CN117091653A - Double-parameter thin film sensor for safety monitoring of energy storage system and preparation method and application thereof - Google Patents
Double-parameter thin film sensor for safety monitoring of energy storage system and preparation method and application thereof Download PDFInfo
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- 238000012544 monitoring process Methods 0.000 title claims abstract description 62
- 238000004146 energy storage Methods 0.000 title claims abstract description 58
- 239000010409 thin film Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010408 film Substances 0.000 claims abstract description 57
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000002109 single walled nanotube Substances 0.000 claims description 40
- 239000002033 PVDF binder Substances 0.000 claims description 39
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 39
- 229920001721 polyimide Polymers 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000011812 mixed powder Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
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- 238000011088 calibration curve Methods 0.000 description 3
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- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01D—MEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
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Abstract
A double-parameter film sensor for safety monitoring of an energy storage system and a preparation method and application thereof relate to a sensor and a preparation method and application thereof. The invention aims to solve the problems that the existing sensor can only detect a single stimulation signal, is difficult to integrate temperature and pressure double signals, has high price, complex supporting facilities and decoupling of optical signals, and restricts the development of the sensor in the field of battery safety monitoring. A double-parameter film sensor for safety monitoring of an energy storage system consists of 4 temperature sensitive layers, 1 pressure sensitive layer, 1 interdigital electrode, 4 far-end electrodes and 4 wires. The method comprises the following steps: 1. preparing slurry; 2. preparing a film; 3. preparing a bottom layer circuit; 4. the sensor is prepared. A dual-parameter thin film sensor for safety monitoring of an energy storage system is implanted into the energy storage system and is used for detecting the temperature and the pressure inside the energy storage system.
Description
Technical Field
The invention relates to a sensor, a preparation method and application thereof.
Background
At present, fossil fuels are increasingly exhausted, and meanwhile, the ecological environment is also subjected to serious examination. In order to solve the environmental deterioration of energy crisis, people develop clean renewable green energy sources such as wind energy, solar energy and the like. These green energy sources require a large number of energy storage stations for storage and grid connection. Therefore, electrochemical energy storage systems represented by lithium ion batteries are widely used and popularized. The lithium ion battery mainly comprises a positive electrode, a diaphragm, electrolyte and a negative electrode, and has excellent energy storage performance because a large amount of lithium ions in the electrolyte are freely inserted and separated from the surface of a negative electrode material of the battery in the charging and discharging process. Under normal operating conditions, the electrochemical reactions within the lithium ion battery are stable and reversible, with internal heat conservation. While when the cell is in an unstable state, the cell internal balance is broken, producing a large amount of "dead lithium" and creating dendrites that pierce the separator causing an internal short circuit in the cell. Internal short circuits generate a large amount of heat and also cause a series of side reactions, such as vaporization of electrolyte, aggravation of electrochemical reaction, etc. The reactions and phenomena in the unbalanced state can affect and break the internal heat balance of the battery, eventually lead to swelling and performance reduction of the battery, even cause thermal runaway of the battery, and cause serious damage to equipment or personnel. Therefore, monitoring battery operation, avoiding thermal runaway, and ensuring safe battery operation are important research points for the development of lithium ion batteries.
At present, many research teams have made a great deal of researches on the aspect of lithium ion battery health monitoring, such as monitoring temperature and pressure changes in the operation process of a lithium battery, researching the triggering temperature of thermal runaway of the battery, developing a battery safety active control system and the like, but all the research bases need stable and accurate sensors to acquire parameters such as the real-time battery temperature, the internal pressure and the like. However, the conventional temperature sensor is basically made of precious metal and has a large volume, and can only be attached to the battery pack housing to monitor the surface temperature of the housing when monitoring the operating temperature of the battery pack. The temperature measured by this measurement means differs from the actual temperature inside the battery by about 10 deg.c. The traditional pressure sensor is mostly of a strain metal structure, has a large size, and cannot monitor the internal pressure change of the battery pack. For bragg grating sensors, the change in internal parameters of the cell can be monitored, although the structure is slim, having a sensitive optical signal response to both ambient temperature and self-deformation. However, the price of the device is high, the supporting facilities are complex, and the optical signals need to be decoupled, so that the development of the device in the field of battery safety monitoring is restricted. In addition, the thin film sensor has thin thickness and small size, and can be directly arranged in the battery pack to monitor the central temperature of the battery pack, the pressure between the battery cells and other parameter changes. The traditional film temperature sensor or film pressure sensor is polymer base material, and the sensor can only detect single stimulus signal, and is difficult to integrate temperature and pressure signals. While the internal space of the battery pack is limited, there is a need to develop an integrated, multi-signal monitoring flexible thin film sensor.
Disclosure of Invention
The invention aims to solve the problems that the existing sensor can only detect a single stimulation signal, is difficult to integrate temperature and pressure double signals, is high in price, complex in supporting facilities and needs decoupling of optical signals, and restricts the development of the sensor in the field of battery safety monitoring, and provides a double-parameter film sensor for safety monitoring of an energy storage system, and a preparation method and application thereof.
A double-parameter film sensor for safety monitoring of an energy storage system consists of 4 temperature sensitive layers, 1 pressure sensitive layer, 1 interdigital electrode, 4 far-end electrodes and 4 wires;
the interdigital electrode is positioned at the center of the sensor, the pressure sensitive layer and the interdigital electrode have the same size, the pressure sensitive layer is positioned right above the interdigital electrode and is tightly contacted with the interdigital electrode, and 4 temperature sensitive layers are distributed at four corners of the sensor;
one end of the 1 st wire is sequentially connected with the four temperature sensitive layers, and the other end of the 1 st wire is connected with the far-end electrode, so that the output of temperature sensing signals is realized;
one end of the 2 nd wire is connected with a temperature sensitive layer close to the far-end electrode, bypasses the pressure sensitive layer, and the other end of the 2 nd wire is connected with the far-end electrode to realize the output of temperature sensing signals;
the 3 rd lead and the 4 th lead are respectively connected with the interdigital electrodes to realize the output of pressure sensing signals.
The preparation method of the double-parameter film sensor for safety monitoring of the energy storage system comprises the following steps:
1. preparing slurry:
placing polyvinylidene fluoride and single-walled carbon nanotubes into a mortar, and grinding to uniformly mix the polyvinylidene fluoride and the single-walled carbon nanotubes to obtain mixed powder; dropwise adding N-methyl pyrrolidone into the mixed powder under the stirring condition, and stirring to obtain black sizing agent;
2. preparing a film:
pouring black paste on a polyimide film, scraping the film by an automatic knife coater, adhering and fixing the uniformly scraped film on a glass plate to avoid deformation, storing in a vacuum oven for drying, and removing the film from the polyimide film after drying to obtain the PVDF/SWCNT composite sensitive material;
3. preparing a bottom layer circuit:
printing a conductive silver paste bottom layer circuit pattern on the polyimide film by using an automatic direct writing machine, wherein the bottom layer circuit pattern is respectively 1 interdigital electrode, 4 far-end electrodes and 4 wires, and drying the polyimide film on a heating table to obtain a bottom layer circuit of the double-parameter film sensor for safety monitoring of an energy storage system;
4. preparing a sensor:
cutting the PVDF/SWCNT composite sensitive material to obtain 4 temperature sensitive layers and 1 pressure sensitive layer; the 4 temperature sensitive layers and the 1 pressure sensitive layer are respectively arranged at the corresponding positions on the bottom layer circuit, so that one end of the 1 st wire is sequentially connected with the four temperature sensitive layers, and the other end is connected with the far-end electrode, and the output of temperature sensing signals is realized; one end of the 2 nd wire is connected with a temperature sensitive layer close to the far-end electrode, bypasses the pressure sensitive layer, and the other end of the 2 nd wire is connected with the far-end electrode to realize the output of temperature sensing signals; the 3 rd lead and the 4 th lead are respectively connected with the interdigital electrodes to realize the output of pressure sensing signals; and then fixing by using an insulated polyimide adhesive tape to obtain the double-parameter film sensor for safety monitoring of the energy storage system.
A dual-parameter thin film sensor for safety monitoring of an energy storage system is implanted into the energy storage system and is used for detecting the temperature and the pressure inside the energy storage system.
The invention has the advantages that:
the double-parameter film sensor for safety monitoring of the energy storage system can effectively monitor the internal temperature and pressure change of the battery, and the preparation method is simple and feasible and is suitable for large-scale popularization and application; the prepared dual-signal sensor is subjected to pressure sensitivity performance test, and the result shows that the device can respond within 200ms after being stimulated by pressure, and the pressure sensitivity characteristic is kept stable after 7000 cycles; the device can perform linear response in the temperature range of 40-90 ℃ and can effectively monitor a thermal runaway temperature node of 80 ℃.
Drawings
Fig. 1 is a schematic structural diagram of a dual-parameter thin film sensor for safety monitoring of an energy storage system, prepared in embodiment 1, in which a is the length of the sensor, b is the width of the sensor, c is the width of the pressure sensitive layer, d is the length of the pressure sensitive layer, e is the length of the temperature sensitive layer, f is the width of the temperature sensitive layer, and g is the inter-finger pitch of the inter-finger electrodes;
FIG. 2 is a physical diagram of a dual-parameter thin film sensor for safety monitoring of an energy storage system prepared in example 1;
FIG. 3 is a scanning electron microscope image, wherein a is a scanning electron microscope image of SWCNT, b is a scanning electron microscope image of PVDF film, c is a low power scanning electron microscope image of PVDF/SWCNT composite sensitive material prepared in step two of example 1, and d is a high power scanning electron microscope image of PVDF/SWCNT composite sensitive material prepared in step two of example 1;
FIG. 4 is a temperature sensitivity of a dual-parameter thin film sensor for safety monitoring of an energy storage system prepared in example 1, wherein a is a curve of current of the sensor along with temperature change, and b is a temperature calibration curve of the sensor;
FIG. 5 is a graph showing the pressure-sensitive performance of a dual-parameter thin film sensor for safety monitoring of an energy storage system prepared in example 1, wherein a is a cycle curve of the sensor for simulation monitoring of the swelling state of a battery, and b is the mechanical cycle performance of the sensor;
fig. 6 is a graph of thermal runaway of a dual-parameter thin film sensor monitoring battery for safety monitoring of an energy storage system prepared in example 1.
Detailed Description
The first embodiment is as follows: the double-parameter film sensor for safety monitoring of the energy storage system comprises 4 temperature sensitive layers, 1 pressure sensitive layer, 1 interdigital electrode, 4 far-end electrodes and 4 wires;
the interdigital electrode is positioned at the center of the sensor, the pressure sensitive layer and the interdigital electrode have the same size, the pressure sensitive layer is positioned right above the interdigital electrode and is tightly contacted with the interdigital electrode, and 4 temperature sensitive layers are distributed at four corners of the sensor;
one end of the 1 st wire is sequentially connected with the four temperature sensitive layers, and the other end of the 1 st wire is connected with the far-end electrode, so that the output of temperature sensing signals is realized;
one end of the 2 nd wire is connected with a temperature sensitive layer close to the far-end electrode, bypasses the pressure sensitive layer, and the other end of the 2 nd wire is connected with the far-end electrode to realize the output of temperature sensing signals;
the 3 rd lead and the 4 th lead are respectively connected with the interdigital electrodes to realize the output of pressure sensing signals.
The second embodiment is as follows: the present embodiment differs from the specific embodiment in that: the length of the double-parameter film sensor for safety monitoring of the energy storage system is 29-31 mm, and the width is 29-31 mm; the length of the pressure sensitive layer is 19-21 mm, and the width is 9-11 mm; the length of the temperature sensitive layer is 2.5 mm-3.5 mm, and the width is 2.5 mm-3.5 mm. The other steps are the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: the lead is a silver wire; the width of the wire is 0.1 mm-0.15 mm; the inter-finger distance of the inter-finger electrodes is 1.9 mm-2.1 mm. The other steps are the same as those of the first or second embodiment.
The specific embodiment IV is as follows: one difference between this embodiment and the first to third embodiments is that: the temperature sensitive layer and the pressure sensitive layer are the same in material and thickness and are PVDF/SWCNT composite polymer film materials, and the preparation method is specifically completed according to the following steps:
1. preparing slurry:
placing polyvinylidene fluoride and single-walled carbon nanotubes into a mortar, and grinding to uniformly mix the polyvinylidene fluoride and the single-walled carbon nanotubes to obtain mixed powder; dropwise adding N-methyl pyrrolidone into the mixed powder under the stirring condition, and stirring to obtain black sizing agent;
2. preparing a film:
and pouring the black paste on a polyimide film, scraping the film by using an automatic knife coater, adhering and fixing the uniformly scraped film on a glass plate to avoid deformation, storing in a vacuum oven for drying, and removing the film from the polyimide film after drying to obtain the PVDF/SWCNT composite sensitive material. The other steps are the same as those of the first to third embodiments.
Fifth embodiment: one to four differences between the present embodiment and the specific embodiment are: the volume ratio of the mass of the polyvinylidene fluoride to the N-methyl pyrrolidone in the first step is (8 g-10 g) 20mL; the volume ratio of the mass of the single-wall carbon nano tube to the N-methyl pyrrolidone in the first step is (1 g-3 g) 20mL; the grinding time in the first step is 20-30 min; the stirring time in the first step is 4-6 h. Other steps are the same as those of the first to fourth embodiments.
Specific embodiment six: the present embodiment differs from the first to fifth embodiments in that: the doctor blade thickness of the doctor blade machine is 19-21 mu m, and the doctor blade speed is 1cm/s; the thickness of the polyimide film in the second step is 100-110 mu m; the temperature of the drying in the second step is 80-90 ℃, and the drying time is 10-12 h. Other steps are the same as those of the first to fifth embodiments.
Seventh embodiment: the embodiment is a preparation method of a double-parameter film sensor for safety monitoring of an energy storage system, which is specifically completed by the following steps:
1. preparing slurry:
placing polyvinylidene fluoride and single-walled carbon nanotubes into a mortar, and grinding to uniformly mix the polyvinylidene fluoride and the single-walled carbon nanotubes to obtain mixed powder; dropwise adding N-methyl pyrrolidone into the mixed powder under the stirring condition, and stirring to obtain black sizing agent;
2. preparing a film:
pouring black paste on a polyimide film, scraping the film by an automatic knife coater, adhering and fixing the uniformly scraped film on a glass plate to avoid deformation, storing in a vacuum oven for drying, and removing the film from the polyimide film after drying to obtain the PVDF/SWCNT composite sensitive material;
3. preparing a bottom layer circuit:
printing a conductive silver paste bottom layer circuit pattern on the polyimide film by using an automatic direct writing machine, wherein the bottom layer circuit pattern is respectively 1 interdigital electrode, 4 far-end electrodes and 4 wires, and drying the polyimide film on a heating table to obtain a bottom layer circuit of the double-parameter film sensor for safety monitoring of an energy storage system;
4. preparing a sensor:
cutting the PVDF/SWCNT composite sensitive material to obtain 4 temperature sensitive layers and 1 pressure sensitive layer; the 4 temperature sensitive layers and the 1 pressure sensitive layer are respectively arranged at the corresponding positions on the bottom layer circuit, so that one end of the 1 st wire is sequentially connected with the four temperature sensitive layers, and the other end is connected with the far-end electrode, and the output of temperature sensing signals is realized; one end of the 2 nd wire is connected with a temperature sensitive layer close to the far-end electrode, bypasses the pressure sensitive layer, and the other end of the 2 nd wire is connected with the far-end electrode to realize the output of temperature sensing signals; the 3 rd lead and the 4 th lead are respectively connected with the interdigital electrodes to realize the output of pressure sensing signals; and then fixing by using an insulated polyimide adhesive tape to obtain the double-parameter film sensor for safety monitoring of the energy storage system.
Eighth embodiment: the present embodiment differs from the seventh embodiment in that: the volume ratio of the mass of the polyvinylidene fluoride to the N-methyl pyrrolidone in the first step is (8 g-10 g) 20mL; the volume ratio of the mass of the single-wall carbon nano tube to the N-methyl pyrrolidone in the first step is (1 g-3 g) 20mL; the grinding time in the first step is 20-30 min; the stirring time in the first step is 4-6 hours; the doctor blade thickness of the doctor blade machine is 19-21 mu m, and the doctor blade speed is 1cm/s; the thickness of the polyimide film in the second step is 100-110 mu m; the temperature of the drying in the second step is 80-90 ℃, and the drying time is 10-12 hours; the thickness of the polyimide film in the third step is 100-110 mu m; and thirdly, drying the mixture on a heating table at the temperature of 80-90 ℃ for 1-1.5 h. The other steps are the same as in embodiment seven.
Detailed description nine: the embodiment is a dual-parameter thin film sensor for safety monitoring of an energy storage system, which is implanted into the energy storage system and is used for detecting the temperature and the pressure inside the energy storage system.
Detailed description ten: the difference between this embodiment and the ninth embodiment is that: the basic unit of the energy storage system is a battery. The other steps are the same as in embodiment nine.
The following examples are used to verify the benefits of the present invention:
example 1: the double-parameter film sensor for safety monitoring of the energy storage system consists of 4 temperature sensitive layers, 1 pressure sensitive layer, 1 interdigital electrode, 4 far-end electrodes and 4 wires;
the interdigital electrode is positioned at the center of the sensor, the pressure sensitive layers are the same as the interdigital electrode in size, the pressure sensitive layers cover the interdigital electrode, and 4 temperature sensitive layers are distributed at four corners of the sensor;
one end of the 1 st wire is sequentially connected with the four temperature sensitive layers, and the other end of the 1 st wire is connected with the far-end electrode, so that the output of temperature sensing signals is realized;
one end of the 2 nd wire is connected with a temperature sensitive layer close to the far-end electrode, bypasses the pressure sensitive layer, and the other end of the 2 nd wire is connected with the far-end electrode to realize the output of temperature sensing signals;
the 3 rd lead and the 4 th lead are respectively connected with the interdigital electrodes to realize the output of pressure sensing signals;
the temperature sensitive layer and the pressure sensitive layer are the same in material and are PVDF/SWCNT composite sensitive materials;
the preparation method of the sensor is specifically completed by the following steps:
1. preparing slurry:
putting 9g of polyvinylidene fluoride (PVDF) and 2g of single-walled carbon nanotubes (SWCNT) into a mortar, grinding for 20min, and uniformly mixing the polyvinylidene fluoride and the single-walled carbon nanotubes to obtain mixed powder; dropwise adding 20mL of N-methylpyrrolidone into the mixed powder under the stirring condition, and stirring for 5 hours at the stirring speed of 200r/min to obtain black sizing agent;
2. preparing a film:
pouring black paste on a polyimide film with the thickness of 100 mu m, scraping the film by an automatic knife coater, pasting and fixing the film with even knife coating on a glass plate to avoid deformation, and drying the film in a vacuum oven with the temperature of 80 ℃ for 12 hours, and removing the film from the polyimide film after drying to obtain the PVDF/SWCNT composite sensitive material;
the doctor blade thickness of the doctor blade machine is 20 mu m, and the doctor blade speed is 1cm/s;
3. preparing a bottom layer circuit:
printing a conductive silver paste bottom layer circuit pattern on a polyimide film with the thickness of 100 mu m by using an automatic direct writing machine, wherein the circuit pattern comprises 1 interdigital electrode, 4 far-end electrodes and 4 wires respectively, and drying the polyimide film on a heating table at 90 ℃ for 1h to obtain a bottom layer circuit of a double-parameter film sensor for safety monitoring of an energy storage system;
4. preparing a sensor:
cutting the PVDF/SWCNT composite sensitive material to obtain 4 temperature sensitive layers and 1 pressure sensitive layer; the 4 temperature sensitive layers and the 1 pressure sensitive layer are respectively arranged at the corresponding positions on the bottom layer circuit, so that one end of the 1 st wire is sequentially connected with the four temperature sensitive layers, and the other end is connected with the far-end electrode, and the output of temperature sensing signals is realized; one end of the 2 nd wire is connected with a temperature sensitive layer close to the far-end electrode, bypasses the pressure sensitive layer, and the other end of the 2 nd wire is connected with the far-end electrode to realize the output of temperature sensing signals; the 3 rd lead and the 4 th lead are respectively connected with the interdigital electrodes to realize the output of pressure sensing signals; then, fixing by using an insulated polyimide adhesive tape to obtain a double-parameter film sensor for safety monitoring of an energy storage system;
the length of the double-parameter film sensor for safety monitoring of the energy storage system is 30mm, and the width of the double-parameter film sensor is 30mm; the width of the pressure sensitive layer is 20mm and the length is 10mm; the length of the temperature sensitive layer is 3mm, and the width is 2mm; drying the conductive silver paste to obtain a wire, wherein the width of the wire is 0.1mm; the inter-digital distance of the inter-digital electrode is 2mm.
Fig. 1 is a schematic structural diagram of a dual-parameter thin film sensor for safety monitoring of an energy storage system, prepared in embodiment 1, in which a is the length of the sensor, b is the width of the sensor, c is the width of the pressure sensitive layer, d is the length of the pressure sensitive layer, e is the length of the temperature sensitive layer, f is the width of the temperature sensitive layer, and g is the inter-finger pitch of the inter-finger electrodes;
FIG. 2 is a physical diagram of a dual-parameter thin film sensor for safety monitoring of an energy storage system prepared in example 1;
FIG. 3 is a scanning electron microscope image, wherein a is a scanning electron microscope image of SWCNT, b is a scanning electron microscope image of PVDF film, c is a low power scanning electron microscope image of PVDF/SWCNT composite sensitive material prepared in step two of example 1, and d is a high power scanning electron microscope image of PVDF/SWCNT composite sensitive material prepared in step two of example 1;
as can be seen from fig. 3 a: SWCNT are curved linear structures; as can be seen from fig. 3 b: the PVDF film is uniform and continuous and has no wrinkles; as can be seen from fig. 3 c: the surface of the film is continuously wrinkled; as can be seen from fig. 3 d, the carbon nanotubes are wrapped by PVDF and uniformly distributed, and the carbon nanotubes are wound and connected to form a stable conductive network, which is the basis of the excellent conductivity and sensitivity pressure-sensitive temperature-sensitive characteristics of the composite film.
FIG. 4 is a temperature sensitivity of a dual-parameter thin film sensor for safety monitoring of an energy storage system prepared in example 1, wherein a is a curve of current of the sensor along with temperature change, and b is a temperature calibration curve of the sensor;
in fig. 4, a is a temperature-sensitive performance test curve of the sensor in an oil bath, when the sensor is applied with a constant voltage of 2V, the temperature gradually rises from 40 ℃ to 90 ℃, the current passing through the device is continuously increased, and the increasing rate and the heating rate are basically consistent. In fig. 4 b is a temperature calibration curve at 5 deg.c intervals, the sensor is made of a material with obvious negative temperature coefficient in the range of 40 deg.c to 90 deg.c, and the thermal runaway trigger temperature of 80 deg.c can be effectively monitored.
FIG. 5 is a graph showing the pressure-sensitive performance of a dual-parameter thin film sensor for safety monitoring of an energy storage system prepared in example 1, wherein a is a cycle curve of the sensor for simulation monitoring of the swelling state of a battery, and b is the mechanical cycle performance of the sensor;
in fig. 5a is a cycle curve of the process of simulating the swelling of the battery by the air bag, applying a constant pressure of 2V to the device and attaching the device to the inside of the battery package, and simultaneously putting the air bag into the battery package and repeatedly injecting 50ml of gas (air) into the air bag through the syringe. The current of the device can be clearly identified to be in a bulge state and a stable state, and the difference is obvious, because when the material is extruded by gas, the contact area between SWCNTs uniformly dispersed in the PVDF film is increased, so that the overall resistance of the material is reduced, and the current passing through the device is increased. The greater the force applied, the more contact between SWCNTs and the greater the current generated. The device can accurately identify the swelling state of the battery and has stability and durability, and b in fig. 5 is a mechanical cycle test curve of the device, the device is applied with a pressure of 1N to 5N in a linear and cycle period of 20s, and the device is monitored for the cycle stability by monitoring the resistance of the device. The device still maintains a stable pressure signal response after 7000 cycles, and the initial resistance drop is due to excessive cycle time and increased contact area between SWCNTs within the material. The resistance value of the device remained unchanged before and after 7000 cycles under the condition of 5N pressure, which indicates that the device has excellent cycle stability.
Fig. 6 is a graph of thermal runaway of a dual-parameter thin film sensor monitoring battery for safety monitoring of an energy storage system prepared in example 1.
FIG. 6 shows a sensor monitoring the performance of a battery during overcharging; the device was placed between two polymer commercial soft pack batteries (purchased from Shenzhen New energy technology Co.) rated at 4V to simulate the internal environment of the battery. To cause thermal runaway of the battery and to detect sensor performance, an over-charge test was performed at a power of 8V, 5A. The temperature and voltage of the battery before 150s are in a stable trend, and as the voltage of the battery rises, lithium dendrites in the battery rapidly grow, and the battery is in an unstable state. During the period of 150s to 480s, the temperature gradually rises, and the pressure curve falls, because the battery expands, and the current measured by the sensor falls due to uneven stress. And as overcharging continues, the pressure curve rises rapidly after 500s and the temperature also rises rapidly, indicating that the battery is now in the thermal runaway triggering phase. The voltage and current curves are suddenly changed to 0 at 600s, the battery explodes at the moment, and the sensor monitoring system is disconnected. The whole monitoring process can record the temperature and the pressure state between the batteries before the batteries are in thermal runaway, each parameter of the batteries rapidly and violently rises 100s before the batteries are in thermal runaway, and the batteries can be identified to be in an unstable state 400s before the batteries are in thermal runaway. Therefore, the device can effectively record the whole process of thermal runaway of the battery, can improve effective data support for a battery management system, and ensures the safety of personnel and equipment.
Claims (10)
1. The double-parameter film sensor for safety monitoring of the energy storage system is characterized by comprising 4 temperature sensitive layers, 1 pressure sensitive layer, 1 interdigital electrode, 4 far-end electrodes and 4 wires;
the interdigital electrode is positioned at the center of the sensor, the pressure sensitive layer and the interdigital electrode have the same size, the pressure sensitive layer is positioned right above the interdigital electrode and is tightly contacted with the interdigital electrode, and 4 temperature sensitive layers are distributed at four corners of the sensor;
one end of the 1 st wire is sequentially connected with the four temperature sensitive layers, and the other end of the 1 st wire is connected with the far-end electrode, so that the output of temperature sensing signals is realized;
one end of the 2 nd wire is connected with a temperature sensitive layer close to the far-end electrode, bypasses the pressure sensitive layer, and the other end of the 2 nd wire is connected with the far-end electrode to realize the output of temperature sensing signals;
the 3 rd lead and the 4 th lead are respectively connected with the interdigital electrodes to realize the output of pressure sensing signals.
2. The dual-parameter thin film sensor for safety monitoring of an energy storage system according to claim 1, wherein the dual-parameter thin film sensor for safety monitoring of the energy storage system is 29-31 mm in length and 29-31 mm in width; the length of the pressure sensitive layer is 19-21 mm, and the width is 9-11 mm; the length of the temperature sensitive layer is 2.5 mm-3.5 mm, and the width is 2.5 mm-3.5 mm.
3. The dual-parameter thin film sensor for energy storage system safety monitoring of claim 1, wherein said conductive wire is a silver wire; the width of the wire is 0.1 mm-0.15 mm; the inter-finger distance of the inter-finger electrodes is 1.9 mm-2.1 mm.
4. The dual-parameter film sensor for safety monitoring of an energy storage system according to claim 1, wherein the temperature sensitive layer and the pressure sensitive layer are the same in material and thickness, and are PVDF/SWCNT composite polymer film materials, and the preparation method is specifically completed by the following steps:
1. preparing slurry:
placing polyvinylidene fluoride and single-walled carbon nanotubes into a mortar, and grinding to uniformly mix the polyvinylidene fluoride and the single-walled carbon nanotubes to obtain mixed powder; dropwise adding N-methyl pyrrolidone into the mixed powder under the stirring condition, and stirring to obtain black sizing agent;
2. preparing a film:
and pouring the black paste on a polyimide film, scraping the film by using an automatic knife coater, adhering and fixing the uniformly scraped film on a glass plate to avoid deformation, storing in a vacuum oven for drying, and removing the film from the polyimide film after drying to obtain the PVDF/SWCNT composite sensitive material.
5. The dual-parameter thin film sensor for energy storage system safety monitoring according to claim 4, wherein the volume ratio of the mass of polyvinylidene fluoride to the volume of N-methyl pyrrolidone in the first step is (8 g-10 g): 20mL; the volume ratio of the mass of the single-wall carbon nano tube to the N-methyl pyrrolidone in the first step is (1 g-3 g) 20mL; the grinding time in the first step is 20-30 min; the stirring time in the first step is 4-6 h.
6. The dual-parameter thin film sensor for safety monitoring of an energy storage system according to claim 4, wherein the doctor blade thickness of the doctor blade machine is 19 μm-21 μm and the doctor blade speed is 1cm/s; the thickness of the polyimide film in the second step is 100-110 mu m; the temperature of the drying in the second step is 80-90 ℃, and the drying time is 10-12 h.
7. The method for preparing the double-parameter film sensor for safety monitoring of an energy storage system as claimed in claim 1, wherein the preparation method is specifically implemented by the following steps:
1. preparing slurry:
placing polyvinylidene fluoride and single-walled carbon nanotubes into a mortar, and grinding to uniformly mix the polyvinylidene fluoride and the single-walled carbon nanotubes to obtain mixed powder; dropwise adding N-methyl pyrrolidone into the mixed powder under the stirring condition, and stirring to obtain black sizing agent;
2. preparing a film:
pouring black paste on a polyimide film, scraping the film by an automatic knife coater, adhering and fixing the uniformly scraped film on a glass plate to avoid deformation, storing in a vacuum oven for drying, and removing the film from the polyimide film after drying to obtain the PVDF/SWCNT composite sensitive material;
3. preparing a bottom layer circuit:
printing a conductive silver paste bottom layer circuit pattern on the polyimide film by using an automatic direct writing machine, wherein the bottom layer circuit pattern is respectively 1 interdigital electrode, 4 far-end electrodes and 4 wires, and drying the polyimide film on a heating table to obtain a bottom layer circuit of the double-parameter film sensor for safety monitoring of an energy storage system;
4. preparing a sensor:
cutting the PVDF/SWCNT composite sensitive material to obtain 4 temperature sensitive layers and 1 pressure sensitive layer; the 4 temperature sensitive layers and the 1 pressure sensitive layer are respectively arranged at the corresponding positions on the bottom layer circuit, so that one end of the 1 st wire is sequentially connected with the four temperature sensitive layers, and the other end is connected with the far-end electrode, and the output of temperature sensing signals is realized; one end of the 2 nd wire is connected with a temperature sensitive layer close to the far-end electrode, bypasses the pressure sensitive layer, and the other end of the 2 nd wire is connected with the far-end electrode to realize the output of temperature sensing signals; the 3 rd lead and the 4 th lead are respectively connected with the interdigital electrodes to realize the output of pressure sensing signals; and then fixing by using an insulated polyimide adhesive tape to obtain the double-parameter film sensor for safety monitoring of the energy storage system.
8. The dual-parameter thin film sensor for safety monitoring of an energy storage system according to claim 7, wherein the volume ratio of the mass of polyvinylidene fluoride to the volume of N-methylpyrrolidone in the first step is (8 g-10 g): 20mL; the volume ratio of the mass of the single-wall carbon nano tube to the N-methyl pyrrolidone in the first step is (1 g-3 g) 20mL; the grinding time in the first step is 20-30 min; the stirring time in the first step is 4-6 hours; the doctor blade thickness of the doctor blade machine is 19-21 mu m, and the doctor blade speed is 1cm/s; the thickness of the polyimide film in the second step is 100-110 mu m; the temperature of the drying in the second step is 80-90 ℃, and the drying time is 10-12 hours; the thickness of the polyimide film in the third step is 100-110 mu m; and thirdly, drying the mixture on a heating table at the temperature of 80-90 ℃ for 1-1.5 h.
9. A dual-parameter thin film sensor for energy storage system safety monitoring as claimed in claim 1, wherein a dual-parameter thin film sensor for energy storage system safety monitoring is implanted in the energy storage system for detecting temperature and pressure inside the energy storage system.
10. A dual-parameter thin film sensor for energy storage system safety monitoring as claimed in claim 1, wherein said energy storage system base unit is a battery.
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