CN117091727A - PEO-based implantable battery temperature sensor and preparation method and application thereof - Google Patents
PEO-based implantable battery temperature sensor and preparation method and application thereof Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K13/00—Thermometers specially adapted for specific purposes
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
- G01K7/16—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements
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Abstract
An implantable battery temperature sensor based on PEO 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 of complex structure, high process requirement, more additional monitoring equipment and high cost of the conventional temperature sensor implanted in the battery. The temperature sensor of the implantable battery based on PEO is characterized in that a temperature sensitive area of the sensor is made of PEO/CMC/Gr conductive composite material, pins are made of silver wires, and two sides of the lower end of the temperature sensitive area are respectively connected with corners of the two pins. The method comprises the following steps: 1. preparing conductive slurry; 2. and printing pins and the temperature sensitive area on the polyimide film in a layering manner, and covering the polyimide film to obtain the PEO-based implantable battery temperature sensor. The sensor is implanted inside the battery for detecting the temperature inside the battery. The present invention can achieve a PEO-based implantable battery temperature sensor.
Description
Technical Field
The invention relates to a sensor, a preparation method and application thereof.
Background
Electrochemical energy storage technologies represented by lithium ion batteries are energy storage technologies that utilize electrochemical reactions to achieve the conversion between electrical energy and chemical energy. The lithium ion battery has the characteristics of high energy density, long cycle life and the like, and is widely applied to various battery energy storage technologies. In the actual use process of the battery, if the lithium ion battery is in thermal runaway, the lithium ion battery has the characteristics of short reaction time, severe combustion and the like. The structure of the lithium ion battery is designed to be limited in charge and discharge times, and the higher the charge and discharge voltage is, the more easily lithium dendrites are generated to pierce the diaphragm to cause internal short circuit, so that the thermal runaway of the battery is caused, and the irreversible influence is generated. The light weight reduces the performance, and the heavy weight causes spontaneous combustion and explosion. Therefore, it is necessary to detect the battery temperature, and to give early warning or cut off thermal runaway in advance.
The development of thin film sensors allows the sensor to be implanted inside the battery. The battery is detected from the inside of the battery, the real-time state of the battery can be reflected more accurately, and along with the continuous development of technologies such as nano printing and the like, temperature-sensitive components are obtained on the flexible substrate through processes such as printing, coating and the like, so that the temperature-sensitive component is low in cost, simple in structure and high in integration level. And because the thin film sensor has the characteristic of small volume, the internal space of the battery is not occupied, the space utilization rate is improved, and the battery capacity is increased. The film temperature sensor manufactured by taking the carbon-based temperature-sensitive material as the conductive filler comprises crystalline flake graphite, carbon black, carbon fiber, carbon nano tube and the like, and has excellent mechanical and electrical properties. The conductive filler establishes a conductive network in the composite material by mixing the carbon-based conductive material with the polymer, and the conductive network changes after the environmental temperature changes, so that the resistance of the temperature-sensitive material changes, and the temperature change is sensed.
There are now some implanted temperature sensors, such as micro sensors that can realize temperature and current dual signal detection, prepared by surface micro mechanical technology. The sensor sensitive layer is constructed by a vacuum evaporation technology, a device structure layer is prepared by adopting a photoetching technology and wet corrosion, and the device structure layer is implanted into a button cell to realize temperature and current signal detection under the working state of the cell. But the structure is complex and the process requirement is relatively high.
The Bragg grating optical fiber temperature sensor can also be used for implantation in a battery, and can realize real-time monitoring of the internal temperature of the battery by utilizing the phenomenon that the grating can refract light under different temperature conditions. Although the battery monitoring technology is widely studied, the further development of the additional monitoring equipment is limited due to the fact that the additional monitoring equipment is more than optical fiber sensing, the manufacturing cost of the miniature sensor is high, and the additional monitoring equipment is difficult to apply to a practical application environment.
Disclosure of Invention
The invention aims to solve the problems of complex structure, high process requirement, more additional monitoring equipment and high cost of the existing implantable battery temperature sensor, and provides a PEO-based implantable battery temperature sensor, a preparation method and application thereof.
The polymer film sensor can be implanted into the lithium ion battery to realize internal temperature early warning due to the advantages of self thinness, low preparation cost and the like; the invention adopts a film temperature sensing device based on PEO thermal expansion material, adopts CMC as material support, and graphite as conductive material to jointly form a binary sensing device. The PEO takes water as a solvent, so that the manufacturing process is not influenced by environmental humidity, and the process is simple; when the battery generates heat to reach a certain temperature, PEO expands when heated, the heated resistance of the sensor increases, the concentration of graphite particles in unit volume decreases, and the temperature sensor can generate abrupt change of an internal conductive path at the characteristic temperature of 80 ℃ so as to trigger an alarm; the structure is simple, and the operation can be realized without additional monitoring equipment; PEO is sensitive to temperature response and has excellent repeatability compared to other polymer sensors.
The temperature sensitive area of the implantable battery temperature sensor based on PEO is made of PEO/CMC/Gr conductive composite material, the pins are made of conductive silver paste, and two sides of the lower end of the temperature sensitive area are respectively connected with the corners of the two pins.
The preparation method of the implantable battery temperature sensor based on PEO comprises the following steps:
1. preparing conductive slurry:
(1) adding polyethylene oxide into deionized water, and performing ultrasonic dispersion to obtain a polyethylene oxide solution; stirring the polyethylene oxide solution to obtain a colorless transparent viscous PEO solution;
(2) uniformly grinding carboxymethyl cellulose and graphite powder in a mortar until the powder has no obvious chromatic aberration, so as to obtain CMC/graphite powder;
(3) adding CMC/graphite powder into PEO solution, adding deionized water for dilution, slowly stirring for a period of time, placing into a vacuum drying oven for standing, and removing air mixed in colloid to obtain conductive slurry;
2. firstly, respectively beating two pins on two sides of the lower end of a temperature sensitive area on a polyimide film by using conductive silver paste, then drying and sintering, and then layering and drawing the conductive paste obtained in the step one on the polyimide film by using a microelectronic printer, and naturally air-drying to obtain the temperature sensitive area of the sensor; and finally covering a polyimide film above the temperature sensitive area to obtain the PEO-based implantable battery temperature sensor.
The principle of the invention is as follows:
1. according to the invention, polyethylene oxide (PEO) is used as a thermal expansion temperature-sensitive material, carboxymethyl cellulose (CMC) is used as a substrate, graphite (Graphite) is used as a conductive material to design a temperature sensor, a temperature-sensitive mechanism of the temperature sensor is analyzed from a microscopic angle, a thin film sensor convenient to implant into a battery is designed, the temperature resistance characteristic of the sensor is researched, the stability, the repeatability and other performances of the sensor are tested, the sensor is used for in-situ detection of the battery, the battery temperature is obtained from the inside, and the thermal runaway temperature response of the battery under the overcharge condition is tested;
2. the PEO-based implantable battery temperature sensor prepared by the invention is used as a flexible material, is very suitable for being implanted into a battery, and the internal temperature of the battery is always higher than that detected by the outside, so that when the sensor is implanted into the battery for in-situ monitoring, the problem can be found earlier, the failure of the battery can be found in advance, and the spontaneous combustion of the battery can be avoided; if the battery is out of control, more time is also striven for the user to avoid danger;
3. according to the invention, under the same area, the interval between the anode and the cathode is reduced, the contact length is enlarged, the electronic conduction is facilitated, and the resistance is reduced; the resistance of the sensing device should not be too great (2859 Ω for the PEO-based implantable battery temperature sensor prepared in example 1 of the present invention), which means that more noise is introduced during signal processing; according to the invention, silver paste is used, the pins and the temperature-sensitive areas are transited by curves, so that the wiring of the pins is ensured to be convenient while the resistance of the material is reduced, and the direction of the pins is at the same side, so that the subsequent implantation is facilitated.
Drawings
Fig. 1 is a schematic structural diagram of a PEO-based implantable battery temperature sensor prepared in example 1, in which the upper and lower polyimide films are not shown, 1 is a temperature sensitive region, 2 is a pin, a is a width of the temperature sensitive region, b is a length of the temperature sensitive region, c is an overall length of the sensor, d is a height at a corner of the pin, and e is a width between two pins;
FIG. 2 is a microscopic topography of a temperature sensitive region PEO/CMC/Gr conductive composite of a PEO-based implantable battery temperature sensor prepared in example 1;
FIG. 3 is an I-V test curve of a PEO-based implantable battery temperature sensor, where curve 1 is the PEO-based implantable battery temperature sensor prepared in example 1, curve 2 is the PEO-based implantable battery temperature sensor prepared in example 2, and curve 3 is the PEO-based implantable battery temperature sensor prepared in example 3;
FIG. 4 is a graph of I-V test curves for the PEO-based implantable battery temperature sensor prepared in example 1 at various temperatures, where the temperature is 30℃ for curve 1, 40℃ for curve 2, 50℃ for curve 3, 60℃ for curve 4, 70℃ for curve 5, and 80℃ for curve 6;
FIG. 5 is a plot of resistance versus temperature for the PEO-based implantable battery temperature sensor prepared in example 1;
FIG. 6 is a graph of temperature cycling response test of the PEO-based implantable battery temperature sensor prepared in example 2;
FIG. 7 is a schematic representation of the implantation of the PEO-based implantable battery temperature sensor prepared in example 1, wherein (a) is the schematic representation of the implantation, (b) is the sensor fixed on top of the positive electrode, and (c) is the schematic representation of the finished soft pack after implantation;
fig. 8 is a graph of the temperature response of the PEO-based implantable battery temperature sensor prepared in example 1 after implantation into a battery versus battery overcharge temperature.
Detailed Description
The first embodiment is as follows: the implantable battery temperature sensor based on PEO is characterized in that a temperature sensitive area of the sensor is made of PEO/CMC/Gr conductive composite materials, pins are made of silver wires, and two sides of the lower end of the temperature sensitive area are respectively connected with corners of the two pins.
The second embodiment is as follows: the present embodiment differs from the specific embodiment in that: the width of the temperature sensitive area is 1.4 mm-1.6 mm, the length of the temperature sensitive area is 3.9 mm-4.1 mm, and the thickness of the temperature sensitive area is 0.14 mm-0.2 mm; the overall length of the sensor is 49.9-50.1 mm, the height of the corner of the pin is 1.9-2.1 mm, the inclination angle of the corner of the pin is 44.9-45.1 degrees, and the width between the two pins is 4.9-5.1 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 preparation method of the PEO/CMC/Gr conductive composite material is specifically completed by the following steps:
1. adding polyethylene oxide into deionized water, and performing ultrasonic dispersion to obtain a polyethylene oxide solution; stirring the polyethylene oxide solution to obtain a colorless transparent viscous PEO solution;
2. uniformly grinding carboxymethyl cellulose and graphite powder in a mortar until the powder has no obvious chromatic aberration, thereby obtaining CMC/graphite powder;
3. adding CMC/graphite powder into PEO solution, adding deionized water for dilution, slowly stirring for a period of time, placing into a vacuum drying oven for standing, and removing air mixed in colloid to obtain conductive slurry; and (3) layering and drawing the conductive paste on the polyimide film by utilizing a microelectronic printer, and naturally airing to obtain a temperature-sensitive area of the sensor, namely the PEO/CMC/Gr conductive composite material. 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 volume ratio of the mass of the polyethylene oxide to the deionized water in the first step is (0.5 g-0.7 g) 10mL; the ultrasonic dispersion time in the first step is 20-30 min, and the ultrasonic dispersion power is 50-60W; and in the first step, stirring the polyethylene oxide solution for 2-3 hours. 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 mass ratio of the carboxymethyl cellulose to the graphite powder in the second step is (0.5 g-0.7 g) to (0.7 g-0.9 g). 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 mass volume ratio of CMC/graphite powder, PEO solution and deionized water in the third step is (1 g-2 g) (10 mL-12 mL) (15 mL-25 mL). Other steps are the same as those of the first to fifth embodiments.
Seventh embodiment: one difference between the present embodiment and the first to sixth embodiments is that: the speed of the slow stirring in the third step is 250 r/min-300 r/min, and the time of the slow stirring is 4 h-5 h; and thirdly, placing the mixture into a vacuum drying oven for standing for 1-2 hours. Other steps are the same as those of embodiments one to six.
Eighth embodiment: the embodiment is a preparation method of an implantable battery temperature sensor based on PEO, which is specifically completed by the following steps:
1. preparing conductive slurry:
(1) adding polyethylene oxide into deionized water, and performing ultrasonic dispersion to obtain a polyethylene oxide solution; stirring the polyethylene oxide solution to obtain a colorless transparent viscous PEO solution;
(2) uniformly grinding carboxymethyl cellulose and graphite powder in a mortar until the powder has no obvious chromatic aberration, so as to obtain CMC/graphite powder;
(3) adding CMC/graphite powder into PEO solution, adding deionized water for dilution, slowly stirring for a period of time, placing into a vacuum drying oven for standing, and removing air mixed in colloid to obtain conductive slurry;
2. firstly, respectively printing two pins on two sides of the lower end of a temperature sensitive area on a polyimide film by using conductive silver paste, then drying and sintering, and then layering and drawing the conductive paste obtained in the step one on the polyimide film by using a microelectronic printer, and naturally air-drying to obtain the temperature sensitive area of the sensor; and finally covering a polyimide film above the temperature sensitive area to obtain the PEO-based implantable battery temperature sensor.
Detailed description nine: the present embodiment differs from the eighth embodiment in that: the volume ratio of the mass of the polyethylene oxide to the deionized water in the step one (1) is (0.5 g-0.7 g) 10mL; the ultrasonic dispersion time in the step one (1) is 20-30 min, and the ultrasonic dispersion power is 50-60W; stirring the polyethylene oxide solution in the step one (1) for 2-3 hours; the mass ratio of the carboxymethyl cellulose to the graphite powder in the step one (2) is (0.5 g-0.7 g) (0.7 g-0.9 g); the mass volume ratio of CMC/graphite powder, PEO solution and deionized water in the step one (3) is (1 g-2 g) (10 mL-12 mL) (15 mL-25 mL); the speed of the slow stirring in the step one (3) is 250 r/min-300 r/min, and the time of the slow stirring is 4 h-5 h; placing the mixture into a vacuum drying oven for standing for 1-2 h in the step one (3); and step two, the temperature of the drying and sintering is 200 ℃, and the time of the drying and sintering is 1-2 h. The other steps are the same as those of embodiment eight.
Detailed description ten: the present embodiment differs from the eighth to ninth embodiments in that: a PEO-based implantable battery temperature sensor is implanted inside the battery for detecting the temperature inside the battery. The other steps are the same as those of embodiments eight to nine.
The following examples are used to verify the benefits of the present invention:
example 1: the preparation method of the implantable battery temperature sensor based on PEO comprises the following steps:
1. preparing conductive slurry:
(1) adding 0.6g of polyethylene oxide (PEO) into 10mL of deionized water, and performing ultrasonic dispersion for 30min under the ultrasonic power of 50W to obtain a polyethylene oxide solution; stirring the polyethylene oxide solution for 2 hours at the stirring speed of 300r/min to obtain a colorless transparent PEO solution;
(2) uniformly grinding 0.6g of carboxymethyl cellulose (CMC) and 0.8g of graphite powder (Gr) in a mortar until the powder has no obvious chromatic aberration, thus obtaining CMC/graphite powder;
(3) adding CMC/graphite powder into PEO solution, adding 20mL of deionized water for dilution, stirring for 4h at 300r/min, placing into a vacuum drying oven for standing for 1h, and removing air mixed in colloid to obtain conductive slurry;
2. firstly, respectively printing two pins on two sides of the lower end of a temperature sensitive area on a polyimide film by using conductive silver paste, then drying and sintering for 2 hours at 200 ℃, and then layering and drawing the conductive paste obtained in the step one on the polyimide film by using a microelectronic printer, and naturally air-drying to obtain the temperature sensitive area of the sensor; finally, covering a polyimide film above the temperature sensitive area to obtain an implantable battery temperature sensor based on PEO;
the width of a temperature sensitive area in the PEO-based implantable battery temperature sensor in the second step is 1.5mm, the length of the temperature sensitive area is 4mm, and the thickness of the temperature sensitive area is 0.15mm; the overall length of the sensor is 50mm, the height of the corner of the pin is 2mm, the inclination angle of the corner of the pin is 45 degrees, and the width between the two pins is 5mm.
Example 2: the difference between this embodiment and embodiment 1 is that: the thickness of the temperature sensitive area in the PEO-based implantable battery temperature sensor described in step two was 0.18mm. Other steps and parameters were the same as in example 1.
Example 3: the difference between this embodiment and embodiment 1 is that: the thickness of the temperature sensitive area in the PEO-based implantable battery temperature sensor described in step two was 0.2mm. Other steps and parameters were the same as in example 1.
Fig. 1 is a schematic structural diagram of a PEO-based implantable battery temperature sensor prepared in example 1, in which the upper and lower polyimide films are not shown, 1 is a temperature sensitive region, 2 is a pin, a is a width of the temperature sensitive region, b is a length of the temperature sensitive region, c is an overall length of the sensor, d is a height at a corner of the pin, and e is a width between two pins;
FIG. 2 is a microscopic topography of a temperature sensitive region PEO/CMC/Gr conductive composite of a PEO-based implantable battery temperature sensor prepared in example 1;
FIG. 2 shows SEM micrographs of PEO/CMC/Gr conductive composites with 40% conductive graphite powder;
as can be seen from fig. 2 (a), the graphite particles are uniformly mixed, the graphite is flaky, the surface is smooth, and no agglomeration phenomenon occurs; as can be seen from fig. 2 (b), the graphite surface has tiny spherical protrusions, and CMC uniformly wraps the graphite particles and PEO particles after melting in water, so as to play a role of stabilizing the structure, and graphite is uniformly fixed in the material.
And testing the I-V characteristic of the sensor, setting a voltage interval to be-2V by using an electrochemical workstation, fixing a sample on a heating table with a sampling step length of 0.01V, connecting a probe and the sensor, and starting a test program. The PEO-based implantable battery temperature sensors prepared in examples 1-3 were the same size, the same material, and only different thickness, and the I-V curves at room temperature are shown in fig. 3;
FIG. 3 is an I-V test curve of a PEO-based implantable battery temperature sensor, where curve 1 is the PEO-based implantable battery temperature sensor prepared in example 1, curve 2 is the PEO-based implantable battery temperature sensor prepared in example 2, and curve 3 is the PEO-based implantable battery temperature sensor prepared in example 3;
as can be seen from fig. 3: the resistance of the PEO-based implantable battery temperature sensor prepared in example 1 was 2859 Ω, the resistance of the PEO-based implantable battery temperature sensor prepared in example 2 was 1883 Ω, and the resistance of the PEO-based implantable battery temperature sensor prepared in example 3 was 933 Ω; the result shows that when the voltage is gradually increased, the resistance has no obvious fluctuation, which indicates that the resistance value of the sensor is stable.
FIG. 4 is a graph of I-V test curves for the PEO-based implantable battery temperature sensor prepared in example 1 at various temperatures, where the temperature is 30℃ for curve 1, 40℃ for curve 2, 50℃ for curve 3, 60℃ for curve 4, 70℃ for curve 5, and 80℃ for curve 6;
in conductive filler filled composites, the resistivity of the composite increases rapidly as the temperature approaches the melting point of the polymer matrix, which is known as the Positive Temperature Coefficient (PTC) effect; as the temperature increases, PEO expands, the number of graphite particles per unit area decreases, and the resistance increases, reflecting a decrease in the slope on the axis of voltage on the horizontal axis and current on the vertical axis, i.e., a decrease in conductance. As the temperature continues to rise, the PEO melts, the conductivity rises and the resistance drops, a phenomenon known as the Negative Temperature Coefficient (NTC) effect. The NTC effect may be due to the polymer structure relaxation leading to conductive chain reformation and the Gr particles re-forming clusters due to their free movement. Finally, the reorganization of the new conductive paths results in a decrease in resistance.
FIG. 5 is a plot of resistance versus temperature for the PEO-based implantable battery temperature sensor prepared in example 1;
as can be seen from fig. 5: between 0 and 440s, as the temperature gradually increases, thermal expansion of the PEO occurs from room temperature, rapidly increasing the electrical resistance and decreasing the current. At 82 ℃ thoroughly melted, 440s-1500s graphite particles gradually reform a new conductive network due to thermal motion, the resistance decreases, the current begins to increase, and the material resistance further decreases compared to the starting state due to the continuous formation of conductive chains by the newly formed graphite conductive network. When the heating is stopped, the resistance gradually recovers, the PEO particles are recovered to the original state again, the carbon chains of the graphite conductive network are broken up, the material resistance gradually decreases, and the material returns to the original position.
It can be seen through experiments that the temperature response of the material is consistent at different resistances, and the response to the same temperature is consistent under the same conditions. As shown in FIG. 5, as the temperature gradually increases, the sample is gradually heated to the molten zone, the resistance of the composite begins to increase and the PTC curve begins to change significantly due to the volume expansion caused by the PEO transitioning from the crystalline state to the amorphous state. Thermal expansion caused by the melting of the PEO grains dilutes the concentration of Gr particles in the amorphous region, resulting in an increase in the electrical resistance of the composite. When the temperature is raised to the melting point of PEO, the crystalline region melts completely and the volume fraction of the amorphous region reaches a maximum. Therefore, at this time the resistance reaches its maximum value and the temperature sensor reaches its saturation region. When heating is continued above the melting point of PEO, an NTC effect occurs. The NTC effect limits the popularization and application of polymer-based PTC materials to a large extent, and no satisfactory theory is currently presented to explain the NTC effect, but it is widely believed that the NTC effect may be due to the conductive chain reformation caused by the relaxation of the polymer structure, and the re-clustering of Gr particles due to their free movement. Finally, the reorganization of the new conductive paths results in a decrease in resistance. During cooling, the volume of PEO in the composite shrinks with temperature changes, mainly because most of the amorphous regions become crystalline regions again. At the same time, the conductive filler is discharged from the crystallized region due to the growth of crystal grains. Both of these factors increase the volume fraction of Gr particles in the amorphous region, and the formation of new conductive networks again leads to a decrease in resistance. When operated below the CMC melting temperature, PEO dominates the PTC behavior of the CMC/PEO binary composite and can maintain its physical morphology unchanged.
FIG. 6 is a graph of temperature cycling response test of the PEO-based implantable battery temperature sensor prepared in example 2;
fig. 6 is a graph showing a repetitive cycle test of a sensor, in which a PEO/CMC/Gr composite material rapidly expands after contacting a heat source, a part of a conductive path is cut off, resistance increases, current decreases to the bottom, and as shown in fig. 5, after stopping heating, the sensor gradually cools and begins to rebound to an origin, unlike a conventional PTC device using only a single polymer filled with a conductive filler, the device composite material is composed of a binary polymer, which can well solve the problem of insufficient temperature reproducibility in a single polymer system. The PTC effect of the binary composite materials employed in the present devices is due to the volumetric expansion caused by the melting of the PEO phase, which breaks the conductive network in the composite material when the temperature approaches the melting point of PEO, resulting in a dramatic increase in resistivity. When PEO is used only as a filler, it is difficult to return to the original form again after the PEO melts because PEO does not have excellent reproducibility. When CMC is added, due to the high melting point of CMC and PEO melting, CMC can act as a framework in the material, and when the temperature reaches the melting point of PEO, PEO becomes molten state while CMC remains unchanged in its physical form, and PEO returns to its original position after being cooled again. The presence of CMC is therefore able to maintain the external morphology of the entire temperature sensor so that it does not change due to PEO physical morphology changes.
FIG. 7 is a schematic representation of the implantation of the PEO-based implantable battery temperature sensor prepared in example 1, wherein (a) is the schematic representation of the implantation, (b) is the sensor fixed on top of the positive electrode, and (c) is the schematic representation of the finished soft pack after implantation;
FIG. 7 shows battery fabrication and implantation, where the sensor cannot be in contact with the electrolyte, as the electrolyte inside the battery can cause corrosion to the device; as shown in FIG. 7, when the sensor is implanted, polyimide film adhesive tape is wound on the surface of the sensor, so that electrolyte is prevented from corroding the sensing area and the wires. Cutting electrode plates with the same size by using a battery cutting machine, respectively using 5 soft package positive electrodes and negative electrodes, sequentially overlapping the battery positive electrodes and the negative electrodes by using a battery lamination machine, separating the battery positive electrodes and the negative electrodes by using a diaphragm, fixing the diaphragm by using a polyimide adhesive tape, tightly attaching the diaphragm, welding the electrode lugs by using a spot welding machine, attaching a sensor on the surface of the battery diaphragm, fixing and sealing, cutting two aluminum plastic films with the thickness of 6cm x 8cm, packaging the intersecting parts of the pin of the sensor and the edges of the aluminum plastic films by using an electrode lug adhesive, and then delivering the aluminum plastic films into a battery aluminum plastic film sealing machine for packaging, and delivering the sealed soft package side edges into a glove box for dropwise adding electrolyte. And (5) feeding the materials into a vacuum machine for standing for 5 minutes, and feeding the materials into a battery sealing machine for sealing under a vacuum environment. Standing for more than 24 hours; the electrolyte is prepared by mixing lithium hexafluorophosphate with a relative molecular mass of 1 mol into an organic solvent of which the ratio of EC to DC to EMC=1:1:1 (vol%) is 100 g.
Fig. 8 is a graph of the temperature response of the PEO-based implantable battery temperature sensor prepared in example 1 after implantation into a battery versus battery overcharge temperature.
FIG. 8 shows the response of a battery overcharge test sensor, as shown in FIG. 8, when the battery is charged with a large current, the temperature rises rapidly to generate heat, the sensor is heated, the resistance increases, and the current decreases; after 50s the sensor bottoms out, at which point the battery has reached a high temperature of 80 c as detected. The overcharged anode (deposited lithium) and the electrolyte solvent react vigorously at high temperatures. Over-charging can lead to Li + Migration to the surface of the negative electrode and precipitation into lithium dendrite, while the positive electrode material is severely delithiated, the structure is changed, and the positive electrode material is promoted to directly react with the electrolyte and release oxygen and reaction heat. After overcharging to some extent, lithium dendrites may pierce the separator, causing thermal runaway. The larger the overcharge ratio, the shorter the thermal runaway trigger time, and the lower the trigger temperature. When the temperature reaches the threshold value of the sensor, the current touches the bottom and can be used as an early warning point at the moment, and the alarm is sent out or the power supply of the battery is cut off by detecting the current resistance change of the sensor.
Claims (10)
1. The temperature sensor is characterized in that a temperature sensitive area of the sensor is made of PEO/CMC/Gr conductive composite materials, pins are made of silver wires, and two sides of the lower end of the temperature sensitive area are respectively connected with corners of the two pins.
2. The PEO-based implantable battery temperature sensor of claim 1, wherein the temperature sensitive region has a width of 1.4mm to 1.6mm, a length of 3.9mm to 4.1mm, and a thickness of 0.14mm to 0.2mm; the overall length of the sensor is 49.9-50.1 mm, the height of the corner of the pin is 1.9-2.1 mm, the inclination angle of the corner of the pin is 44.9-45.1 degrees, and the width between the two pins is 4.9-5.1 mm.
3. The PEO-based implantable battery temperature sensor of claim 1, wherein the preparation of the PEO/CMC/Gr conductive composite is accomplished by:
1. adding polyethylene oxide (PEO) into deionized water, and performing ultrasonic dispersion to obtain a polyethylene oxide solution; stirring the polyethylene oxide solution to obtain a colorless transparent viscous PEO solution;
2. uniformly grinding carboxymethyl cellulose and graphite powder in a mortar until the powder has no obvious chromatic aberration, thereby obtaining CMC/graphite powder;
3. adding CMC/graphite powder into PEO solution, adding deionized water for dilution, slowly stirring for a period of time, placing into a vacuum drying oven for standing, removing air mixed in colloid to obtain conductive slurry, layering and drawing by using the conductive slurry, and naturally air-drying to obtain a temperature-sensitive area of the sensor, namely the PEO/CMC/Gr conductive composite material.
4. A PEO-based implantable battery temperature sensor according to claim 3, wherein the mass to deionized water volume ratio of polyethylene oxide in step one is (0.5 g to 0.7 g) 10mL; the ultrasonic dispersion time in the first step is 20-30 min, and the ultrasonic dispersion power is 50-60W; and in the first step, stirring the polyethylene oxide solution for 2-3 hours.
5. A PEO-based implantable battery temperature sensor according to claim 3, characterized in that the mass ratio of carboxymethyl cellulose to graphite powder in step two is (0.5 g-0.7 g): (0.7 g-0.9 g).
6. A PEO-based implantable battery temperature sensor according to claim 3, wherein the mass to volume ratio of CMC/graphite powder, PEO solution and deionized water in step three is (1 g-2 g): (10 mL-12 mL): (15 mL-25 mL).
7. A PEO-based implantable battery temperature sensor according to claim 3, wherein the slow agitation in step three is at a speed of 250r/min to 300r/min for a period of 4h to 5h; and thirdly, placing the mixture into a vacuum drying oven for standing for 1-2 hours.
8. A method for preparing a PEO-based implantable battery temperature sensor according to claim 1, characterized in that the preparation of the sensor is specifically accomplished by the steps of:
1. preparing conductive slurry:
(1) adding polyethylene oxide into deionized water, and performing ultrasonic dispersion to obtain a polyethylene oxide solution; stirring the polyethylene oxide solution to obtain a colorless transparent viscous PEO solution;
(2) uniformly grinding carboxymethyl cellulose and graphite powder in a mortar until the powder has no obvious chromatic aberration, so as to obtain CMC/graphite powder;
(3) adding CMC/graphite powder into PEO solution, adding deionized water for dilution, slowly stirring for a period of time, placing into a vacuum drying oven for standing, and removing air mixed in colloid to obtain conductive slurry;
2. firstly, respectively printing two pins on two sides of the lower end of a temperature sensitive area on a polyimide film by using conductive silver paste, then drying and sintering, and then layering and drawing the conductive paste obtained in the step one on the polyimide film by using a microelectronic printer, and naturally air-drying to obtain the temperature sensitive area of the sensor; and finally covering a polyimide film above the temperature sensitive area to obtain the PEO-based implantable battery temperature sensor.
9. The method of preparing a PEO-based implantable battery temperature sensor according to claim 8, wherein the mass to deionized water volume ratio of the polyethylene oxide in step one (1) is (0.5 g to 0.7 g): 10mL; the ultrasonic dispersion time in the step one (1) is 20-30 min, and the ultrasonic dispersion power is 50-60W; stirring the polyethylene oxide solution in the step one (1) for 2-3 hours; the mass ratio of the carboxymethyl cellulose to the graphite powder in the step one (2) is (0.5 g-0.7 g) (0.7 g-0.9 g); the mass volume ratio of CMC/graphite powder, PEO solution and deionized water in the step one (3) is (1 g-2 g) (10 mL-12 mL) (15 mL-25 mL); the speed of the slow stirring in the step one (3) is 250 r/min-300 r/min, and the time of the slow stirring is 4 h-5 h; placing the mixture into a vacuum drying oven for standing for 1-2 h in the step one (3); and step two, the temperature of the drying and sintering is 200 ℃, and the time of the drying and sintering is 1-2 h.
10. Use of a PEO-based implantable battery temperature sensor according to claim 1, wherein the PEO-based implantable battery temperature sensor is implanted inside the battery for detecting the temperature inside the battery.
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