A high temperature thermal initiator and its preparation method and application

Abstract

The application discloses a high-temperature thermal initiator and a preparation method and application thereof. Raw materials such as oxidants, reducing agents and binders are prepared into a slurry, the slurry is attached to a lead wire, and a core is obtained through drying. Finally, the core is wrapped with a wire skin and coated with a moisture-proof curing glue, and finally a high-temperature thermal initiator with an induction temperature of 350 DEG C ± 50 DEG C is prepared. The high-temperature thermal initiator can be applied to application scenarios with gradually increasing temperature and high ignition temperature, such as energy storage power stations and the like, so that the fire extinguishing device can be quickly started to implement fire extinguishing after ignition, the best fire extinguishing performance is ensured, and a large disaster caused by the influence of fire extinguishing medium settlement or escape on the fire extinguishing effect due to the early start of the fire extinguishing device is avoided.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of fire extinguishing, and particularly relates to a high-temperature thermal initiator and a preparation method and application thereof. BACKGROUND

[0002] Due to the very large construction project of pumped storage power station, with the maturity of battery energy storage technology, battery pack energy storage is gradually active in energy storage power station, at present, energy storage technology is widely applied in many fields such as new energy vehicles, isolated microgrid, plant network side, user side and power grid side. With the construction and application of energy storage power station project, its fire hazard gradually appears. In recent years, fire and explosion accidents of energy storage power station occur frequently, according to incomplete statistics, in the past 10 years, more than 30 large-capacity energy storage power station fire and explosion accidents occurred at home and abroad, most of the accidents used lithium ion batteries, and two accidents used lead-acid batteries and sodium-sulfur batteries, causing personnel casualties or major losses of property. It can be seen that it is obviously very important to do well in the fire safety of energy storage power station.

[0003] The fire hazard of the energy storage power station mainly includes two aspects of fire hazard of lithium battery and fire hazard of electrical equipment. The fire hazard of lithium battery mainly comes from its structure, which is directly related to the material composition of the battery. In the case of abuse, such as battery overheating, excessive charging and discharging, battery design defects and short circuit caused by raw material defects, etc., chemical reaction occurs between the internal battery materials, a large amount of heat and gas is generated by the decomposition of electrolyte, and thermal runaway of the battery is caused. In large-scale lithium battery energy storage system, the battery pack has the characteristics of high density and 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 large-capacity energy storage unit. Lithium ion battery fire is quite different from ordinary fire. As an energy aggregate, it is easy to cause chain combustion and explosion reaction of surrounding batteries after thermal runaway occurs, and lithium ion battery will release oxygen during spontaneous combustion, which is easy to cause rekindling. The danger of electrical equipment is due to the existence of a large number of auxiliary electrical equipment in the energy storage power station. When the line is electrified, short-circuited, overloaded, aged, and other unsafe use of electrical equipment produces local high temperature, which causes the combustible material in the electrical equipment to ignite, thereby making the entire energy storage system have fire hazard. As can be seen from the above, the fire occurring in the energy storage industry is gradually warming up and the ignition temperature is relatively high. The conventional automatic fire extinguishing device uses a thermal sensitive wire to start, such as Chinese patents CN1524594A, CN114404841A, CN113108257A, CN102688577B, CN207950358U, CN103736232A, etc. all use thermal sensitive wire to respond to the temperature of the outside world and start the fire extinguishing device. However, the starting temperature of the conventional thermal sensitive wire is about 170 DEG C. When it is applied to the fire extinguishing of the energy storage industry, the problem of premature ignition of the thermal initiator and the premature spraying of the fire extinguishing device may occur. On the one hand, the solid fire extinguishing medium may gradually settle, and on the other hand, if the fire extinguishing space is not sealed, the fire extinguishing medium sprayed by the fire extinguishing device may gradually escape with the air flow, causing the space to be extinguished when the fire occurs to be unable to successfully extinguish the fire due to the low concentration of the fire extinguishing medium. SUMMARY

[0004] In order to solve the above technical problems, the present application provides a kind of medicine that is prepared by using oxidizing agent, reducing agent, adhesive and additive, then the medicine is attached to lead wire to prepare medicine core, wire skin is wound on the surface of medicine core, and moisture-proof curing glue is coated, to prepare high temperature thermal initiator, so that its sensing temperature is 350 DEG C±50 DEG C.

[0005] In order to achieve the above purpose, the present application provides a kind of high temperature thermal initiator, which is composed of lead wire, medicine core and wire skin.

[0006] Preferably, the lead wire is cotton thread, polyester thread or polyester thread.

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

[0008] Preferably, the oxidizing agent is any one of metal-free molecular perovskite, glycidyl azide polymer, potassium perchlorate-based molecular perovskite;

[0009] The reducing agent is any one of potassium hydrogen phthalate, potassium tartrate, potassium hydrogen terephthalate, potassium benzoate, potassium hydrogen tartrate, potassium tert-butoxide, 4-nitrophenyl potassium sulfate, monopotassium citrate;

[0010] The binder is one or more of hydroxyl-terminated polybutadiene, dibutyl itaconate;

[0011] The additive is one or more of propargyl malonate dimethyl, tetramethyl terephthalonitrile oxide, isocyanate;

[0012] Preferably, the high-temperature thermal initiator is an online moisture-proof curing glue coated on the skin.

[0013] The application also provides a preparation method of a high-temperature thermal initiator, comprising the following steps:

[0014] (1) Screen the oxidizing agent, reducing agent, binder and additive respectively, and preliminarily mix to obtain a mixture;

[0015] (2) Disperse and mix the mixture uniformly with a solvent to form a slurry;

[0016] (3) Attach the slurry on a lead wire through an extrusion process, and dry to obtain a drug core;

[0017] (4) Wind a skin on the surface of the drug core, and coat a moisture-proof curing glue, to obtain a high-temperature thermal initiator.

[0018] Preferably, the screen mesh used in step (1) is 180-200 mesh;

[0019] The solvent used in step (2) is any one of acetone, ethyl acetate, methanol, ethanol;

[0020] The drying temperature in step (3) is 40-100℃.

[0021] Preferably, the diameter of the lead wire in step (3) is 0.5-1mm, and the diameter of the prepared drug core is 1.5-2mm.

[0022] Preferably, the skin in step (4) is a polyester tape with a thickness of 1-3mm, and the moisture-proof curing glue is a polyethylene glue with a thickness of 1-2mm.

[0023] The application also provides an application of the high-temperature thermal initiator in a fire extinguishing device of an energy storage power station.

[0024] The application has the beneficial effect that: the application uses perovskite and the like as an oxidizing agent, and a medicament is prepared from the oxidizing agent, a binder and an additive, the medicament is attached to a lead wire to prepare a core, a wire skin is wound on the surface of the dried core, and a moisture-proof curing glue is coated, thereby preparing a high-temperature thermal initiator, the induction temperature of the high-temperature thermal initiator is 350 DEG C + / - 50 DEG C, and the high-temperature thermal initiator can be applied to a gradually warming and high-ignition-temperature scene, such as an energy storage power station, thereby improving the applicability of the fire extinguishing device to the scene and ensuring that the fire extinguishing device can accurately extinguish fire when starting to spray. DETAILED DESCRIPTION

[0025] The technical solutions of the application are further explained and described below in combination with specific embodiments, and it should be noted that the following embodiments are only preferred embodiments of the application and should not be construed as limiting the application, and the protection scope of the application should be subject to the content recorded in the claims. The modifications and replacements of the technical solutions of the application made by those skilled in the art without creative labor fall within the protection scope of the application.

[0026] Embodiment 1

[0027] (1) 65% of the non-metallic molecule perovskite, 15% of the hydrogen potassium terephthalate, 17% of the hydroxyl-terminated butadiene and 3% of the isocyanate were weighed according to the proportion, respectively passed through a 180-mesh sieve, and preliminarily mixed to obtain a mixed material;

[0028] (2) The mixed material was placed in a mixer, 20% of ethanol was added, and the mixed material was stirred, dispersed and uniformly mixed to obtain a slurry, and the slurry was transferred to a hopper of an extruder;

[0029] (3) The cotton thread with a diameter of 0.5 mm was used as a lead wire and was placed in a lead wire machine, and the lead wire machine and the extruder were started, so that the slurry was uniformly mixed in the extruder and was attached to the lead wire, and the lead wire was dried at 50 DEG C to form a core, wherein the diameter of the core was 1.5 mm;

[0030] (4) The wire skin with a thickness of 1 mm was placed in a wrapping machine, then the core was passed through the wrapping machine, a layer of wire skin was wound on the surface of the core, and then the wound core was passed through a coating machine to coat a layer of moisture-proof curing glue with a thickness of 1 mm, and a high-temperature thermal initiator was obtained after molding.

[0031] Embodiment 2

[0032] (1) 65% of the polyazide glycidyl ether, 15% of the potassium benzoate, 17% of the polyitaconic acid dibutyl ester and 3% of the propargyl malonic acid dimethyl ester were weighed according to the proportion, respectively passed through a 180-mesh sieve, and preliminarily mixed to obtain a mixed material;

[0033] (2) Put the mixed material into the mixing machine, add ethanol (20% by mass fraction), stir and disperse, mix uniformly to obtain a slurry, and transfer the slurry to the hopper of the extruder;

[0034] (3) Put the 1.0 mm polyester thread as a lead into the lead machine, start the lead machine and the extruder, make the slurry uniformly mixed in the extruder, and then attach it to the lead, dry at 60°C to form a core, wherein the diameter of the core is 2.0 mm;

[0035] (4) Put the thread skin with a thickness of 2 mm into the wrapping machine, then pass the core through the wrapping machine to wrap a layer of thread skin on the surface of the core, then pass the wrapped thread core through the coating machine to coat a layer of moisture-proof curing glue with a thickness of 1.5 mm, and obtain a high-temperature thermal initiator after molding.

[0036] Example 3

[0037] (1) Weigh 65% potassium perchlorate-based molecular perovskite, 15% potassium tert-butoxide, 17% hydroxyl-terminated butadiene, and 3% propargyl malonate dimethyl ester through a 180 mesh sieve, and preliminarily mix to obtain a mixed material;

[0038] (2) Put the mixed material into the mixing machine, add ethanol (20% by mass fraction), stir and disperse, mix uniformly to obtain a slurry, and transfer the slurry to the hopper of the extruder;

[0039] (3) Put the 1.0 mm polyester thread as a lead into the lead machine, start the lead machine and the extruder, make the slurry uniformly mixed in the extruder, and then attach it to the lead, dry at 60°C to form a core, wherein the diameter of the core is 2.0 mm;

[0040] (4) Put the thread skin with a thickness of 2 mm into the wrapping machine, then pass the core through the wrapping machine to wrap a layer of thread skin on the surface of the core, then pass the wrapped thread core through the coating machine to coat a layer of moisture-proof curing glue with a thickness of 1.5 mm, and obtain a high-temperature thermal initiator after molding.

[0041] Example 4

[0042] (1) Weigh 65% polyazide glycidyl ether, 15% monopotassium citrate, 17% polyitaconic acid dibutyl ester, and 3% tetramethyl terephthalonitrile oxide through a 180 mesh sieve, and preliminarily mix to obtain a mixed material;

[0043] (2) Put the mixed material into the mixing machine, add ethanol (20% by mass fraction), stir and disperse, mix uniformly to obtain a slurry, and transfer the slurry to the hopper of the extruder;

[0044] (3) Put the cotton thread with a diameter of 1.0 mm as a lead into the lead machine, start the lead machine and the extruder, make the slurry mix uniformly in the extruder and then adhere to the lead, dry at 60°C to form a core, wherein the diameter of the core is 2 mm;

[0045] (4) Put the thread skin with a thickness of 2 mm into the wrapping, then pass the core through the wrapping machine to wrap a layer of thread skin on the surface of the core, then pass the wrapped thread core through the coating machine to coat a layer of moisture-proof curing glue with a thickness of 1.5 mm, and obtain a high-temperature thermal initiator after molding.

[0046] Example 5

[0047] (1) Put 40% metal-free molecular perovskite, 30% potassium tartrate, 15% terminal hydrocarbyl butadiene and 15% tetramethyl terephthalate oxide through a 180-mesh sieve according to the proportion, and preliminarily mix to obtain a mixture;

[0048] (2) Put the mixture into the mixing machine, add acetone (20% by mass fraction), stir, disperse and mix uniformly to obtain a slurry, and transfer the slurry to the hopper of the extruder;

[0049] (3) Put the polyester thread with a diameter of 0.5 mm as a lead into the lead machine, start the lead machine and the extruder, make the slurry mix uniformly in the extruder and then adhere to the lead, dry at 60°C to form a core, wherein the diameter of the core is 1.8 mm;

[0050] (4) Put the thread skin with a thickness of 1 mm into the wrapping, then pass the core through the wrapping machine to wrap a layer of thread skin on the surface of the core, then pass the wrapped thread core through the coating machine to coat a layer of moisture-proof curing glue with a thickness of 1.8 mm, and obtain a high-temperature thermal initiator after molding.

[0051] Example 6

[0052] (1) Put 40% metal-free molecular perovskite, 30% potassium tartrate, 15% terminal hydrocarbyl butadiene and 15% tetramethyl terephthalate oxide through a 180-mesh sieve according to the proportion, and preliminarily mix to obtain a mixture;

[0053] (2) Put the mixture into the mixing machine, add acetone (20% by mass fraction), stir, disperse and mix uniformly to obtain a slurry, and transfer the slurry to the hopper of the extruder;

[0054] (3) Put the polyester thread with a diameter of 0.5 mm as a lead into the lead machine, start the lead machine and the extruder, make the slurry mix uniformly in the extruder and then adhere to the lead, dry at 60°C to form a core, wherein the diameter of the core is 1.8 mm;

[0055] (4) Put the wire skin with a thickness of 2 mm into the wrapping, then pass the core through the wrapping machine to wrap a layer of wire skin on the surface of the core, then pass the wrapped core through the coating machine to coat a layer of moisture-proof curing glue with a thickness of 1.5 mm, and obtain the high-temperature thermal initiator after molding.

[0056] Example 7

[0057] (1) Take 60% glycidyl azide, 25% phthalic acid, 13% polyitaconic acid dibutyl ester, and 2% isocyanate by proportion, respectively pass through a 180-mesh screen, and preliminarily mix to obtain a mixture;

[0058] (2) Put the mixture into a mixer, add methanol (20% by mass fraction), stir and disperse, mix uniformly to obtain a slurry, and transfer the slurry to the hopper of the extruder;

[0059] (3) Put cotton thread with a diameter of 1.0 mm as a lead into the lead machine, start the lead machine and the extruder, make the slurry uniformly mixed in the extruder, and then adhere to the lead, dry at 60°C to form a core, wherein the diameter of the core is 2 mm;

[0060] (4) Put the wire skin with a thickness of 3 mm into the wrapping, then pass the core through the wrapping machine to wrap a layer of wire skin on the surface of the core, then pass the wrapped core through the coating machine to coat a layer of moisture-proof curing glue with a thickness of 1 mm, and obtain the high-temperature thermal initiator after molding.

[0061] Comparative Example 1

[0062] Xi'an Angfei Fire-fighting Technology Co., Ltd. AF-RM1 type thermal sensitive wire.

[0063] Comparative Example 2

[0064] Hunan Nanling Fire-fighting Technology Co., Ltd. NX03-170 type thermal sensitive wire.

[0065] Comparative Example 3

[0066] (1) Take 65% nitrocellulose, 15% hydrogen potassium terephthalate, 17% hydroxyl-terminated butadiene, and 3% isocyanate by proportion, respectively pass through a 180-mesh screen, and preliminarily mix to obtain a mixture;

[0067] (2) Put the mixture into a mixer, add ethanol (20% by mass fraction), stir and disperse, mix uniformly to obtain a slurry, and transfer the slurry to the hopper of the extruder;

[0068] (3) Put cotton thread with a diameter of 1.0 mm as a lead into the lead machine, start the lead machine and the extruder, make the slurry uniformly mixed in the extruder, and then adhere to the lead, dry at 50°C to form a core, wherein the diameter of the core is 2 mm;

[0069] (4) Place a 2mm thick wire sheath inside the wrapping, then pass the core through the wrapping machine to wrap a layer of wire sheath on the surface of the core, and then pass the wrapped core through the coating machine to coat a 1mm thick moisture-proof curing adhesive. After molding, a high-temperature thermal initiator is obtained.

[0070] Result detection:

[0071] The high-temperature thermal initiators prepared in the above embodiments and comparative examples were placed in an oven with a programmed temperature rise of 10℃ / min for start-up temperature testing. The results are shown in Table 1.

[0072] The high-temperature heat initiator is installed on the fire extinguishing device, and the extinguishing medium used is 130g aerosol extinguishing medium, using a 2m... 3 The experimental model was heated according to the thermal runaway temperature rise model of the energy storage battery to start the thermal initiator. A particle collector was used to collect the suspended extinguishing medium and calculate its concentration. The concentration of the extinguishing medium in the protected space was simulated and tested when the energy storage battery was thermally runaway and caught fire. The results are shown in Table 1.

[0073] Table 1. Start-up temperature and extinguishing medium concentration of high-temperature thermal initiators prepared with different formulations.

[0074]

[0075] The thermal initiator prepared in this invention has an activation temperature between 330-370℃, which meets the design temperature range of 350℃±50℃. Compared with the commercially available thermal initiators in Comparative Examples 1-2, the activation temperature is significantly higher, making it applicable to scenarios with gradually rising temperatures and high ignition temperatures, such as energy storage power stations. This facilitates the precise timing of fire suppression system activation for extinguishing the fire. Furthermore, when the thermal initiators prepared in Examples 1-7 activate the extinguishing medium for discharge, due to the later activation time, the concentration of the extinguishing medium is 60 g / m³ when the protected space ignites. 3 The above is consistent with the theoretical design concentration of 65 g / m³. 3 The results are basically consistent, but the concentration of the extinguishing medium in Comparative Examples 1-2 is only half of the theoretical value. Therefore, it shows that the thermal initiator prepared by the present invention can delay the discharge time of the extinguishing device, ensure that the extinguishing device has the maximum extinguishing concentration when extinguishing fire, and thus greatly increase the extinguishing efficiency.

Claims

1. A high temperature thermal initiator characterized by: The high-temperature thermal initiator is composed of a lead wire, a core and a wire skin; The core is composed of 40-70% oxidizing agent, 10-30% reducing agent, 5-15% adhesive and 2-20% additive; The oxidizing agent is glycidyl azide polymer; The reducing agent is any one of hydrogen potassium phthalate, potassium tartrate, hydrogen potassium terephthalate, potassium benzoate, hydrogen potassium tartrate, potassium tert-butoxide, 4-nitrophenyl potassium sulfate and monopotassium citrate; The adhesive is any one of hydroxyl-terminated polybutadiene and dibutyl itaconate; The additive is any one of 2,2-propargyl malonic acid dimethyl ester, tetramethyl p-phenylenediamine oxide and isocyanate.

2. A high temperature thermal initiator according to claim 1, characterized in that: The lead wire is cotton thread, polyester thread or polyester thread.

3. A high temperature thermal initiator according to claim 1, wherein: The high-temperature thermal initiator is coated with moisture-proof curing glue on the wire skin.

4. A process for the preparation of a high temperature thermal initiator as claimed in any one of claims 1 to 3, characterised in that: The method comprises the following steps: (1) Screen the oxidizing agent, reducing agent, adhesive and additive respectively, and then preliminarily mix to obtain a mixture; (2) Disperse and mix the mixture with a solvent to form a slurry; (3) Attach the slurry to the lead wire through an extrusion process, and dry to obtain the core; (4) Wind a polyester tape on the surface of the core as the wire skin, and coat a polyethylene glue on the wire skin through an extruder to obtain the high-temperature thermal initiator.

5. The method of claim 4, wherein: The screen mesh used in step (1) is 180-200 mesh; The solvent used in step (2) is any one of acetone, ethyl acetate, methanol and ethanol; The drying temperature in step (3) is 40-100℃.

6. The method of claim 4, wherein: The diameter of the lead wire in step (3) is 0.5-1mm, and the diameter of the prepared core is 1.5-2mm.

7. The method of claim 4, wherein: The wire skin in step (4) is a polyester tape with a thickness of 1-3mm, and the moisture-proof curing glue is a polyethylene glue with a thickness of 1-2mm.

8. Application of the high-temperature thermal initiator of any one of claims 1-3 or prepared by the preparation method of any one of claims 4-7 in a fire extinguishing device of an energy storage power station.

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