper use, such as overheating, overcharging / over-discharging, or short circuits resulting from battery design flaws or the use of substandard raw materials, leads to chemical reactions between the internal battery materials. The resulting electrolyte decomposition generates significant heat and flammable gases, leading to thermal runaway within the battery. In large-scale energy storage systems with lithium batteries, battery packs are characterized by high density and a centralized distribution.Lithium battery modules are connected in series to form a single battery pack, and multiple battery packs are connected in parallel to form a high-capacity energy storage unit. Lithium-ion battery fires differ significantly from conventional fires. As energy-intensive components, they readily trigger chain reactions of combustion and explosions in surrounding batteries after a thermal runaway. Furthermore, lithium-ion batteries release oxygen upon spontaneous combustion, making them susceptible to reignition. The fire hazards associated with electrical installations result from the numerous auxiliary electrical devices present in energy storage power plants.If these electrical systems are used improperly—for example, due to leaks, short circuits, overloads, or aging—the resulting locally high temperatures can ignite flammable materials within the electrical systems. This creates a fire hazard for the entire energy storage system. In summary, fires in the energy storage industry are always accompanied by a gradual temperature increase and relatively high ignition thresholds. Conventional automatic fire extinguishing devices currently use heat-sensitive wires for temperature-dependent activation. Examples include the Chinese patents CN1524594A, CN114404841A, CN113108257A, CN102688577B, CN207950358U, CN103736232A, etc. These rely on heat-sensitive wires to react to ambient temperatures and activate the fire extinguishing devices.However, the activation temperature of conventional heat-sensitive wires is around 170 °C. When used for fire suppression in the energy storage industry, the problem arises of premature ignition of the thermal trigger, leading to premature release of the fire extinguishing device. Firstly, if the prematurely released extinguishing agent is solid, it can gradually settle. Secondly, if the extinguishing chamber is not sealed, the extinguishing agent sprayed by the device gradually disperses with the airflow, resulting in the fire not being successfully extinguished due to the insufficient concentration of the extinguishing agent in the chamber. CONTENT OF THE PRESENT INVENTION

[0004] In view of the aforementioned technical problems, the present invention provides for a high-temperature thermal trigger manufactured as follows: first, a compound consisting of an oxidizing agent, a reducing agent, a binder, and an additive is prepared; then, the compound is applied to an ignition wire to form a core; subsequently, a wire sheath is wound around the core surface, followed by the application of a moisture-resistant curing adhesive. This achieves an induction temperature of 350 °C ± 50 °C.

[0005] To achieve the above-mentioned objectives, the present invention provides a high-temperature thermal trigger consisting of an ignition wire, a core and a wire sheath.

[0006] Preferably, the ignition wire is a cotton thread, a polyester thread or a polyester yarn.

[0007] Preferably, the core consists of 40-70% oxidizing agent, 10-30% reducing agent, 5-15% binder and 2-20% additive.

[0008] Preferably, the oxidizing agent is one of the following: metal-free molecular perovskite, polyazide glycidyl ether or potassium perchlorate-based molecular perovskite;

[0009] The reducing agent is one of the following: potassium hydrogen phthalate, potassium tartrate, potassium hydrogen terephthalate, potassium benzoate, potassium hydrogen tartrate, potassium tert-butoxide, potassium 4-nitrobenzene sulfate or potassium monocitrate.

[0010] The binder is one or more of the following: hydroxyl-terminated polybutadiene or di-n-butylitaconic acid ester;

[0011] The additive is one or more of the following: dimethylallyl malonate, tetramethyl terephthalonitrile oxide or isocyanate;

[0012] Preferably, the high-temperature thermal trigger is a moisture-resistant curing adhesive that is applied to the wire sheathing.

[0013] The present invention further provides a manufacturing process for a high-temperature thermal release, comprising the following steps: (1) Separate sieving of oxidizing agent, reducing agent, binder and additive, followed by a preliminary mixing to obtain a mixture; (2) Disperse and mix the mixture uniformly with a solvent to form a slurry; (3) Applying the slurry to a firing wire by an extrusion process, followed by drying to obtain a core; (4) Wrapping a wire sheath around the core surface and applying a moisture-resistant curing adhesive to obtain a high-temperature thermal trigger.

[0014] Preferably the mesh size of the sieve used in the sieving process described in step (1) is 180 to 200 meshes;

[0015] The solvent in step (2) is one of acetone, ethyl acetate, methanol or ethanol.

[0016] The drying temperature in step (3) is 40-100°C.

[0017] Preferably the diameter of the ignition wire in step (3) is 0.5 to 1 mm and the diameter of the produced core is 1.5 to 2 mm.

[0018] Preferably, the wire sheathing in step (4) is a polyester tape with a thickness of 1-3 mm and the moisture-resistant curing adhesive is a polyethylene adhesive with a thickness of 1-2 mm.

[0019] The present invention further provides for the use of a high-temperature thermal trigger in a fire extinguishing device for energy storage power plants.

[0020] The advantageous effects of the present invention are as follows: By using substances such as perovskite as an oxidizing agent, the present invention produces a composition of the oxidizing agent, binder, and additive. This composition is then applied to an ignition wire to form a core. After drying, the core surface is wrapped with a wire sheath and coated with a moisture-resistant curing adhesive, thereby producing a high-temperature thermal trigger with an induction temperature of 350 °C ± 50 °C, making it suitable for scenarios with gradual temperature increases and elevated ignition thresholds, such as in energy storage power plants. This improves the applicability of the fire extinguishing device in various scenarios and ensures precise fire suppression upon activation and release of the fire extinguishing device. DETAILED DESCRIPTION

[0021] The technical solutions of the present invention are explained in more detail below with reference to specific embodiments. It should be noted that the embodiments described below represent only preferred embodiments of the present invention and should not be interpreted as limiting the scope of the present invention. The scope of protection of the present invention is determined by the content of the claims. Modifications or replacements of the technical solutions of the present invention by those skilled in the art, which do not require creative work, are within the scope of protection of the present invention. First embodiment (1) Weighing out 65% metal-free molecular perovskite, 15% potassium hydrogen terephthalate, 17% hydroxy-terminated butadiene and 3% isocyanate according to the specified proportions and sieving each material through a 180-mesh sieve, followed by a preliminary mixing to obtain a mixture; (2) Place the mixture in a mixer, add ethanol (20 wt%), stir to disperse it and mix evenly to form a slurry, then transfer the slurry into the extruder hopper; (3) Inserting a cotton thread with a diameter of 0.5 mm as ignition wire into the ignition wire machine, starting the ignition wire machine and the extruder so that the slurry is applied to the ignition wire after uniform mixing in the extruder, forming a core after drying at 50 °C, the core having a diameter of 1.5 mm; (4) Inserting a 1 mm thick wire sheath into a winding machine, then passing the core through the winding machine, winding a layer of wire sheath around the core surface, then passing the wrapped core wire through a coating machine to apply a 1 mm thick layer of moisture-resistant curing adhesive, and obtaining a high-temperature thermal release after forming. Second embodiment (1) Weighing out 65% polyazide glycidyl ether, 15% potassium benzoate, 17% di-n-butylitaconic acid ester and 3% dimethyl 2,2-propynyl malonate according to the specified proportions and sieving each material through a 180-mesh sieve, followed by a preliminary mixing to obtain a mixture; (2) Place the mixture in a mixer, add ethanol (20 wt%), stir to disperse it and mix evenly to form a slurry, then transfer the slurry into the extruder hopper; (3) Inserting a 1.0 mm polyester thread as ignition wire into the ignition wire machine, starting the ignition wire machine and the extruder so that the slurry is applied to the ignition wire after uniform mixing in the extruder, forming a core after drying at 60 °C, the core having a diameter of 2.0 mm; (4) Inserting a 2 mm thick wire sheath into a winding machine, then passing the core through the winding machine, wrapping a layer of wire sheath around the core surface, then passing the wrapped core wire through a coating machine to apply a 1.5 mm thick layer of moisture-resistant curing adhesive, and obtaining a high-temperature thermal release after forming. Third example (1) Weighing out 65% molecular perovskite based on potassium perchlorate, 15% potassium tert-butoxide, 17% hydroxy-terminated butadiene and 3% dimethylallyl malonate according to the specified proportions and sieving each material through a 180-mesh sieve, followed by a preliminary mixing to obtain a mixture; (2) Place the mixture in a mixer, add ethanol (20 wt%), stir to disperse it and mix evenly to form a slurry, then transfer the slurry into the extruder hopper; (3) Inserting a 1.0 mm polyester yarn as ignition wire into an ignition wire machine, starting the ignition wire machine and the extruder so that the slurry is applied to the ignition wire after uniform mixing in the extruder, forming a core after drying at 50 °C, the core having a diameter of 2 mm; (4) Inserting a 3 mm thick wire sheath into a winding machine, then passing the core through the winding machine, wrapping a layer of wire sheath around the core surface, then passing the wrapped core wire through a coating machine to apply a 2 mm thick layer of moisture-resistant curing adhesive, and obtaining a high-temperature thermal release after forming. Fourth embodiment (1) Weighing out 65% polyazide glycidyl ether, 15% potassium monocitrate, 17% di-n-butylitaconic acid ester and 3% tetramethyl terephthalonitrile oxide according to the specified proportions and sieving each material through a 180-mesh sieve, followed by a preliminary mixing to obtain a mixture; (2) Place the mixture in a mixer, add ethanol (20 wt%), stir to disperse it and mix evenly to form a slurry, then transfer the slurry into the extruder hopper; (3) Inserting a cotton thread with a diameter of 1.0 mm as ignition wire into an ignition wire machine, starting the ignition wire machine and the extruder so that the slurry is applied to the ignition wire after uniform mixing in the extruder, forming a core after drying at 60 °C, the core having a diameter of 2 mm; (4) Inserting a 2 mm thick wire sheath into a winding machine, then passing the core through the winding machine, wrapping a layer of wire sheath around the core surface, then passing the wrapped core wire through a coating machine to apply a 1.5 mm thick layer of moisture-resistant curing adhesive, and obtaining a high-temperature thermal release after forming. Fifth embodiment (1) Weighing out 40% metal-free molecular perovskite, 30% potassium tartrate, 15% hydrocarbon-terminated butadiene and 15% tetramethyl terephthalonitrile oxide according to the specified proportions and sieving each material through a 180-mesh sieve, followed by a preliminary mixing to obtain a mixture; (2) Place the mixture into a mixer, add acetone (20 wt%), stir to disperse it and mix evenly to form a slurry, then transfer the slurry into the extruder hopper; (3) Inserting a polyester thread with a diameter of 0.5 mm as ignition wire into an ignition wire machine, starting the ignition wire machine and the extruder so that the slurry is applied to the ignition wire after uniform mixing in the extruder, forming a core after drying at 60 °C, the core having a diameter of 1.8 mm; (4) Inserting a 1 mm thick wire sheath into a winding machine, then passing the core through the winding machine, wrapping a layer of wire sheath around the core surface, then passing the wrapped core wire through a coating machine to apply a 1.8 mm thick layer of moisture-resistant curing adhesive, and obtaining a high-temperature thermal release after forming. Sixth embodiment (1) Weighing out 70% metal-free molecular perovskite, 10% potassium 4-nitrobenzene sulfate, 5% hydrocarbon-terminated butadiene and 15% tetramethyl terephthalonitrile oxide according to the specified proportions and sieving each material through a 180-mesh sieve, followed by a preliminary mixing to obtain a mixture; (2) Place the mixture into a mixer, add ethyl acetate (20 wt%), stir to disperse it and mix evenly to form a slurry, then transfer the slurry into the extruder hopper; (3) Inserting a polyester yarn with a diameter of 0.5 mm as ignition wire into an ignition wire machine, starting the ignition wire machine and the extruder so that the slurry is applied to the ignition wire after uniform mixing in the extruder, forming a core after drying at 50 °C, the core having a diameter of 1.5 mm; (4) Inserting a 2 mm thick wire sheath into a winding machine, then passing the core through the winding machine, wrapping a layer of wire sheath around the core surface, then passing the wrapped core wire through a coating machine to apply a 1.5 mm thick layer of moisture-resistant curing adhesive, and obtaining a high-temperature thermal release after forming. Seventh embodiment (1) Weighing out 60% polyazide glycidyl ether, 25% potassium hydrogen terephthalate, 13% di-n-butyl itaconic acid ester and 2% isocyanate according to the specified proportions and sieving each material through a 180-mesh sieve, followed by a preliminary mixing to obtain a mixture; (2) Place the mixture into a mixer, add methanol (20 wt%), stir to disperse it and mix evenly to form a slurry, then transfer the slurry into the extruder hopper; (3) Inserting a cotton thread with a diameter of 1.0 mm as ignition wire into an ignition wire machine, starting the ignition wire machine and the extruder so that the slurry is applied to the ignition wire after uniform mixing in the extruder, forming a core after drying at 60 °C, the core having a diameter of 2 mm; (4) Inserting a 3 mm thick wire sheath into a winding machine, then passing the core through the winding machine, wrapping a layer of wire sheath around the core surface, then passing the wrapped core wire through a coating machine to apply a 1 mm thick layer of moisture-resistant curing adhesive, and obtaining a high-temperature thermal release after forming. First comparative example

[0022] Heat-sensitive wire of type AF-RM1 from Xi'an Angfei Brandschutztechnik GmbH. Second comparative example

[0023] Heat-sensitive wire type NX03-170 from Hunan Nanling Brandschutztechnik GmbH. Third comparative example (1) Weighing out 65% nitrocellulose, 15% potassium hydrogen terephthalate, 17% hydroxy-terminated butadiene and 3% isocyanate according to the specified proportions and sieving each material through a 180-mesh sieve, followed by a preliminary mixing to obtain a mixture; (2) Place the mixture in a mixer, add ethanol (20 wt%), stir to disperse it and mix evenly to form a slurry, then transfer the slurry into the extruder hopper; (3) Inserting a cotton thread with a diameter of 1.0 mm as ignition wire into an ignition wire machine, starting the ignition wire machine and the extruder so that the slurry is applied to the ignition wire after uniform mixing in the extruder, forming a core after drying at 50 °C, the core having a diameter of 2 mm; (4) Inserting a 2 mm thick wire sheath into a winding machine, then passing the core through the winding machine, wrapping a layer of wire sheath around the core surface, then passing the wrapped core wire through a coating machine to apply a 1 mm thick layer of moisture-resistant curing adhesive, and obtaining a high-temperature thermal release after forming. Results review:

[0024] The high-temperature thermal releases produced in the exemplary embodiments and comparative examples described above were subjected to an activation temperature test in an oven with a programmed temperature ramp of 10 °C / min. The results are shown in Table 1.

[0025] A high-temperature thermal trigger was installed on the fire extinguishing device. 130 g of aerosol fire extinguishing agent was used. In a 2 m 3In a large experimental model, the temperature was increased according to the model for the thermal pass of an energy storage battery to activate the thermal trigger. The suspended fire extinguishing agent was collected with a particle sampler, and its concentration was calculated. The concentration of the fire extinguishing agent in the protected space during a thermal pass fire of the energy storage battery was simulated and tested. The results are shown in Table 1. Table 1: Activation temperatures and concentrations of the fire extinguishing agent of the high-temperature thermal triggers produced using different formulations Activation temperature (°C) Concentration of fire extinguishing agent in the protected space during a fire (g / m³) 3 ) First embodiment 361 64 Second embodiment 342 62 Third example 355 63 Fourth embodiment 337 61 Fifth embodiment 345 62 Sixth embodiment 351 61 Seventh embodiment 358 63 First comparative example 167 32 Second comparative example 172 35 Third comparative example 186 39

[0026] The thermal release device manufactured according to the invention has an activation temperature between 330 and 370 °C, thus fulfilling the designed temperature range of 350 °C ± 50 °C. Compared to the commercially available thermal releases in Comparative Examples 1 and 2, the activation temperature is significantly higher. This makes it suitable for scenarios with gradual temperature increases and elevated ignition thresholds, such as in energy storage power plants. This enables activation of the fire extinguishing device at a precise moment of fire outbreak in order to release the extinguishing agent in a controlled manner. Furthermore, the thermal releases manufactured in Exemplary Examples 1-7 exhibited a delayed activation time when activating the extinguishing agent for release. Consequently, a concentration of 60 g / m³ of extinguishing agent is released in the protected space when a fire breaks out. 3or more. This concentration essentially corresponds to the theoretically designed concentration of 65 g / m³. 3 , whereas the concentration of the fire extinguishing agent in comparative examples 1-2 was only half the theoretical value. Thus, it is shown that the thermal trigger produced according to the invention can delay the release time of the fire extinguishing device and thus ensure the maximum extinguishing agent concentration during fire suppression, thereby significantly increasing fire suppression efficiency. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] CN 1524594A

[0003] CN 114404841A

[0003] CN 113108257A

[0003] CN 102688577B

[0003] CN 207950358U

[0003] CN 103736232A

[0003]

Claims

[1] High-temperature thermal release, characterized by , that the high-temperature thermal trigger consists of a firing wire, a core and a wire sheath. [2] High-temperature thermal release according to claim 1, characterized by that the ignition wire is a cotton thread, a polyester thread or a polyester yarn. [3] High-temperature thermal release according to claim 1, characterized by that the core consists of 40-70% oxidizing agent, 10-30% reducing agent, 5-15% binder and 2-20% additive. [4] High-temperature thermal release according to claim 3, characterized by , that the oxidizing agent is one of the following: metal-free molecular perovskite, polyazide glycidyl ether or potassium perchlorate-based molecular perovskite; The reducing agent is one of the following: potassium hydrogen phthalate, potassium tartrate, potassium hydrogen terephthalate, potassium benzoate, potassium hydrogen tartrate, potassium tert-butoxide, potassium 4-nitrobenzene sulfate or potassium monocitrate; The binder is one of the following: hydroxyl-terminated polybutadiene or di-n-butylitaconic acid ester; the additive is one of the following: dimethyl 2,2-propynyl malonate, tetramethyl terephthalonitrile oxide or isocyanate; [5] High-temperature thermal release according to claim 1, characterized by , that the high-temperature thermal trigger is a moisture-resistant curing adhesive that is applied to the wire sheathing. [6] Manufacturing process for a high-temperature thermal release according to any one of claims 1 to 5, characterized by that it includes the following steps: (1) Separate sieving of oxidizing agent, reducing agent, binder and additive, followed by a preliminary mixing to obtain a mixture; (2) Disperse and mix the mixture uniformly with a solvent to form a slurry; (3) Applying the slurry to the ignition wire by an extrusion process, followed by drying to obtain a core; (4) Wrapping a polyester tape as a wire sheath around the core surface and applying a polyethylene adhesive as a moisture-resistant curing adhesive by means of an extruder to obtain a high-temperature thermal trigger. [7] Manufacturing process according to claim 6, characterized by , that the mesh size of the sieve used in the sieving described in step (1) is 180 to 200 meshes; the solvent in step (2) is one of acetone, ethyl acetate, methanol or ethanol; The drying temperature in step (3) is 40-100°C. [8] Manufacturing process according to claim 6, characterized by , that the diameter of the ignition wire in step (3) is 0.5 to 1 mm and the diameter of the produced core is 1.5 to 2 mm. [9] Manufacturing process according to claim 6, characterized by , that the wire sheathing in step (4) is a polyester tape with a thickness of 1-3 mm and the moisture-resistant curing adhesive is a polyethylene adhesive with a thickness of 1-2 mm. [10] Use of a high-temperature thermal release according to one of claims 1 to 5 or of a high-temperature thermal release manufactured according to the manufacturing process according to one of claims 6 to 9 in a fire extinguishing device for energy storage power plants.