CN111013052A - Water-gas composite lithium ion battery fire control method - Google Patents
Water-gas composite lithium ion battery fire control method Download PDFInfo
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- CN111013052A CN111013052A CN201911346094.7A CN201911346094A CN111013052A CN 111013052 A CN111013052 A CN 111013052A CN 201911346094 A CN201911346094 A CN 201911346094A CN 111013052 A CN111013052 A CN 111013052A
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C3/00—Fire prevention, containment or extinguishing specially adapted for particular objects or places
- A62C3/16—Fire prevention, containment or extinguishing specially adapted for particular objects or places in electrical installations, e.g. cableways
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C31/00—Delivery of fire-extinguishing material
- A62C31/02—Nozzles specially adapted for fire-extinguishing
- A62C31/05—Nozzles specially adapted for fire-extinguishing with two or more outlets
- A62C31/07—Nozzles specially adapted for fire-extinguishing with two or more outlets for different media
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C31/00—Delivery of fire-extinguishing material
- A62C31/02—Nozzles specially adapted for fire-extinguishing
- A62C31/12—Nozzles specially adapted for fire-extinguishing for delivering foam or atomised foam
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
本发明公开了一种水气复合的锂离子电池火灾控制方法，包括气体灭火剂熄灭明火和细水雾冷却降温。气体灭火剂在锂离子电池热失控后立刻响应，高效的扑灭明火，同时降低火焰产生的热浮力，降低烟雾浓度；随后释放细水雾，细水雾颗粒在没有明火，热浮力、烟雾浓度较小的情况下到达锂离子电池表面，降低锂离子电池表面温度，冷却电池，从而防止电池组发生连锁热失控。本发明所提出的灭火方法能够迅速的熄灭电池火灾，使细水雾颗粒更容易得到达电池表面，降低电池温度，阻断热失控的传播，解决了锂离子电池火灾中电池难以降温，容易复燃及引发电池组连锁热失控的问题，从而降低锂离子电池火灾的危险性。
The invention discloses a fire control method for a lithium ion battery combined with water and gas. The gas fire extinguishing agent responds immediately after the thermal runaway of the lithium-ion battery, effectively extinguishing the open fire, and at the same time reducing the thermal buoyancy generated by the flame and reducing the smoke concentration; then it releases a fine water mist, and the fine water mist particles have a higher thermal buoyancy and smoke concentration when there is no open fire. It can reach the surface of the lithium-ion battery in small cases, reduce the surface temperature of the lithium-ion battery, and cool the battery, thereby preventing the chain thermal runaway of the battery pack. The fire extinguishing method proposed by the invention can quickly extinguish the battery fire, make the fine water mist particles more easily reach the surface of the battery, reduce the temperature of the battery, block the spread of thermal runaway, and solve the problem that the battery is difficult to cool down in a lithium ion battery fire, and it is easy to recover. It can reduce the risk of lithium-ion battery fire and cause the problem of interlocking thermal runaway of the battery pack.
Description
Technical Field
The invention belongs to the field of lithium ion battery fire suppression in the technical field of safety, and particularly relates to a water-gas composite lithium ion battery fire control method.
Background
In recent years, lithium ion batteries have been widely used in the fields of energy storage power stations, consumer electronics, new energy vehicles, and the like because of their advantages of high energy density, long cycle life, environmental friendliness, and small self-discharge. At present, the conservation quantity of lithium ion batteries and lithium electric vehicles in China shows a trend of increasing year by year, and the status of the lithium ion batteries as the post industry of the new energy industry cannot swing within a period of time in the future. However, lithium ion batteries are very dangerous in some abuse situations and are prone to fire and explosion. Because the battery is closely arranged in the battery pack, after a single battery is out of control due to heat, if the single battery cannot effectively extinguish the fire and cool down in time, the fire of the lithium battery can be rapidly developed, the thermal out-of-control chain reaction of the whole battery pack is caused, and then large-scale fire or explosion accidents occur, and huge economic loss or even casualties are caused. Therefore, the development of a fire extinguishing method capable of effectively extinguishing the battery fire and inhibiting the thermal runaway propagation of the lithium battery has important significance.
At present, the fire-fighting technology suitable for lithium ion battery fire is few, and the existing fire-fighting method has poor effect and has great defects and shortcomings. The existing lithium battery fire extinguishing method mainly adopts single gas fire extinguishing, such as fire extinguishing agents of heptafluoropropane and perfluorohexanone. They can capture free radicals in combustion, block chain reaction and quickly extinguish open fire, but their cooling capacity is very limited and cannot reduce the internal temperature of the battery. Although there is no open fire outside, the reaction inside the battery is still in progress, and the surface temperature of the battery is still very high, which may continue to transfer heat to the adjacent battery, induce thermal runaway of the adjacent battery, cause thermal runaway chain reaction of the battery pack, and fail to effectively control the lithium battery fire. The water mist has the advantages of environmental protection, low water consumption, less harm to protected objects, strong cooling capacity and the like, and can be used for extinguishing lithium ion battery fire. The fine water mist has smaller particles, so that the surface area of the fine water mist is greatly increased compared with that of water with the same volume, thereby enhancing the heat exchange efficiency and playing a good cooling effect. But the smaller particles also make it difficult for the droplets to penetrate the smoke and plume buoyancy to reach the cell surface. Therefore, the single use of the water mist can hardly achieve good effect on extinguishing the battery fire. Studies of plum-Uygur autonomous region and the like show that the spraying intensity of the water mist is 2.5L/(min m)2) And the fire disaster of 18650 type lithium cobalt oxide lithium ion batteries cannot be effectively suppressed or extinguished under the condition that the height of the spray head is 2.4 m.
The invention provides a more efficient fire extinguishing method aiming at the characteristics of lithium ion battery fires, namely the fire extinguishing method has the functions of quickly extinguishing fire and cooling, can quickly extinguish open fire, prevent flame from spreading, can reduce the temperature of a battery, prevent the occurrence of thermal runaway chain reaction in a battery pack, realize quick action at the initial stage of the lithium ion battery fire and prevent the further damage of the battery fire.
Disclosure of Invention
The invention aims to provide a water-gas composite lithium ion battery fire control method, which complements the advantages of a gas fire extinguishing agent and a water mist fire extinguishing agent, provides a fire extinguishing method with the functions of quick fire extinguishing and cooling, and overcomes the defects of the existing battery fire extinguishing technology. The battery fire is controlled within a controllable range, the battery fire is prevented from further spreading, the personnel and property loss is reduced, and the safety of the battery pack is improved.
In order to solve the above problems and achieve the above object, the present invention has the technical solution: a fire control method for a water-gas composite lithium ion battery. The method mainly comprises two parts, namely extinguishing open fire by using a gas extinguishing agent and cooling by using water mist: the gas extinguishing agent responds immediately after the lithium ion battery is out of control due to heat, so that open fire is efficiently extinguished, meanwhile, the thermal buoyancy generated by flame is weakened, and the smoke concentration is reduced; when the open fire disappears and the smoke concentration is reduced, the water mist is released, the water mist particles can more easily reach the surface of the lithium ion battery, the surface temperature of the lithium ion battery is reduced, and the battery is cooled, so that the battery pack is prevented from chain thermal runaway.
Further, the gas extinguishing agent responds when the lithium battery is out of control due to heat; the gas fire extinguishing agent has the characteristics of suffocation, chemical inhibition and the like, can quickly extinguish an open fire, reduce the smoke concentration, weaken the buoyancy generated by fire plumes after the open fire disappears, and simultaneously reduce the reaction rate in the battery.
Furthermore, the gas fire extinguishing agent adopts a fire extinguishing agent capable of quickly extinguishing open fire, such as heptafluoropropane and perfluorohexanone fire extinguishing agents, which can capture free radicals in combustion, block chain reaction, quickly extinguish open fire, are non-conductive, cannot cause electrical fire and have a good inhibiting effect on battery fire; or carbon dioxide extinguishing agent with suffocation and oxygen isolation functions is selected. The fire extinguishing agents can quickly extinguish the open fire of the lithium ion battery, and keep proper fire extinguishing concentration in the ring to prevent the battery from reigniting.
Further, the gas fire extinguishing agent is stored in a storage tank and is sprayed out through an atomizing spray head under the drive of pressure, and for the perfluorohexanone fire extinguishing agent, nitrogen is selected for driving, and according to NFP2001 standard, nitrogen with the pressure of 2.0-3.0 MPa can be filled according to different working conditions. The shower nozzle is arranged inside the battery module, and the damage of flame to the shower nozzle is reduced to the battery relief valve top to one side. The dosage of the fire extinguishing agent is different according to different working conditions, so that open fire can be extinguished.
Because the latent heat of evaporation of water is large, the fine water mist particles are small, the particle size is 10-200 mu m, the heat exchange capacity is strong, the cooling effect is very good, an electrical fire cannot be caused, and the battery can be rapidly cooled when the fine water mist is sprayed on the surface of the battery.
Further, the fine water mist particles are difficult to reach the surface of the battery due to the influence of buoyancy of the plume because the fine water mist particles are small. After the gas extinguishing agent is released, open fire is extinguished, the thermal buoyancy is weakened, and meanwhile, the perfluorohexanone has the capacity of reducing the smoke concentration, so that fine water mist particles can reach the surface of the battery, the temperature of the battery is reduced, and the propagation of thermal runaway of the battery is hindered.
Furthermore, the water mist device can be a bottle group type or a pump group type, the bottle group type is adopted in the invention, nitrogen is selected for driving, the nitrogen is sprayed out through the water mist spray head, the spray head is arranged in the battery module, the battery safety valve is obliquely arranged above the water mist spray head, the spray head has a larger mist cone angle, and all single batteries in the battery pack can be covered after the water mist is sprayed out. The amount of water and the spraying strength are different according to different working conditions, so that the battery can be cooled, and the battery pack is prevented from chain thermal runaway.
Furthermore, the gas fire extinguishing agent responds immediately after the single battery is ignited, so that open fire is extinguished, and the smoke concentration is reduced. After the fire extinguishing concentration in the battery module is reached, the battery is ensured not to be re-ignited, and the release of the gas fire extinguishing agent is stopped. And then immediately releasing water mist to cool the battery pack and prevent thermal runaway chain reaction in the battery pack.
The invention has the advantages that:
1. the method adopts the compounding of the gaseous extinguishing agent and the fine water mist, so that the advantages of the gaseous extinguishing agent and the fine water mist are complementary, the defect of using a single extinguishing agent is overcome, and the method has the functions of high-efficiency fire extinguishing and cooling;
2. the method uses the gas extinguishing agent to quickly extinguish open fire, prevent flame from spreading, reduce smoke concentration and thermal buoyancy and provide convenience for subsequent cooling; 3. the method adopts the fine water mist to cool the battery, the fine water mist has small particle size, strong heat exchange capability and small influence on the battery, and can take away a large amount of heat generated by thermal runaway of the battery, thereby preventing the battery pack from generating chain thermal runaway.
Drawings
FIG. 1 is a diagram of a lithium ion battery water-gas composite fire extinguishing device;
FIG. 2 is a layout diagram of a lithium ion battery;
FIG. 3 is a graph of surface temperature and voltage of a battery over time for a blank combustion test;
FIG. 4 is a graph showing the surface temperature and voltage of a battery in a water-gas composite fire extinguishing experiment as a function of time;
fig. 5 is a diagram of thermal runaway mass loss of a battery.
Description of the major element numbers:
1: test cavity
2: test unit
3: fire extinguishing storage tank
4: electromagnetic valve
5: conveying pipeline
6: spray head
7: clamp apparatus
8: heat insulation cotton
9: heating plate
10: lithium ion battery
Detailed Description
The invention is further described below with reference to the accompanying drawings and the detailed description.
The method mainly comprises two parts, namely extinguishing open fire by a gas extinguishing agent and cooling by water mist.
The main implementation process of the fire extinguishing method is as follows:
as shown in fig. 1 and 2, a heating sheet 9 is used as a heat source to induce thermal runaway of a lithium ion battery 10, the periphery of the lithium ion battery is wrapped by heat insulation cotton to simulate a scene that the batteries in a module are close to each other and heat dissipation is difficult, the batteries are fixed by a clamp 7, and the heat insulation cotton 8, the heating sheet 9 and the batteries are bound together to prevent the batteries from bulging. After lithium ion battery 10 takes place the thermal runaway back, the relief valve department spouts the running fire, and gaseous extinguishing agent solenoid valve 4 starts, and the extinguishing agent in the storage tank 3 that puts out a fire is by pressure drive, along conveying line 5, sprays on the battery through shower nozzle 6, extinguishes open fire fast. The gas fire extinguishing agent adopts a fire extinguishing agent capable of extinguishing open fire quickly, the perfluorohexanone fire extinguishing agent is used in the method, free radicals in combustion can be captured, chain reaction is blocked, open fire can be extinguished quickly, the gas fire extinguishing agent is non-conductive, electric fire can not be caused, a good inhibiting effect on battery fire can be achieved, and meanwhile, the perfluorohexanone fire extinguishing agent can reduce smoke concentration. After the open fire disappears, the gaseous extinguishing agent continues to be released for a period of time, so that the gaseous extinguishing agent in the environment in the module reaches the extinguishing concentration, and the battery cannot be re-ignited. And then closing the electromagnetic valve of the gas fire extinguishing agent, opening a water mist battery valve, and spraying the water mist on the battery through a spray head along a conveying pipeline under the high-pressure driving of nitrogen. At the moment, the smoke concentration is low, open fire does not exist, the thermal buoyancy is low, and the fine water mist particles are easy to attach to the surface of the battery. The fine water mist particles are small, the heat exchange capacity is high, the cooling effect is good, an electrical fire cannot be caused, the batteries can be rapidly cooled when the fine water mist particles are sprayed on the surfaces of the batteries, the temperature of the batteries is reduced, the heat transfer between adjacent batteries is hindered, and the battery pack is prevented from chain thermal runaway reaction. The water consumption and the spraying strength are different according to different working conditions.
To verify the effectiveness of the water-gas recombination lithium ion thermal runaway fire extinguishing method, an analysis is performed below by means of a simulation example.
The first embodiment is as follows:
a water-gas composite fire extinguishing experiment is carried out on the lithium iron phosphate lithium ion battery with the nominal capacity of 243Ah, and a blank experiment of complete combustion and a fire extinguishing experiment of water-gas composite are designed for comparative analysis in order to verify the effect of the water-gas composite fire extinguishing method. Before the start of the experiment, the sample cell was cycled three times at 0.1C rate before being charged to 100% SOC at 0.1C rate. Then, the heating plate was arranged in the manner shown in FIG. two, and 500W was used to induce thermal runaway. The blank combustion test does not release the fire extinguishing agent, and the water-gas composite fire extinguishing test releases 2 minutes of perfluorohexanone (2L) after thermal runaway, extinguishes open fire and reduces smoke concentration. Then the electromagnetic valve of the gas fire extinguishing agent is closed, and the water mist (1.3L) is released for 2 minutes to cool the battery. The temperature and mass changes of the two sets of experiments were compared.
As shown in fig. 3 and 4, the water-gas composite fire extinguishing experiment can quickly extinguish the battery fire and reduce the surface temperature of the battery. When the fire extinguishing agent is not applied, the temperature of the battery is continuously increased after thermal runaway, wherein the temperature of the side surface is the highest and reaches 525.5 ℃, and the maximum temperatures of the upper part of the front surface of the battery and the anode are 490 ℃ and 485 ℃ respectively. After the perfluorohexanone is released, the open fire is extinguished, but the reaction inside the battery is violent, a large amount of heat is released, and the temperature continues to rise. And then releasing the fine water mist, and cooling the battery after the fine water mist is released, but because the battery capacity is large, the thermal runaway reaction is severe, and the heat released by the battery is larger than the heat taken away by the fine water mist, the temperature of the battery is still increased. However, the reaction rate is effectively slowed down by the fine water mist, the surface temperature of the battery is reduced to different degrees, and the maximum temperature of the battery anode is reduced by 205.3 ℃. Other measuring points are wrapped by heat insulation cotton, so that heat dissipation is difficult, but the maximum temperatures above the front surface and in the center of the side surface are respectively reduced by 106.8 ℃ and 68 ℃ under the cooling of water mist. If the water quantity is increased, the cooling effect is better.
As shown in fig. 5, for the blank burning test, the mass was significantly decreased when the safety valve was opened, and then the mass was stably decreased at a slower rate, and when the thermal runaway occurred in the battery, the mass decrease rate was increased until the thermal runaway was terminated, and the mass was stable. During the experiment, the cell lost 1136g of mass altogether. When the water-gas composite fire extinguishing is carried out, after the perfluorohexanone fire extinguishing agent is applied, although open fire is extinguished, the internal temperature of the battery is still high, the reaction is still carried out, and the quality reduction rate is still high. And after the water mist is released, the battery quality reduction rate is obviously reduced, and the internal reaction of the battery is slowed down because the water mist cools the surface of the battery. The final cell had a total loss of 955g, 181g less than complete combustion.
In conclusion, the water-gas composite fire extinguishing method combining the gas fire extinguishing agent and the water mist can effectively extinguish the lithium ion battery fire, reduce the surface temperature of the battery, inhibit the reaction in the battery, effectively inhibit the heat transfer among the batteries and prevent the thermal runaway propagation, thereby improving the safety of the battery pack.
The present embodiments are illustrative only, and do not limit the scope of the invention, and modifications and variations that may be made by those skilled in the art without departing from the principles of the invention are to be considered as within the scope of the invention.
Claims (6)
1. A fire control method for a water-gas composite lithium ion battery is characterized by comprising the following steps: the method comprises two parts, namely open fire extinguishing by the gas extinguishing agent and cooling by the fine water mist, wherein the gas extinguishing agent immediately responds after the lithium ion battery is out of control due to heat, so that the open fire is efficiently extinguished, meanwhile, the thermal buoyancy generated by flame is reduced, and the smoke concentration is reduced; and then, releasing the fine water mist, wherein the fine water mist particles can more easily reach the surface of the lithium ion battery under the conditions of no open fire, small thermal buoyancy and small smoke concentration, so that the surface temperature of the lithium ion battery is reduced, and the battery is cooled, thereby preventing the battery pack from generating chain thermal runaway.
2. The fire control method of the water-gas composite lithium ion battery of claim 1, characterized in that: the gas extinguishing agent responds when the lithium battery is out of control due to heat; the gas fire extinguishing agent has the characteristics of suffocation and chemical inhibition, and can quickly extinguish the open fire, after the open fire disappears, the buoyancy generated by the fire plume is weakened, and meanwhile, the smoke concentration and the reaction rate in the battery are reduced.
3. The fire control method of the water-gas composite lithium ion battery of claim 1, characterized in that: the evaporation latent heat of water is great, and thin water smoke has very good cooling ability, sprays the battery surface and can cool off the battery fast, but because thin water smoke granule is less, receives the influence of plume buoyancy, and thin water smoke granule is difficult to reach the battery surface, and after open flame extinguishes, thin water smoke granule then can reach the battery surface very easily, cools off the battery to hinder thermal runaway's propagation.
4. The fire control method of the water-gas composite lithium ion battery of claim 1, characterized in that: the gas fire extinguishing agent adopts a fire extinguishing agent capable of quickly extinguishing open fire, such as heptafluoropropane and perfluorohexanone fire extinguishing agents capable of inhibiting and blocking chain reaction, and has a good inhibiting effect on battery fire; or carbon dioxide extinguishing agents capable of suffocating and isolating oxygen are selected, the extinguishing agents can quickly extinguish the open fire of the lithium ion battery, and proper extinguishing concentration is maintained in the environment to prevent the battery from reigniting.
5. The fire control method of the water-gas composite lithium ion battery of claim 1, characterized in that: the water mist particles are small, the particle size is 10-200 mu m, the heat exchange capacity is strong, the cooling effect is good, an electrical fire cannot be caused, the pre-action of the gas extinguishing agent is small, the water mist particles can reach the surface of the battery more easily, the temperature of the battery is reduced, and the propagation of thermal runaway of the battery is hindered.
6. The fire control method of the water-gas composite lithium ion battery of claim 1, characterized in that: gaseous fire extinguishing agent is stored in the storage tank, and by pressure drive through atomizer blowout, the quantity of fire extinguishing agent should be different according to the operating mode of difference, guarantees to put out the naked light, and thin water smoke device can be bottle group formula also can be pump module formula, through thin water smoke nozzle blowout, guarantees to atomize, and thin water smoke particle diameter is less, and the quantity of water should be different according to the operating mode of difference, guarantees to cool off the battery, prevents that the group battery from taking place chain thermal runaway.
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| CN112043993A (en) * | 2020-08-31 | 2020-12-08 | 南京南瑞继保电气有限公司 | An energy storage battery compartment firefighting system and firefighting method thereof |
| CN112044002A (en) * | 2020-09-16 | 2020-12-08 | 四川建安伟业建筑工程有限公司 | Suspension type water smoke fire extinguishing and extinguishing system |
| CN112044002B (en) * | 2020-09-16 | 2022-03-15 | 四川建安伟业建筑工程有限公司 | Suspension type water smoke fire extinguishing and extinguishing system |
| CN112717306A (en) * | 2021-03-31 | 2021-04-30 | 中国电力科学研究院有限公司 | Fire extinguishing system and method for energy storage power station or battery container |
| CN113030373A (en) * | 2021-04-13 | 2021-06-25 | 中国科学技术大学 | Fire extinguishing agent performance test and fire extinguishing product detection device |
| CN113917344A (en) * | 2021-09-08 | 2022-01-11 | 东风时代(武汉)电池***有限公司 | Power battery thermal runaway test protection method, power battery device and system |
| CN116271674A (en) * | 2022-08-05 | 2023-06-23 | 北京理工大学 | A kind of low-conductivity water-based fire extinguishing agent for lithium ion battery and preparation method |
| CN116271674B (en) * | 2022-08-05 | 2024-04-05 | 北京理工大学 | A low-conductivity water-based fire extinguishing agent for lithium-ion batteries and preparation method thereof |
| CN115671640A (en) * | 2022-08-30 | 2023-02-03 | 北京理工大学 | High-cooling-performance water-based fire extinguishing agent for lithium ion battery and preparation method thereof |
| CN115671640B (en) * | 2022-08-30 | 2023-11-24 | 北京理工大学 | A high cooling water-based fire extinguishing agent for lithium-ion batteries and its preparation method |
| CN116059562A (en) * | 2023-01-30 | 2023-05-05 | 武汉理工大学 | Collaborative fire extinguishing method and device in limited space |
| CN118376938A (en) * | 2024-04-07 | 2024-07-23 | 武汉理工大学 | Lithium ion battery jet flow fire and heat radiation hazard evaluation method, device and storage medium |
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