Thermal protection of lithium ion batteries
A method for extinguishing a flame and terminating thermal runaway in a device powered by a lithium ion battery. The disclosure also provides a system for extinguishing fires generated by lithium ion batteries exhibiting thermal runaway.
1 . A method for extinguishing a flame and terminating thermal runaway in a device powered by a lithium ion battery, which comprises: (a) providing an enclosure; (b) providing the device positioned within the enclosure, wherein the device comprises and is powered by the lithium ion battery; (c) providing a source of a thermal runaway termination agent, wherein the source comprises a container and a two-way control valve, wherein the container contains the thermal runaway termination agent, the two-way control valve is attached to an opening in the container, and the thermal runaway termination agent comprises a nonflammable haloolefin; (d) providing a temperature sensitive tube containing an inert gas or a thermal runaway termination agent at a predetermined pressure and temperature suitable for normal operating conditions of the device, wherein the tube has two ends, wherein (i) one end is in communication with the control valve and the other end is capped, (ii) the tube is located within the enclosure and comprises a temperature sensor for detection of a threshold temperature, and (iii) the tube is disposed in proximity to the lithium ion battery; and (e) providing a heat stimulus, which generates a flame and initiates thermal runaway, whereupon the temperature sensitive tube ruptures, creating an opening in the temperature sensitive tube and causing release of the inert gas or thermal runaway termination agent within the temperature sensitive tube through the heat stimulus-created opening in the temperature sensitive tube and into the enclosure, resulting in a pressure drop within the temperature sensitive tube which actuates the control valve to deliver the thermal runaway termination agent from the storage container through the control valve to the temperature sensitive tube and out of the heat stimulus-created opening in the temperature sensitive tube and into the enclosure; wherein the delivery of the thermal runaway termination agent is characterized by a discharge time, a thermal runaway termination agent concentration, and hold time, thereby extinguishing the flame and terminating thermal runaway and preventing reignition following the extinguishment of the flame, wherein the thermal runaway termination agent comprises an amount of the nonflammable haloolefin sufficient to provide a concentration of 13% to 30% v/v (volume/volume) of the nonflammable haloolefin when delivered to the enclosure, wherein the discharge time ranges from 18 seconds to 180 seconds, and wherein the hold time ranges from 10 to to 60 minutes, wherein the nonflammable haloolefin is chosen from one or more of E-HFO-1336mzz, Z-HFO-1336mzz, Z-HCFO-1233zd, HCFO-1233xf, Z-HCFO-1224yd, E-HCFO-1224yd, E-HFO-1438ezy, Z-HFO-1438ezy, HBFO-1233xfB.
2 . The method of claim 1 wherein the temperature sensitive tube contains an inert gas and wherein the inert gas is chosen from nitrogen, argon, helium, carbon dioxide, and mixtures thereof.
3 . The method of claim 1 wherein the two-way control valve has at least three ports.
4 . The method of claim 1 , wherein the device is chosen from datalogger, telecommunication equipment, personal electronic equipment, power tool, energy storage system, data center, electric motor vehicle, and electric bicycle.
5 . The method of claim 1 , wherein the lithium ion battery comprises an anode chamber comprising an anode, a cathode chamber comprising a cathode and a semipermeable membrane, which separates the anode chamber from the cathode chamber and wherein the anode is constructed of graphite protected with a solid electrolyte interphase layer and the cathode is constructed of a lithium metal oxide chosen from LiCoO 2 , LiFePO 4 , LiMn 2 O 4 or LiNiMnCoO 2 and wherein the anode chamber and cathode chamber are each filled with a liquid electrolyte which is a flammable organic carbonate chosen from ethylene carbonate or diethyl carbonate, which contains a lithium salt chosen from LiPF 6 , LiAsF 6 , LiClO 4 , LiBF 4 , or LiCF 3 SO 3 .
6 . The method of claim 1 , wherein the heat stimulus is the result of applied heat to the enclosure from an external source.
7 . The method of claim 1 , wherein the heat stimulus is the result of applied heat to the enclosure from an internal source and wherein the internal source is due to the LIB overheating due to a mechanical event or electrical event or a defect event.
8 . The method of claim 1 , wherein the device comprises a single cell configuration or multiple cell configuration, and whereby the method achieves flame extinguishment, terminating thermal runaway and cooling sufficient to prevent reignition.
9 . The method of claim 1 wherein the nonflammable haloolefin is chosen from one or more of E-HFO-1336mzz, Z-HFO-1336mzz, Z-HCFO-1224yd, E-HCFO-1224yd, E-HFO-1438ezy, Z-HFO-1438ezy, HBFO-1233xfB.
10 . A method for extinguishing a flame and terminating thermal runaway in a device powered by a lithium ion battery, which comprises: (a) providing an enclosure; (b) providing the device positioned within the enclosure, wherein the device comprises and is powered by the lithium ion battery; (c) providing a source of a thermal runaway termination agent, wherein the source comprises a container and a three-way control valve, wherein the container contains the thermal runaway termination agent, the three-way control valve is attached to an opening in the container, and the thermal runaway termination agent comprises a nonflammable haloolefin; (d) providing a temperature sensitive tube containing an inert gas or a thermal runaway termination agent at a predetermined pressure and temperature suitable for normal operating conditions of the device, wherein the tube has two ends, wherein (i) one end is in communication with the three-way control valve and the other end is capped, (ii) the tube is located within the enclosure and comprises a temperature sensor for detection of a threshold temperature, and (iii) the tube disposed in proximity to the lithium ion battery; (e) providing a nozzle-connecting tube which is in communication with the three-way control valve on one end and terminates in a nozzle proximal to the lithium ion battery at the other end of the nozzle-connecting tube; and (f) providing a heat stimulus, which generates a flame and initiates thermal runaway, whereupon the temperature sensitive tube ruptures, creating an opening in the temperature sensitive tube (“heat stimulus-created opening”) and causing release of the inert gas or thermal runaway termination agent within the temperature sensitive tube through the heat stimulus-created opening in the temperature sensitive tube and into the enclosure, resulting in a pressure drop within the temperature sensitive tube which actuates the three-way control valve to deliver the thermal runaway termination agent from the storage container through the three-way control valve to the nozzle-connecting tube, resulting in the release of the thermal runaway termination agent from the nozzle into the enclosure; wherein the delivery of the thermal runaway termination agent is characterized by a discharge time, a thermal runaway termination agent concentration, and hold time, thereby extinguishing the flame and terminating thermal runaway and preventing reignition following the extinguishment of the flame, wherein the thermal runaway termination agent comprises an amount of the nonflammable haloolefin sufficient to provide a concentration of 13% to 30% v/v (volume/volume) of the nonflammable haloolefin when delivered to the enclosure, wherein the discharge time ranges from 18 seconds to 180 seconds, and wherein the hold time ranges from 10 to 60 minutes, wherein the nonflammable haloolefin is chosen from one or more of E-HFO-1336mzz, Z-HFO-1336mzz, Z-HCFO-1233zd, HCFO-1233xf, Z-HCFO-1224yd, E-HCFO-1224yd, E-HFO-1438ezy, Z-HFO-1438ezy, HBFO-1233xfB.
11 . The method of claim 10 wherein the temperature sensitive tube contains an inert gas and wherein the inert gas is chosen from nitrogen, argon, helium, carbon dioxide, and mixtures thereof.
12 . The method of claim 10 , wherein the device is chosen from datalogger, telecommunication equipment, personal electronic equipment, power tool, energy storage system, data center, electric motor vehicle, and electric bicycle.
13 . The method of claim 10 , wherein the lithium ion battery comprises an anode chamber comprising an anode, a cathode chamber comprising a cathode, and a semipermeable membrane, which separates the anode chamber from the cathode chamber and wherein the anode is constructed of graphite protected with a solid electrolyte interphase layer and the cathode is constructed of a lithium metal oxide chosen from LiCoO 2 , LiFePO 4 , LiMn 2 O 4 or LiNiMnCoO 2 and wherein the anode chamber and cathode chamber are each filled with a liquid electrolyte which is a flammable organic carbonate chosen from ethylene carbonate or diethyl carbonate, which contains a lithium salt chosen from LiPF 6 , LiAsF 6 , LiClO 4 , LiBF 4 , or LiCF 3 SO 3 .
14 . The method of claim 10 , wherein the heat stimulus is the result of applied heat to the enclosure from an external source.
15 . The method of claim 10 , wherein the heat stimulus is the result of applied heat to the enclosure from an internal source, and wherein the internal source is due to the LIB overheating due to a mechanical event or electrical event or a defect event.
16 . The method of claim 10 , wherein the device comprises a single cell configuration or multiple cell configuration, and whereby the method achieves flame extinguishment, terminating thermal runaway and cooling sufficient to prevent reignition.
17 . The method of claim 10 wherein the nonflammable haloolefin is chosen from one or more of E-HFO-1336mzz, Z-HFO-1336mzz, Z-HCFO-1224yd, E-HCFO-1224yd, E-HFO-1438ezy, Z-HFO-1438ezy, HBFO-1233xfB.
18 . A fire protection system which comprises: (a) an enclosure; (b) a device, positioned within the enclosure, wherein the device comprises and is powered by a lithium ion battery; (c) a source of a thermal runaway termination agent, wherein the source comprises a container and a two-way control valve, wherein the container contains the thermal runaway termination agent, the two-way control valve is attached to an opening in the container, and the thermal runaway termination agent comprises a nonflammable haloolefin; and (d) a temperature sensitive tube containing an inert gas or a thermal runaway termination agent at a predetermined pressure and temperature suitable for normal operating conditions of the device, wherein the tube has two ends, wherein (i) one end is in communication with the two-way control valve and the other end is capped, (ii) the tube is located within the enclosure and comprises a temperature sensor for detection of a threshold temperature, and (iii) the tube is disposed in proximity to the lithium ion battery, and the tube is burstable upon sensing a threshold temperature;
wherein when the temperature sensitive tube bursts upon sensing the threshold temperature, creating an opening in the temperature sensitive tube and causing release of the inert gas or thermal runaway termination agent within the temperature sensitive tube through the heat stimulus-created opening in the temperature sensitive tube and into the enclosure, resulting in a pressure drop within the temperature sensitive tube which actuates the two-way control valve to deliver the thermal runaway termination agent from the container through the two-way control valve to the temperature sensitive tube and out of the heat stimulus-created opening in the temperature sensitive tube and into the enclosure, wherein the delivery of the thermal runaway termination agent is characterized by a discharge time, a thermal runaway termination agent concentration, and hold time, thereby extinguishing the flame and terminating thermal runaway and preventing reignition following the extinguishment of the flame, wherein the thermal runaway termination agent comprises an amount of the nonflammable haloolefin sufficient to provide a concentration of 13% to 30% v/v (volume/volume) of the nonflammable haloolefin when delivered to the enclosure, wherein the discharge time ranges from 18 seconds to 180 seconds, and wherein the hold time ranges from 10 to 60 minutes, wherein the nonflammable haloolefin is chosen from one or more of E-HFO-1336mzz, Z-HFO-1336mzz, Z-HCFO-1233zd, HCFO-1233xf, Z-HCFO-1224yd, E-HCFO-1224yd, E-HFO-1438ezy, Z-HFO-1438ezy, HBFO-1233xfB.
19 . The fire protection system of claim 18 , wherein the device is chosen from datalogger, telecommunication equipment, personal electronic equipment, power tool, energy storage system, data center, electric motor vehicle, and electric bicycle.
20 . The fire protection system of claim 18 wherein the nonflammable haloolefin is chosen from one or more of E-HFO-1336mzz, Z-HFO-1336mzz, Z-HCFO-1224yd, E-HCFO-1224yd, E-HFO-1438ezy, Z-HFO-1438ezy, HBFO-1233xfB.
21 . A fire protection system which comprises: (a) an enclosure; (b) a device, positioned within the enclosure, wherein the device comprises and is powered by a lithium ion battery; (c) a source of a thermal runaway termination agent, wherein the source comprises a container and a three-way control valve, wherein the container contains the thermal runaway termination agent, the three-way control valve is attached to an opening in the container, and the thermal runaway termination agent comprises a nonflammable haloolefin; and (d) a temperature sensitive tube containing an inert gas or a thermal runaway termination agent at a predetermined pressure and temperature suitable for normal operating conditions of the device, wherein the temperature sensitive tube has two ends, wherein (i) one end is in communication with the three-way control valve and the other end is capped, (ii) the temperature sensitive tube is located within the enclosure and comprises a temperature sensor for detection of a threshold temperature, and (iii) the temperature sensitive tube disposed in proximity to the lithium ion battery, and the temperature sensitive tube is burstable upon sensing a threshold temperature;
and (e) a nozzle-connecting tube which is in communication with the three-way control valve on one end and terminates in a nozzle proximal to the lithium ion battery at the other end of the nozzle-connecting tube; wherein when the temperature sensitive tube bursts upon sensing the threshold temperature, creating an opening in the temperature sensitive tube (“heat stimulus-created opening”) and causing release of the inert gas or thermal runaway termination agent within the temperature sensitive tube through the heat stimulus-created opening in the temperature sensitive tube and into the enclosure, resulting in a pressure drop within the temperature sensitive tube which actuates the three-way control valve to deliver the thermal runaway termination agent from the container through the three-way control valve to the nozzle-connecting tube, resulting in the release of the thermal runaway termination agent from the nozzle into the enclosure; wherein the delivery of the thermal runaway termination agent is characterized by a discharge time, a thermal runaway termination agent concentration, and hold time, thereby extinguishing the flame and terminating thermal runaway and preventing reignition following the extinguishment of the flame, wherein the thermal runaway termination agent comprises an amount of the nonflammable haloolefin sufficient to provide a concentration of 13% to 30% v/v (volume/volume) of the nonflammable haloolefin when delivered to the enclosure, wherein the discharge time ranges from 18 seconds to 180 seconds, and wherein the hold time ranges from 10 to 60 minutes, wherein the nonflammable haloolefin is chosen from one or more of E-HFO-1336mzz, Z-HFO-1336mzz, Z-HCFO-1233zd, HCFO-1233xf, Z-HCFO-1224yd, E-HCFO-1224yd, E-HFO-1438ezy, Z-HFO-1438ezy, HBFO-1233xfB.
22 . The fire protection system of claim 21 , wherein the device is chosen from datalogger, telecommunication equipment, personal electronic equipment, power tool, energy storage system, data center, electric motor vehicle, and electric bicycle.
23 . The fire protection system of claim 21 wherein the nonflammable haloolefin is chosen from one or more of E-HFO-1336mzz, Z-HFO-1336mzz, Z-HCFO-1224yd, E-HCFO-1224yd, E-HFO-1438ezy, Z-HFO-1438ezy, HBFO-1233xfB.