CN104882639A - Method and device for restraining and preventing thermal runaway of lithium ion battery - Google Patents
Method and device for restraining and preventing thermal runaway of lithium ion battery Download PDFInfo
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- CN104882639A CN104882639A CN201510207554.3A CN201510207554A CN104882639A CN 104882639 A CN104882639 A CN 104882639A CN 201510207554 A CN201510207554 A CN 201510207554A CN 104882639 A CN104882639 A CN 104882639A
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- lithium ion
- ion battery
- thermal runaway
- spray
- inert gas
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a method and a device for restraining and preventing thermal runaway of a lithium ion battery. According to the method, a liquid inert gas is utilized to perform spraying refrigeration and fire fighting on a faulted lithium ion battery. The method comprises the following steps: A, selecting spraying time; B, determining the spraying quantity of a sprayed gas; C, determining a spraying mode, wherein the spraying mode refers to continuous spraying or interrupted spraying. The device comprises a control cabinet, a storage tank, a main control valve, a secondary control valve, a nozzle, a detector and a safety valve, wherein the control cabinet is a manual button control cabinet or an automatic control cabinet provided with a PLC (Programmable Logic Controller); the detector comprises a temperature sensor used for monitoring the temperature of one or more battery monomers. The method and the device have the advantages that dual effects of refrigeration and fire fighting are achieved, a security mode is complete in functions, stable, safe, reliable and efficient, a vaporization product of the liquid inert gas is nontoxic, environmentally friendly and clean as well as free from secondary damages on battery equipment.
Description
Technical field
The present invention relates to and suppress and stop lithium ion battery thermal runaway method and device, is method and the device of the propagation suppressing the generation of lithium ion battery thermal runaway and stop Li-ion batteries piles thermal runaway.
Background technology
Voltage is high owing to having for lithium ion battery, energy density is large, have extended cycle life and the advantage such as good high and low temperature discharge performance, and its range of application is more and more extensive.But the potential in the application safety problem of lithium ion battery has become bottleneck for its development of restriction, is particularly useful for the Li-ion batteries piles of dynamical system, due to containing more cell, its safety problem is also more outstanding.
Usual researcher attempts from improvement battery material, improves monomer and modular structure, raising cell peripheral circuit reliability, these three aspects solve lithium ion battery security problem, but up to the present effect is unsatisfactory, the security incident of lithium ion battery still constantly occurs.Therefore, a kind of new thinking is badly in need of to improve the fail safe of lithium ion battery.
At present, people start trial stops lithium ion battery thermal runaway by the relevant security implementations of outside batteries.
CN 102470261 A discloses a kind of method prevented or prevent lithium ion battery burning, reaches by the aqueous solution and gel extinguishant using calcium salt the danger reducing lithium ion battery burning.But the aqueous solution of calcium salt can conduct electricity, it acts on battery, can increase the risk of battery short circuit undoubtedly.
US 6,599,656 B2 disclose a kind of method stoping lithium ion battery thermal runaway, by increasing the tank body being mounted with the mixture of carbon dioxide or nitrogen and argon gas in Li-ion batteries piles, when detecting abnormal conditions, make these high-pressure inert gas be ejected into battery ambient, expulsion fuel gas and oxygen, thus reach fire-retardant object.But cells burst only aggravates and can not determine thermal runaway process, thus, the propagation of thermal runaway in battery pack can not be blocked completely by inject high pressure inert gas.
US 2013/0312947 A1 and US 2013/0316198 A1 discloses a kind of Li-ion batteries piles design of cooling fluid ejecting extinguishing.During normal use; cold-producing medium is stored in tank with the form of high-pressure liquid; when BMS detects emergencies such as occurring thermal runaway; high-pressure refrigerant (R-123) sprays from default pipeline; stamp out the flames, in the vaporization of thermal runaway battery surface, absorb amount of heat, and dilute flammable electrolyte; thus block thermal runaway propagation, protect whole battery pack safety.The cold-producing medium of the electrical equipment such as R-123 Chang Zuowei air-conditioning, refrigerator, but fire extinguishing effectiveness is unsatisfactory, and also R-123 is a kind of greenhouse gas, also can produce ozone layer simultaneously and destroy, because of, these some countries have started restriction and have used.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides and suppress and stop lithium ion battery thermal runaway method and device, to fault lithium ion battery refrigeration and fire extinguishing double action by liquid inert gas, security mode is multiple functional, stable, safe, reliable, usefulness is high, and liquid inert gas vaporized product is nontoxic, environmental protection, cleaning, do not have secondary injury to battery apparatus.
The present invention suppresses and the technical scheme of prevention lithium ion battery thermal runaway method is:
A kind of suppression and prevention lithium ion battery thermal runaway method, it uses liquid inert gas to carry out spray refrigeration and fire extinguishing to fault lithium ion battery, and step comprises:
A, choose spray opportunity: when battery cell reaches uniform temperature, namely open spray equipment;
B, determine to spray the spray flux of gas: with the latent heat of vaporization gauge of liquid inert gas, the latent heat of vaporization amount of liquid inert gas is 0.1 ~ 10 times of battery cell thermal runaway thermal discharge;
C, determine spray mode: spray mode is for spray continuously or be interrupted spray.
Further technical scheme is:
Described suppression and stop lithium ion battery thermal runaway method, its liquid inert gas is liquid nitrogen, liquid argon and the liquid carbon dioxide one in them, or two kinds, or three kinds of combinations.
Described suppression and prevention lithium ion battery thermal runaway method, in its step A, open spray equipment when battery cell temperature reaches 60 DEG C ~ 140 DEG C.
The method of described suppression and prevention lithium ion battery thermal runaway, its liquid inert gas spray flux, to rise, is determined by following formula:
h＝0.1～10 Q / R （1）
In formula: h is liquid inert gas spray flux:
Q is battery cell thermal runaway thermal discharge;
R is often liter of liquid inert gas latent heat of vaporization amount.
Described suppression and prevention lithium ion battery thermal runaway method, battery cell thermal runaway thermal discharge Q and often liter of liquid inert gas latent heat of vaporization amount r is determined by following formula:
Q＝m
1q
1+ m
2q
2+…+ m
nq
n-----（2）
In formula: q is the calorific value of the combustible material of composition lithium ion battery;
M is the quality of the combustible material of composition lithium ion battery.
The method of described suppression and prevention lithium ion battery thermal runaway, its liquid inert gas spray mode is continuously spray or and interruption spray.
Described suppression and prevention lithium ion battery thermal runaway method, the active material just very ternary material of the battery cell of its lithium ion battery, or LiFePO4, or LiMn2O4.
Described suppression and prevention lithium ion battery thermal runaway method, its battery cell capacity equals to be less than 500AH.
Described suppression and prevention lithium ion battery thermal runaway method, its battery cell shape is cylindricality.
Described suppression and prevention lithium ion battery thermal runaway method, its battery cell shape is selected from cylindrical, or square, or multi-edge column-shaped.
For the inventive method suppression and stop lithium ion battery thermal runaway device technique scheme to be: it comprises control cubicle, holding vessel, master control valve, sub-control valve, nozzle, detector and safety valve; Described control cubicle is manual knob control cubicle, or for being provided with the automatic control cabinet of PLC programmable logic controller (PLC); Described detector comprises temperature sensor, for monitoring one or more battery cell temperature.
Further technical scheme is:
Described suppression and prevention lithium ion battery thermal runaway device, its detector is also provided with Smoke Sensor and/or voltage sensor.
Principle of the present invention and effect are:
1, the generation of battery thermal runaway is suppressed: when emergencies such as " thermal runaways " soon occurs lithium ion battery temperature anomaly in other words, (battery temperature reaches within 60 DEG C ~ 140 DEG C scopes), liquid inert gas is after default pipeline ejection, at fail battery surface vaporization, absorb amount of heat, battery temperature is reduced, suppresses the exothermic auxiliary reaction of inside battery, thus reach the generation suppressing battery thermal runaway;
2, the propagation of thermal runaway in Li-ion batteries piles is blocked: when a monomer of Li-ion batteries piles thermal runaway occurs, or when thermal runaway cannot stop, stamped out the flames by coating liquid inert gas, and, liquid inert gas is when battery surface vaporization, low temperature " cloud and mist " is formed, the thermal shock produced when can completely cut off fail battery thermal runaway and dangerous injecting substances around fail battery; Meanwhile, expand liquid inert gas spray scope, carry out pre-cooled to surrounding normal battery, battery temperature is dropped to less than 0 DEG C, thus the propagation of effective blocking-up thermal runaway in Li-ion batteries piles.
3, the present invention suppresses and stops lithium ion battery thermal runaway by suppressing and stoping lithium ion battery thermal runaway device.This device comprises control cubicle, holding vessel, master control valve, sub-control valve, evaporator, nozzle, detector) and for the safety valve of pipeline overpressure relief; When lithium ion battery breaks down, by the Sensor monitoring one or more battery cell of detector by comprising temperature, smog and voltage, when discovery fault, surveying to start manually or automatically suppresses and stops lithium ion battery thermal runaway device to carry out putting out a fire and freezing, and completes the security work to lithium battery group.
Compared with prior art, the invention has the beneficial effects as follows:
By liquid inert gas to fault lithium ion battery refrigeration and fire extinguishing double action, effectively overcome the deficiency of prior art lithium ion battery security mode function singleness, stability and safety reliability, and the problem of inefficiency; Meanwhile, liquid inert gas vaporized product is all clean gas that is nontoxic, environmental protection, does not cause secondary injury to battery apparatus.
Accompanying drawing explanation
Fig. 1 is the schematic diagram implementing extinguishing device of the present invention and detector.
In figure: 1-control cubicle; 2-holding vessel; 3-master control valve; 4-sub-control valve; 5-nozzle; 6-detector; 7-safety valve.
Embodiment
the present invention suppressed in conjunction with the embodiments and stop the technical scheme of lithium ion battery thermal runaway method to be described further as follows:
embodiment 1:that the present invention suppresses and stops the basic embodiment of lithium ion battery thermal runaway method.Described method uses liquid inert gas to carry out spray refrigeration and fire extinguishing to fault lithium ion battery, and step comprises:
A, choose spray opportunity: when battery cell reaches uniform temperature, namely open spray equipment;
B, determine to spray the spray flux of gas: with the latent heat of vaporization gauge of liquid inert gas, the latent heat of vaporization amount of liquid inert gas is 0.1 ~ 10 times of battery cell thermal runaway thermal discharge;
C, determine spray mode: spray mode is for spray continuously or be interrupted spray, chooses by the quantity of battery cell.
Described step is with A, spray opportunity, B, spray flux, and C sprays mode order and implements, or parallel practice, or contrary order is implemented.
embodiment 2:it is embodiment 1 further embodiment.Described liquid inert gas is liquid nitrogen, liquid argon and the liquid carbon dioxide one in them, or two kinds, or three kinds of combinations.In described step A, when battery cell temperature reaches 60 DEG C ~ 140 DEG C, open spray equipment.
Described liquid inert gas spray flux, to rise, is determined by following formula:
h＝0.1～10 Q / R （1）
In formula: h is liquid inert gas spray flux:
Q is battery cell thermal runaway thermal discharge;
R is often liter of liquid inert gas latent heat of vaporization amount, is well known data.
Described battery cell thermal runaway thermal discharge Q is determined by following formula:
Q＝m
1q
1+ m
2q
2+…+ m
nq
n-----（2）
In formula: q is the calorific value of the combustible material of composition lithium ion battery;
M is the quality of the combustible material of composition lithium ion battery.
Described liquid inert gas spray mode is continuously spray or and is interrupted spray.The active material of the battery cell of described lithium ion battery is tertiary cathode material, or LiFePO4, or LiMn2O4.Battery cell capacity equals to be less than 500AH.Battery cell shape is cylindricality.Battery cell shape is selected from cylindrical, or square, or multi-edge column-shaped.
embodiment 3:it is a preferred embodiment.As different from Example 2: described liquid inert gas elects liquid nitrogen as, in described step A, when battery cell temperature reaches 120 DEG C, open spray equipment.In step B, determine that the spray flux of spray gas is the latent heat of vaporization gauge with liquid inert gas, the latent heat of vaporization amount of liquid inert gas is 0.5 times of battery cell thermal runaway thermal discharge; The active material just very LiFePO4 of the battery cell of described lithium ion battery.Battery cell capacity is 1.5AH.Battery cell shape is cylindrical.Described liquid inert gas spray mode is continuously spray 1 time, and be 5s to battery cell spray time, sprayed the whole device of rear closedown, after 10min, battery temperature is inhibited and tends to be steady, and battery is intact.
embodiment 4:it is another preferred embodiment.As different from Example 2: described liquid inert gas elects liquid nitrogen as, in described step A, when battery cell temperature reaches 100 DEG C, open spray equipment.In step B, determine that the spray flux of spray gas is the latent heat of vaporization gauge with liquid inert gas, the latent heat of vaporization amount of liquid inert gas is 1 times of battery cell thermal runaway thermal discharge; The active material just very LiMn2O4 of the battery cell of described lithium ion battery.Battery cell capacity is 500AH.Battery cell shape is for round square.Described liquid inert gas spray mode is for being interrupted spray, and stop after battery cell spray time is 5s, continue spray 5s after 30s, so repeat 3 times, sprayed the whole device of rear closedown, after 10min, battery temperature is inhibited and tends to be steady, and battery is intact.
embodiment 5:it is another preferred embodiment.As different from Example 2: described liquid inert gas elects liquid nitrogen as, in described step A, when battery cell temperature reaches 140 DEG C, open spray equipment.In step B, determine that the spray flux of spray gas is the latent heat of vaporization gauge with liquid inert gas, the latent heat of vaporization amount of liquid inert gas is 10 times of battery cell thermal runaway thermal discharge; The active material just very LiMn2O4 of the battery cell of described lithium ion battery.Battery cell capacity is 500AH.Battery cell shape is for round square.Described liquid inert gas spray mode is for being interrupted spray, and stop after battery cell spray time is 5s, continue spray 5s after 30s, so repeat 5 times, sprayed the whole device of rear closedown, after 10min, battery temperature is inhibited and tends to be steady, and battery is intact.
In conjunction with the accompanying drawings and embodiments to being described further as follows for the suppression of the inventive method and the technical scheme of prevention lithium ion battery thermal runaway device:
embodiment 6:it is a basic embodiment.As shown in Figure 1, for suppression and the prevention lithium ion battery thermal runaway device of the inventive method, it comprises control cubicle 1, holding vessel 2, master control valve 3, sub-control valve 4, nozzle 5, detector 6 and safety valve 7; Described control cubicle 1 is manual knob control cubicle, or for being provided with the automatic control cabinet of PLC programmable logic controller (PLC); Described detector 6 comprises temperature sensor, for monitoring one or more battery cell temperature.Have evaporator in described holding vessel 2, described safety valve 7 is each parts, particularly pipeline pressure relief device.
embodiment 7:it is a preferred embodiment.Described suppression and prevention lithium ion battery thermal runaway device, its detector 7 is also provided with Smoke Sensor and/or voltage sensor.
embodiment 8:that of being equal to embodiment 3 simulates embodiment.Get 15cm electric furnace heating wire good, put insulator (for avoiding short circuit) folding after be placed in 1.5AH cylindrical battery monomer (1.5AH cylindrical battery be Horizontal electrode, box hat packaging, positive electrode is LiFePO4) left side, connect a voltage regulator by high temperature wire and heat.Left and right sides in the middle part of monomer and between monomer, metal connector settles thermocouple respectively.The thermocouple of electric furnace heating wire and monomer surface uses copper wire binding fixing, to avoid departing from original position in blast.
Subsequently, with electric furnace heating wire by Unit heating, until when temperature reaches 120 DEG C, stop heating and spray liquid nitrogen (institute spray 0.5 times that the total latent heat of vaporization of liquid nitrogen is battery cell thermal runaway thermal discharge) by extinguishing device to monomer, lasting spray 5s after close extinguishing device.After 10min, battery temperature is inhibited and tends to be steady, and battery is intact.
embodiment 9:that of being equal to embodiment 5 simulates embodiment.By 500AH rectangular cell respectively by being assembled into 3 monomer modules.The active material just very LiMn2O4 of battery cell.Get 50cm electric furnace heating wire good, put insulator, be placed on the left of A monomer after folding, connect a voltage regulator by high temperature wire and heat.Left and right sides in the middle part of each monomer and between each monomer, metal connector settles thermocouple respectively.The thermocouple of electric furnace heating wire and monomer surface uses copper wire binding fixing, to avoid departing from original position in blast.Subsequently, with electric furnace heating wire by A Unit heating, until A monomer " is lighted ", battery cell temperature reaches 140 DEG C, 10s after A monomer is on fire, stops heating and sprays liquid nitrogen (spray 10 times that the total latent heat of vaporization of liquid nitrogen is battery cell thermal runaway thermal discharge) by extinguishing device to module, stop after continuing spray 5s, continue spray 5s after 30s, so repeat 5 times, finally close extinguishing device.Battery module fray-out of flame and each monomer temperature tend to be steady.
Claims of the present invention is not limited to above-described embodiment.
Claims (12)
1. suppress and stop a lithium ion battery thermal runaway method, it is characterized in that, it uses liquid inert gas to carry out spray refrigeration and fire extinguishing to fault lithium ion battery, and step comprises:
A, choose spray opportunity: when battery cell reaches uniform temperature, namely open spray equipment;
B, determine to spray the spray flux of gas: with the latent heat of vaporization gauge of liquid inert gas, the latent heat of vaporization amount of liquid inert gas is 0.1 ~ 10 times of battery cell thermal runaway thermal discharge;
C, determine spray mode: spray mode is for spray continuously or be interrupted spray.
2. suppression according to claim 1 and stop lithium ion battery thermal runaway method, is characterized in that, described liquid inert gas is liquid nitrogen, liquid argon and the liquid carbon dioxide one in them, or two kinds, or three kinds of combinations.
3. suppression according to claim 1 and prevention lithium ion battery thermal runaway method, is characterized in that, in described step A, open spray equipment when battery cell temperature reaches 60 DEG C ~ 140 DEG C.
4. the method for suppression according to claim 1 and prevention lithium ion battery thermal runaway, is characterized in that, described liquid inert gas spray flux, to rise, is determined by following formula:
h＝0.1～10 Q /R （1）
In formula: h is liquid inert gas spray flux:
Q is battery cell thermal runaway thermal discharge;
R is often liter of liquid inert gas latent heat of vaporization amount.
5. suppression according to claim 4 and prevention lithium ion battery thermal runaway method, it is characterized in that, battery cell thermal runaway thermal discharge Q and often liter of liquid inert gas latent heat of vaporization amount r is determined by following formula:
Q＝m
1q
1+ m
2q
2+…+ m
nq
n-----（2）
In formula: q is the calorific value of the combustible material of composition lithium ion battery;
M is the quality of the combustible material of composition lithium ion battery.
6. the method for suppression according to claim 1 and prevention lithium ion battery thermal runaway, is characterized in that, described liquid inert gas spray mode is continuously spray or and interruption spray.
7. suppression according to claim 1 and prevention lithium ion battery thermal runaway method, is characterized in that, the active material just very ternary material of the battery cell of described lithium ion battery, or LiFePO4, or LiMn2O4.
8. suppression according to claim 1 and prevention lithium ion battery thermal runaway method, it is characterized in that, described battery cell capacity equals to be less than 500AH.
9. suppression according to claim 1 and prevention lithium ion battery thermal runaway method, it is characterized in that, described battery cell shape is cylindricality.
10. suppression according to claim 1 and prevention lithium ion battery thermal runaway method, it is characterized in that, described battery cell shape is selected from cylindrical, or square, or multi-edge column-shaped.
11. 1 kinds of suppression for method described in claim 1 and prevention lithium ion battery thermal runaway device, it is characterized in that, it comprises control cubicle (1), holding vessel (2), master control valve (3), sub-control valve (4), nozzle (5), detector (6) and safety valve (7); Described control cubicle (1) is manual knob control cubicle, or for being provided with the automatic control cabinet of PLC programmable logic controller (PLC); Described detector (7) comprises temperature sensor, for monitoring one or more battery cell temperature.
12. suppression according to claim 11 and prevention lithium ion battery thermal runaway device, it is characterized in that, detector (7) is also provided with Smoke Sensor and/or voltage sensor.
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