CN115047030A - Gas sensor for lithium battery thermal runaway early warning and preparation method thereof - Google Patents
Gas sensor for lithium battery thermal runaway early warning and preparation method thereof Download PDFInfo
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Abstract
The application discloses a gas sensor for early warning of lithium battery thermal runaway and a preparation method thereof, and the gas sensor for early warning of lithium battery thermal runaway comprises: a base and a bridge structure; the functional side of the substrate is provided with a heat dissipation cavity, and the bridge structure is arranged in the opening range of the cavity of the heat dissipation cavity in a hanging manner; the bridge structure comprises a first structural layer, a heating resistance layer and a second structural layer which are sequentially stacked along the direction far away from the heat dissipation cavity, wherein the first structural layer is close to the heat dissipation cavity. The gas sensor for the lithium battery thermal runaway early warning, which is prepared by the application, has the advantages of high response speed, high sensitivity, long service life, high anti-interference performance, low power consumption, small volume, simple and convenient preparation method and the like, and has higher application value.
Description
Technical Field
The application relates to the technical field of lithium battery state monitoring, in particular to a gas sensor for lithium battery thermal runaway early warning and a preparation method thereof.
Background
Along with a large amount of popularizations of lithium cell, lithium cell monitoring is especially important to battery operation safety, prevents to cause inevitable loss because the lithium cell became invalid, and the lithium cell then can release gases such as hydrogen, carbon monoxide, carbon dioxide and methane in the inefficacy earlier stage, because hydrogen has good thermal conductance principle, consequently through monitoring the hydrogen concentration of lithium cell release, can realize the state control to the lithium cell.
The traditional gas sensor generally adopts a catalytic combustion principle, a palladium resistance principle, an electrochemical principle, a metal oxide semiconductor principle, a thermal conduction principle and the like to realize the monitoring function of the external environment. Specifically, the sensor realized by utilizing the catalytic combustion principle needs to be participated by oxygen, and the catalyst is easy to lose efficacy due to organic silicon poisoning in the lithium battery pack; the sensor realized by using the palladium resistance principle has extremely low response speed, and the hydrogen concentration value can be obtained usually within minutes or even tens of minutes; the sensor realized by the electrochemical principle has short service life and needs to be replaced frequently; the principle of the metal oxide semiconductor is easy to be interfered and misreport, the service life of the gas sensitive material is generally not more than 3 years, the response time of the existing sensor utilizing the thermal conductivity principle also needs tens of seconds, and the quick early warning effect is not enough.
Therefore, an improved gas sensor solution is needed to solve the above technical problems.
Disclosure of Invention
In order to solve the problems in the prior art, the embodiment of the application provides a technical scheme of a gas sensor for early warning of thermal runaway of a lithium battery and a preparation method thereof, wherein the technical scheme is as follows:
in one aspect, a gas sensor for early warning of thermal runaway of a lithium battery is provided, which comprises a substrate and a bridge structure;
a heat dissipation cavity is arranged on the functional side of the substrate, and the bridge structure is arranged in the range of the cavity opening of the heat dissipation cavity in a hanging manner;
the bridge structure comprises a first structural layer, a heating resistance layer and a second structural layer which are sequentially stacked in the direction away from the heat dissipation cavity, wherein the first structural layer is close to the heat dissipation cavity.
Furthermore, the gas sensor for the early warning of the thermal runaway of the lithium battery also comprises at least one environment temperature sensing structure arranged on the substrate, and the environment temperature sensing structure is arranged adjacent to the bridge-type structure;
the environment temperature sensing structure comprises a third structure layer, a temperature resistance layer and a fourth structure layer which are sequentially stacked along the direction far away from the substrate.
Furthermore, the environment temperature sensing structure further comprises at least two pad structures, and two ends of the heating resistance layer in the bridge structure are respectively connected with the at least two pad structures;
the pad structure is arranged on one side of the third structure layer far away from the substrate.
Further, the pad structure includes a resistance pad layer and a metal protection layer, the resistance pad layer is disposed on the third structure layer, and the metal protection layer is disposed on the resistance pad layer.
Furthermore, two ends of the temperature resistance layer are respectively connected with the at least two pad structures.
Further, the heating resistor layer is arranged in a serpentine on the first structural layer.
Further, the thickness of the heating resistance layer is 0.1 um-2 um.
Further, the heating resistance layer, the temperature resistance layer, the first structural layer and the second structural layer are all formed through annealing treatment, the temperature of the annealing treatment is greater than or equal to 400 ℃, and the time of the annealing treatment is greater than or equal to 4 h.
Further, the material of the metal protection layer includes at least one of gold, platinum, silver and aluminum.
Further, the material of the first structure layer includes any one or more of silicon oxide, silicon nitride, aluminum oxide, phosphosilicate glass and borosilicate glass.
In another aspect, a method for preparing the gas sensor for warning the thermal runaway of the lithium battery is provided, which includes the following steps:
providing a substrate;
performing film deposition on the substrate to form a heat insulating layer on the substrate;
depositing a metal film on one side of the heat insulating layer far away from the substrate to form a first metal film;
etching the first metal film to form a temperature resistance layer, a heating resistance layer and a resistance pad layer at preset positions;
performing thin film deposition on the temperature resistance layer and the heating resistance layer at one side far away from the heat insulation layer to form a protection layer;
depositing a metal film on one side of the resistance pad layer, which is far away from the heat-insulating layer, so as to form a second metal film;
carrying out patterning treatment and etching treatment on the protective layer to form a bridge structure;
etching the area corresponding to the bridge structure on the substrate to form a heat dissipation cavity, so as to obtain the gas sensor for early warning of thermal runaway of the lithium battery; the bridge structure is arranged at the opening of the cavity of the heat dissipation cavity in a suspended manner.
The application provides a gas sensor for early warning of thermal runaway of lithium battery and a preparation method thereof, and the gas sensor has the following technical effects:
1. the gas sensor for the lithium battery thermal runaway early warning, which is prepared by the application, has the advantages of high response speed, high sensitivity, long service life, high anti-interference performance, low power consumption, small volume, simple and convenient preparation method and the like, and has higher application value.
2. A gas sensor for early warning of lithium cell thermal runaway in this application is through setting up heat dissipation chamber and unsettled bridge type structure that sets up on the heat dissipation chamber, so that the gas sensor who uses for the early warning of lithium cell thermal runaway has good adiabatic characteristic, reduce gas sensor's consumption, improve gas sensor's interference killing feature, and simultaneously, the detection face of the resistive heating layer of still being convenient for all exposes in the gaseous environment that awaits measuring, increase the contact range to hydrogen detection, so that resistive heating layer contacts hydrogen as far as, and then improve the sensitivity of the gas sensor who is used for the early warning of lithium cell thermal runaway.
3. The gas sensor prepared in the application is utilized to detect gas, a chemical reaction process is avoided, the thermal stability state can be achieved within hundred milliseconds, and the response speed of the gas sensor for lithium battery thermal runaway early warning can be obviously improved.
4. A gas sensor for early warning of lithium cell thermal runaway in this application cooperates high accuracy measurement circuit, can detect out 0.05% concentration hydrogen at least, has broken through the limit that the gas sensor that the tradition was used for early warning of lithium cell thermal runaway detects hydrogen concentration, and then enlarges the scope value that detects hydrogen concentration to improve the detection precision of the gas sensor who is used for early warning of lithium cell thermal runaway, have wider application scene.
5. The gas sensor prepared in the application is utilized to detect gas, and materials which are easy to be poisoned or interfered by other gases such as catalysts, gas-sensitive materials and the like are not used, so that the service life of the gas sensor is effectively prolonged.
6. Utilize the gas sensor who prepares in this application to carry out the in-process that detects to gas, all not use consumptive material such as chemical reagent and chemical reaction material, have characteristics such as stable performance and long service life.
7. This application is through setting up first structural layer and second structural layer at heating resistor layer both ends face to and set up third structural layer and fourth structural layer at the both ends face of temperature resistance layer, with the stability of reinforcing heating resistor layer and temperature resistance layer, and then make gas sensor have anti-oxidant, anti sublimation and anti electron migration's characteristic.
8. The heating resistor layer, the temperature resistance layer, the first structural layer and the second structural layer which are arranged in the application are all formed through annealing treatment, and the heating resistor layer, the temperature resistance layer, the first structural layer and the second structural layer are made of high-temperature-resistant materials, so that the stability of detection of the gas sensor in a high-temperature environment is enhanced.
9. The preparation method of the gas sensor for the early warning of the thermal runaway of the lithium battery is simple to operate, low in cost and convenient for mass production.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a gas sensor for warning of thermal runaway of a lithium battery according to an embodiment of the present disclosure;
fig. 2 is a first top view of a gas sensor for warning of thermal runaway of a lithium battery according to an embodiment of the present disclosure;
fig. 3 is a second top view of the gas sensor for warning of thermal runaway of a lithium battery according to the embodiment of the present application;
fig. 4 is a third top view of the gas sensor for warning of thermal runaway of a lithium battery according to the embodiment of the present application;
fig. 5 is a fourth top view of the gas sensor for warning of thermal runaway of a lithium battery according to the embodiment of the present application;
fig. 6 is a schematic diagram illustrating a relationship between a resistance value and a response time of a heating resistor layer of the gas sensor for warning thermal runaway of a lithium battery provided in the embodiment of the present application under the same hydrogen concentration;
fig. 7 is a schematic flowchart of a manufacturing method of a gas sensor for warning of thermal runaway of a lithium battery according to an embodiment of the present disclosure;
wherein the reference numerals correspond to: 100-a substrate; 101-a heat dissipation cavity; a 200-bridge type structure; 201-a first structural layer; 202-a heating resistor layer; 203-a second structural layer; 301-a third structural layer; 302-temperature resistive layer; 303-a fourth structural layer; 400-pad structure; 401-resistance pad layer; 402-metal protective layer.
Detailed Description
The technical solutions in the embodiments of the present application will be described clearly and completely with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It should be noted that the terms "first," "second," and the like in the description and claims of this application and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It should be understood that the data so used may be interchanged under appropriate circumstances such that embodiments of the application described herein may be implemented in sequences other than those illustrated or described herein.
Example 1:
referring to fig. 1 to 6, the following describes in detail the gas sensor for warning of thermal runaway of a lithium battery with reference to fig. 1 to 6, it should be noted that in this embodiment, since hydrogen has good thermal conductivity, the state of the lithium battery is monitored by monitoring the concentration of hydrogen released from the lithium battery, and specifically, the gas sensor for warning of thermal runaway of a lithium battery includes: a substrate 100 and a bridge structure 200;
wherein, the functional side of the substrate 100 is provided with a heat dissipation cavity 101, and the bridge structure 200 is suspended in the cavity opening range of the heat dissipation cavity 101; the bridge structure 200 includes a first structural layer 201, a heating resistor layer 202, and a second structural layer 203, which are sequentially stacked in a direction away from the heat dissipation cavity 101, where the first structural layer 201 is disposed close to the heat dissipation cavity 101.
In the embodiment of the present application, the functional side of the substrate 100 is a side of the substrate 100 facing the bridge structure 200, that is, the heat dissipation cavity 101 is disposed on a side of the substrate 100 facing the bridge structure 200, the bridge structure 200 is disposed in a suspended manner on the functional side of the substrate 100, and the heat dissipation cavity 101 is disposed on a side of the substrate 100 facing the bridge structure 200, so that the detection surfaces of the resistive heating layers 202 in the bridge structure 200 are exposed to the gas environment to be detected, the contact range of the gas detection is increased, so that the resistive heating layers are in contact with the gas as much as possible, the sensitivity of the gas sensor for the lithium battery thermal runaway pre-warning is improved, the response speed to hydrogen is increased, meanwhile, the bridge structure 200 is suspended in an open range of the cavity of the heat dissipation cavity 101, so as to dissipate heat generated by the gas sensor for the lithium battery thermal runaway pre-warning during the hydrogen detection, and greatly reduce the heat capacity of the gas sensor for the lithium battery thermal runaway pre-warning, the gas sensor for the early warning of the thermal runaway of the lithium battery has the characteristic of quick response and higher application value.
In a specific embodiment, an experiment is performed on the response speed of the gas sensor for the early warning of the thermal runaway of the lithium battery prepared in the present application, and an experimental result is shown in fig. 6, where an abscissa of the gas sensor is response time and an ordinate of the gas sensor is a resistance value of the heating resistor layer 202, as can be seen from fig. 6, when the response time is 0.06 second, the heating resistor layer 202 reaches a thermal stable state, so that the detection of the hydrogen concentration in the current environment is facilitated, and then the response speed of the gas sensor for the early warning of the thermal runaway of the lithium battery can be significantly improved, the monitoring of the thermal runaway state of the lithium battery is more effectively and reliably realized, and the safety performance of the lithium battery is improved.
Specifically, the bridge structure 200 may serve as a sensing structure for detecting hydrogen concentration, for example, the hydrogen concentration of an environment where a gas sensor currently used for lithium battery thermal runaway early warning is located is sensed through a heating resistor layer 202 in the bridge structure 200, wherein a principle that the heating resistor layer 202 in the bridge structure 200 detects hydrogen is a principle that hydrogen has high heat conduction, and presence of hydrogen is sensed, so that the gas sensor used for lithium battery thermal runaway early warning determines whether a detected object is about to be in a failure state according to the detected hydrogen concentration, and monitoring of the detected object is achieved.
In practical application, the heating resistor layer 202 is used to provide a heat source for the gas sensor, so as to determine a hydrogen concentration value corresponding to a temperature change value according to the temperature change value of the heating resistor layer 202, for example, when the gas sensor for the early warning of the thermal runaway of the lithium battery detects the hydrogen concentration, the heating resistor layer 202 is required to provide the heat source, under a hydrogen-free environment, the temperature of the heating resistor layer 202 is kept unchanged, when hydrogen exists, because the thermal conductivity of the hydrogen is extremely high, the temperature of the heating resistor layer 202 is rapidly reduced, so that the concentration of the hydrogen in the current environment is determined according to the temperature change value of the heating resistor layer 202, so as to realize the detection of the hydrogen, it should be noted that the gas sensor for the early warning of the thermal runaway of the lithium battery prepared by the application can detect the hydrogen with the lowest concentration of 0.05% on the premise of being matched with a high-precision measurement circuit, the limit of the traditional gas sensor for the lithium battery thermal runaway early warning for detecting the hydrogen concentration is broken through, the range value of the detected hydrogen concentration is further enlarged, the detection precision of the gas sensor for the lithium battery thermal runaway early warning is improved, a chemical reaction process does not exist in the process of detecting the gas, and the gas sensor has a wide application scene.
Specifically, the heating resistor layer 202 may be coupled to an external control circuit, and coupled to the external control circuit through the heating resistor layer 202, so that the heating resistor layer 202 provides a heat source for the gas sensor for the early warning of thermal runaway of the lithium battery, where the external control circuit is configured to provide constant current sources, constant voltage sources, or constant resistance sources with different preset values.
It should be noted that, in the process of detecting gas by using the gas sensor prepared in the embodiment of the present application, materials which are easily poisoned or interfered by other gases, such as a catalyst, a gas sensitive material, etc., are not used, so that the service life of the gas sensor is effectively prolonged; in the process of detecting the gas by using the gas sensor prepared by the embodiment of the application, consumable substances such as chemical reagents, chemical reaction materials and the like are not used, the detection process of the hydrogen concentration is realized only according to the corresponding relation between the temperature change value of the heating resistance layer 202 and the hydrogen concentration, and the gas sensor has the characteristics of stable performance, high anti-interference performance, long service life and the like.
In an embodiment, the substrate 100 may be a silicon substrate, or may be other substrate materials, which is not limited herein.
In an optional embodiment, the gas sensor for early warning of thermal runaway of a lithium battery further comprises at least one environment temperature sensing structure disposed on the substrate, the environment temperature sensing structure is disposed adjacent to the bridge-type structure 200, wherein the environment temperature sensing structure comprises a third structure layer 301, a temperature resistance layer 302 and a fourth structure layer 303 which are sequentially stacked in a direction away from the substrate 100.
In the embodiment of the present application, the first structural layer 201 and the third structural layer 301 are thin film layers made of the same predetermined material, and the second structural layer 203 and the fourth structural layer 303 are thin film layers made of the same predetermined material, for example, the first structural layer 201 has good thermal insulation property in the present application, and also has a function of supporting and protecting the heating resistor layer 202, specifically, on one hand, the first structural layer 201 is located between the substrate 100 and the heating resistor layer 202, and is used for isolating the substrate 100 from the heating resistor layer 202, so as to prevent the substrate 100 and the heating resistor layer 202 from transferring heat, and further the heat of the heating resistor layer 202 cannot be transferred to the substrate 100, so as to effectively reduce the heat capacity of the gas sensor for early warning thermal runaway of the lithium battery, and thus greatly improve the thermal response speed of the gas sensor for early warning thermal runaway of the lithium battery, on the other hand, the first structural layer 201 is used for supporting and protecting the heating resistor layer 202, the heating resistor layer 202 is a metal thin film resistance wire, and the structure is fragile, so that the heating resistor layer 202 is easily damaged.
The heating resistor 201 can be used as a temperature measuring resistor, and the working temperature can be represented according to different resistance values at different temperatures, so that the current hydrogen concentration value can be represented according to the difference value of the thermal conductivities of hydrogen and air.
Further, the third structural layer 301 is used to support and protect the temperature resistance layer 302, the temperature resistance layer 302 is a metal thin film resistance wire, the structure is fragile, and it is very easy to damage the temperature resistance layer 302, the temperature resistance layer 302 is used to detect an ambient temperature value, and then the temperature change value of the heating resistance layer 202 is subjected to error correction according to the ambient temperature value, so as to determine a more accurate hydrogen concentration value, so as to realize a hydrogen detection process, if the temperature resistance layer 302 is damaged, the ambient temperature cannot be sensed, when the ambient temperature changes sharply, the heating resistance layer 202 has a larger error when detecting the hydrogen concentration value, and once hydrogen leakage occurs, a serious safety accident may be caused.
It should be noted that, in the gas sensor prepared by the present application, the first structural layer 201 and the second structural layer 203 are disposed on two end faces of the heating resistor layer 202, and the third structural layer 301 and the fourth structural layer 303 are disposed on two end faces of the temperature resistor layer 302, so as to enhance the stability of the heating resistor layer 202 and the temperature resistor layer 302, and further, the gas sensor has the characteristics of oxidation resistance, sublimation resistance, and electromigration resistance.
In an alternative embodiment, the heating resistor layer 202, the temperature resistor layer 302, the first structural layer 201 and the second structural layer 203 are all formed by annealing treatment, wherein the temperature of the annealing treatment is greater than or equal to 400 ℃, and the time of the annealing treatment is greater than or equal to 4 h.
In the embodiment of the present application, the heating resistor layer 202, the temperature resistor layer 302, the first structural layer 201, and the second structural layer 203 are all formed by annealing, and then the heating resistor layer 202, the temperature resistor layer 302, the first structural layer 201, and the second structural layer 203 are all made of high temperature resistant materials, so as to adapt to the high temperature annealing process, and further enhance the stability of the gas sensor in detection in a high temperature environment.
It should be noted that, the lateral distance between the temperature resistance layer 302 and the heat dissipation cavity 101 is greater than or equal to the preset distance, so as to ensure the accuracy of the measured temperature variation value.
In an alternative embodiment, the ambient temperature sensing structure further comprises at least two pad structures 401, two ends of the heating resistor layer 202 in the bridge structure 200 are respectively connected to the at least two pad structures 400,
wherein the pad structure 400 is disposed on a side of the third structure layer 301 facing away from the substrate 100.
In an alternative embodiment, the pad structure 400 includes a resistance pad layer 401 and a metal protection layer 402, the resistance pad layer 401 is disposed on the third structure layer 301, and the metal protection layer 402 is disposed on the resistance pad layer 401.
In an alternative embodiment, the two ends of the temperature resistive layer 302 are connected to at least two pad structures 400, respectively.
In the embodiment of the present application, two ends of the heating resistor layer 202 in the bridge structure 200 are respectively connected to different pad structures 400, on one hand, the heating resistor layer 202 can be coupled to an external control circuit through the resistor pad layer 401 in the pad structures 400, and on the other hand, the bridge structure 200 is supported to be suspended on the heat dissipation cavity 101, thereby increasing the stability of the bridge structure 200.
The two ends of the temperature resistance layer 302 are also connected to different pad structures 400, wherein the pad structure 400 for connecting the temperature resistance layer 302 is different from the pad structure 400 for connecting the heating resistance layer 202, specifically, please refer to fig. 2-5, and it can be seen from fig. 2-5 that the position and shape of the resistance pad layer 401 in the pad structure 400 can be determined according to the layout that the bridge structure 200 is suspended on the heat dissipation cavity 101, so that the bridge structure 200 can be stably suspended on the heat dissipation cavity 101, and the detection stability of the gas sensor for warning the thermal runaway of the lithium battery is increased.
Specifically, the layout of the bridge-type structure 200 suspended on the heat dissipation cavity 101 may include the layouts shown in fig. 2-5, and as can be seen from fig. 2, the heating resistor layer 202 in the bridge-type structure 200 is arranged on the diagonal corner of the heat dissipation cavity 101, so as to increase the contact area between the gas sensor for the early warning of the thermal runaway of the lithium battery and hydrogen, and further improve the sensitivity of the gas sensor for the early warning of the thermal runaway of the lithium battery; as can be seen from fig. 3, the heating resistor layer 202 in the bridge structure 200 is arranged in the middle of the heat dissipation cavity 101, and the heating resistor layer 202 is arranged in a serpentine line along the connecting line perpendicular to the two pad structures 400 connecting the temperature resistor layers 302; as can be seen from fig. 4, the heating resistor layer 202 in the bridge structure 200 is arranged on a diagonal of the heat dissipation cavity 101, and the first structural layer 201 is further present along the other diagonal of the heat dissipation cavity 101, and the temperature resistor layer 302 is half-enclosed on both sides of the heat dissipation cavity 101, so as to increase the stability of the bridge structure 200 without changing the response speed of the gas sensor for lithium battery thermal runaway pre-warning, and further improve the accuracy of detecting the hydrogen concentration by the gas sensor for lithium battery thermal runaway pre-warning; as can be seen from fig. 5, the heating resistor layer 202 in the bridge structure 200 is disposed on one side of the heat dissipation cavity 101, and the first structural layer 201 with a preset curve shape is further disposed on the heat dissipation cavity 101, so as to increase the stability of the bridge structure 200, and at the same time, increase the contact area for detecting hydrogen, thereby improving the sensitivity of the gas sensor for the early warning of thermal runaway of the lithium battery.
In an alternative embodiment, the heating resistor layer 202 is arranged in a serpentine pattern on the first structural layer 201.
In one embodiment, the first structural layer 201 is disposed on the heat dissipation chamber 101 in a serpentine manner, and the second structural layer 203 is disposed on the heating resistor layer 202 in a serpentine manner, so that the bridge structure 200 is disposed in a serpentine manner to improve the accuracy of the heating resistor layer 202 in detecting the hydrogen concentration.
Specifically, the heating resistor layer 202 is designed to be a serpentine line and arranged on the first structural layer 201, so that in the gas sensor for the early warning of the thermal runaway of the lithium battery with limited volume and space, the resistance value of the heating resistor layer 202 is increased to a preset resistance value, and in a limited length, the resistance value of the heating resistor layer 202 arranged in the serpentine line is greater than that of the heating resistor layer 202 arranged in a straight line, so that the accuracy of detecting hydrogen by the gas sensor for the early warning of the thermal runaway of the lithium battery is remarkably improved.
In an alternative embodiment, the heating resistor layer 202 has a thickness of 0.1um to 2 um.
Further, the thickness of the heating resistor layer 202 can also be 0.1um ~ 0.5um, 0.1um ~ 1um, 0.5um ~ 1.5um, 0.5um ~ 2um, 1um ~ 2um and 1.5um ~ 2um etc., preferably, the thickness of the heating resistor layer 202 is 0.5um ~ 1.5um to support the bridge type structure 200 and hang in the air on the heat dissipation cavity 101, increase the steadiness of the bridge type structure 200.
It should be noted that the thickness of the temperature resistance layer 302 is equal to the thickness of the heating resistance layer 202, and is not described herein again.
In another embodiment, the thickness of the first structural layer 201 may be 0.1um to 5 um.
Further, the thickness of the first structural layer 201 can also be 0.1 um-2 um, 0.1 um-4 um, 0.5 um-3 um, 1 um-5 um, 2 um-4 um, 3 um-5 um, etc., preferably, the thickness of the first structural layer 201 is 0.5 um-3 um, so as to support the heating resistance layer 202 in the bridge structure 200 and increase the stability of the bridge structure 200.
It should be noted that the thickness of the third structural layer 301 is equal to the thickness of the first structural layer 201, and is not described herein again.
In another embodiment, the thickness of the second structure layer 203 may be 0.05um to 5 um.
Further, the thickness of the second structure layer 203 can also be 0.05um to 2um, 0.05um to 1um, 0.05um to 1.5um, 0.2um to 1um, 1.5um to 5um, 2um to 5um, etc., preferably, the thickness of the second structure layer 203 is 0.05um to 1.5um, so as to protect the heating resistor layer 202 in the bridge structure 200, and ensure that the heating resistor layer 202 is not exposed in the air.
It should be noted that the thickness of the fourth structure layer 303 is equal to the thickness of the second structure layer 203, and is not described herein again.
In another embodiment, the thickness of the resistance pad layer 401 may be 0.1um to 2 um.
Further, the thickness of resistance pad layer 401 can also be 0.1um ~ 0.5um, 0.1um ~ 1um, 0.5um ~ 1.5um, 0.5um ~ 2um, 1um ~ 2um and 1.5um ~ 2um etc. preferably, the thickness of resistance pad layer 401 is 0.5um ~ 1.5um to support bridge type structure 200 and suspend on heat dissipation chamber 101, increase bridge type structure 200's steadiness.
In another embodiment, the thickness of the metal protection layer 402 is 0.1um to 1 um.
Further, the thickness of metal protection layer 402 still can be 0.1um ~ 0.5um, 0.1um ~ 1um, 0.5um ~ 1um, 0.2um ~ 0.9um and 0.2um ~ 0.5um etc. preferably, the thickness of metal protection layer 402 is 0.5um ~ 1um to resistance welding dish layer 401, avoid resistance welding dish layer 401 to receive the influence of other factors, and lead to being used for the gas sensor damage of lithium cell thermal runaway early warning.
Through the thickness description of the heating resistor layer 202, the temperature resistor layer 302, the resistance pad layer 401, the metal protection layer 402, the first structural layer 201, the second structural layer 203, the third structural layer 301 and the fourth structural layer 303, it can be known that the volume of the gas sensor for the early warning of the lithium battery thermal runaway is small, so that the sensitivity of the gas sensor for the early warning of the lithium battery thermal runaway is improved. It should be noted that, the thickness of the substrate 100 is not specifically defined in the present application, and the application condition of the substrate 100 may be satisfied.
In an alternative embodiment, the material of the metal protection layer 402 includes, but is not limited to, at least one of gold, platinum, silver and aluminum.
In an alternative embodiment, the materials of the first structural layer 201 and the third structural layer 301 include, but are not limited to, any one or more of silicon oxide, silicon nitride, aluminum oxide, phosphosilicate glass, and borosilicate glass.
In another embodiment, the material of the heating resistor layer 202 includes, but is not limited to, any one or more of platinum, nickel, tungsten, aluminum, gold, rhenium, and chromium.
In another embodiment, the materials of the second structure layer 203 and the fourth structure layer 303 include, but are not limited to, any one or more of silicon oxide, silicon nitride, aluminum oxide, phosphosilicate glass, and borosilicate glass.
In practical application, the monitoring process for monitoring the lithium battery state by utilizing the gas sensor for the lithium battery thermal runaway early warning is as follows:
in the process of monitoring the lithium battery by using the gas sensor for the early warning of the thermal runaway of the lithium battery, if the lithium battery is about to fail, a large amount of hydrogen is released, the hydrogen released by the lithium battery enters the heat dissipation cavity 101 in the gas sensor for the early warning of the thermal runaway of the lithium battery, and the temperature of the heating resistance layer 202 is rapidly reduced due to the extremely high thermal conductivity of the hydrogen, so that the hydrogen concentration in the current environment is determined according to the temperature change value of the heating resistance layer 202 and further based on the corresponding relation between the temperature change value of the heating resistance layer 202 and the hydrogen concentration, thereby realizing the state monitoring of the lithium battery,
according to the technical scheme, the method has the following advantages:
1. the gas sensor for the lithium battery thermal runaway early warning, which is prepared by the application, has the advantages of high response speed, high sensitivity, long service life, high anti-interference performance, low power consumption, small volume, simple and convenient preparation method and the like, and has higher application value.
2. A gas sensor for early warning of lithium cell thermal runaway in this application is through setting up heat dissipation chamber and unsettled bridge type structure that sets up on the heat dissipation chamber, so that the gas sensor who uses for the early warning of lithium cell thermal runaway has good adiabatic characteristic, reduce gas sensor's consumption, improve gas sensor's interference killing feature, and simultaneously, the detection face of the resistive heating layer of still being convenient for all exposes in the gaseous environment that awaits measuring, increase the contact range to hydrogen detection, so that resistive heating layer contacts hydrogen as far as, and then improve the sensitivity of the gas sensor who is used for the early warning of lithium cell thermal runaway.
3. The gas sensor prepared in the application has no chemical reaction process in the process of detecting gas, and can reach a thermal stable state in hundreds of milliseconds, so that the response speed of the gas sensor for the lithium battery thermal runaway early warning can be obviously improved.
4. A gas sensor for early warning of lithium cell thermal runaway in this application cooperates high accuracy measurement circuit, can detect out 0.05% concentration hydrogen minimum, has broken through the limit that the gas sensor that the tradition was used for early warning of lithium cell thermal runaway detected hydrogen concentration, and then enlarges the scope value that detects gas concentration to improve the detection precision of the gas sensor who is used for early warning of lithium cell thermal runaway, have wider application scene.
5. The gas sensor prepared in the application is utilized to detect gas, and materials which are easy to be poisoned or interfered by other gases such as catalysts, gas-sensitive materials and the like are not used, so that the service life of the gas sensor is effectively prolonged.
6. Utilize the gas sensor who prepares in this application to carry out the in-process that detects to gas, all not use consumptive material such as chemical reagent and chemical reaction material, have characteristics such as stable performance and long service life.
7. This application is through setting up first structural layer and second structural layer at heating resistor layer both ends face to and set up third structural layer and fourth structural layer at the both ends face of temperature resistance layer, with the stability of reinforcing heating resistor layer and temperature resistance layer, and then make gas sensor have anti-oxidant, anti sublimation and anti electron migration's characteristic.
8. The heating resistor layer, the temperature resistance layer, the first structural layer and the second structural layer which are arranged in the application are all formed through annealing treatment, and the heating resistor layer, the temperature resistance layer, the first structural layer and the second structural layer are made of high-temperature-resistant materials, so that the stability of detection of the gas sensor in a high-temperature environment is enhanced.
Example 2:
the embodiment of the present application further provides a method for preparing the gas sensor for warning of thermal runaway of a lithium battery, please refer to fig. 7, which is a schematic flow chart of the method for preparing the gas sensor for warning of thermal runaway of a lithium battery according to the embodiment of the present application, and the method includes the following steps:
s1: a substrate 100 is provided.
In the practice of the present application, the substrate 100 may be a silicon substrate, or may be other substrate materials, which are not limited herein.
S2: the substrate 100 is subjected to thin film deposition to form a heat insulating layer on the substrate 100.
In this application embodiment, the thickness of heat insulation layer still can be 0.1um ~ 2um, 0.1um ~ 4um, 0.5um ~ 3um, 1um ~ 5um, 2um ~ 4um and 3um ~ 5um etc. preferably, the thickness of heat insulation layer is 0.5um ~ 3um, and the heat insulation layer can regard as the heat resistance layer 202 and the heat insulation layer of basement 100, still can be used to support heat resistance layer 202 to bridge type structure 200 is unsettled at heat dissipation chamber 101 cavity opening part.
The first structural layer 201 and the third structural layer 301 are both heat insulating layers, and the thickness of the first structural layer 201 and the thickness of the third structural layer 301, and the material of the first structural layer 201 and the material of the third structural layer 301 are the same.
It should be noted that the thin film deposition may include one of thermal oxidation, Plasma Enhanced Chemical Vapor Deposition (PECVD), Low Pressure Chemical Vapor Deposition (LPCVD), electron beam evaporation, magnetron sputtering, screen printing, spin-on sintering, and atomic layer deposition, and the method of using the thin film deposition may be determined according to specific practical situations, and is not limited in particular.
S3: and performing metal film deposition on the side of the heat insulating layer far away from the substrate 100 to form a first metal film.
S4: the first metal thin film is subjected to etching treatment, and the temperature resistance layer 302, the heating resistance layer 202, and the resistance pad layer 401 are formed on predetermined positions.
In the embodiment of the present application, the temperature resistance layer 302, the heating resistance layer 202, and the resistance pad layer 401 are all formed by patterning the first metal film, where the patterning refers to manufacturing a structure with a specific pattern by using a photolithography and etching method, a photolithography and peeling method, or a screen printing method.
Specifically, the thickness of the heating resistor layer 202 is 0.1um ~ 2um, furthermore, the thickness of the heating resistor layer 202 can also be 0.1um ~ 0.5um, 0.1um ~ 1um, 0.5um ~ 1.5um, 0.5um ~ 2um, 1um ~ 2um and 1.5um ~ 2um etc., preferably, the thickness of the heating resistor layer 202 is 0.5um ~ 1.5um, so that the supporting bridge structure 200 is unsettled on the heat dissipation cavity 101, increase the steadiness of the bridge structure 200.
In another embodiment, the thickness of the temperature resistance layer 302 is 0.1um to 2um, further, the thickness of the temperature resistance layer 302 can also be 0.1um to 0.5um, 0.1um to 1um, 0.5um to 1.5um, 0.5um to 2um, 1um to 2um and 1.5um to 2um, etc., preferably, the thickness of the temperature resistance layer 302 is 0.5um to 1.5um, in order to detect the inside ambient temperature of the gas sensor for the early warning of the lithium battery thermal runaway, in order to ensure the safety of the gas sensor for the early warning of the lithium battery thermal runaway.
In another embodiment, the thickness of the resistance pad layer 401 may be 0.1um to 2um, further, the thickness of the resistance pad layer 401 may also be 0.1um to 0.5um, 0.1um to 1um, 0.5um to 1.5um, 0.5um to 2um, 1um to 2um, 1.5um to 2um, and the like, preferably, the thickness of the resistance pad layer 401 is 0.5um to 1.5um, so as to support the bridge structure 200 suspended on the heat dissipation cavity 101, and increase the stability of the bridge structure 200.
It should be noted that the resistance pad layer 401 is used to connect the temperature resistance layer 302 with an external control circuit, so as to enable the external control circuit to provide a constant voltage source, a constant current source, or a constant resistance source for the temperature resistance layer 302, and the resistance pad layer 401 is also used to connect the heating resistance layer 202 with the external control circuit, so as to enable the external control circuit to provide a constant voltage source, a constant current source, or a constant resistance source for the heating resistance layer 202.
S5: thin film deposition is performed on the sides of the temperature resistive layer 302 and the heating resistive layer 202 away from the insulator layer to form a protective layer.
In the embodiment of the present application, the protection layer is used to isolate the temperature resistance layer 302 and the heating resistance layer 202 from air, so as to prevent the temperature resistance layer 302 and the heating resistance layer 202 from being exposed to air, and to enable the temperature resistance layer 302 and the heating resistance layer 202 to react with oxygen in air, thereby protecting the temperature resistance layer 302 and the heating resistance layer 202.
Specifically, the thickness of protective layer can be 0.05um ~ 5um, furtherly, the thickness of protective layer still can be 0.05um ~ 2um, 0.05um ~ 1um, 0.05um ~ 1.5um, 0.2um ~ 1um, 1.5um ~ 5um and 2um ~ 5um etc. preferably, the thickness of protective layer is 0.05um ~ 1.5um to heating resistor layer 202 and temperature resistance layer 302 in the protection bridge type structure 200, ensure that heating resistor layer 202 and temperature resistance layer 302 can not expose in the air.
The second structural layer 203 and the fourth structural layer 303 are both protective layers, and the thicknesses of the second structural layer 203 and the fourth structural layer 303, and the materials of the second structural layer 203 and the fourth structural layer 303 are the same.
S6: and depositing a metal film on the side of the resistance pad layer 401 far away from the heat-insulating layer to form a second metal film.
Specifically, second metallic film's thickness is 0.1um ~ 1um, furtherly, second metallic film's thickness still can be for 0.1um ~ 0.5um, 0.1um ~ 1um, 0.5um ~ 1um, 0.2um ~ 0.9um and 0.2um ~ 0.5um etc, preferably, second metallic film's thickness is 0.5um ~ 1um, so that protection resistance welding dish layer 401, avoid resistance welding dish layer 401 to receive the influence of other factors, and lead to the gas sensor who is used for lithium cell thermal runaway early warning to damage.
The metal protection layer 402 is a second metal film, and the material and thickness of the metal protection layer 402 are the same as those of the second metal film.
In an alternative embodiment, the heating resistor layer 202, the temperature resistor layer 302, the first structural layer 201 and the second structural layer 203 are all formed by annealing treatment, wherein the temperature of the annealing treatment is greater than or equal to 400 ℃, and the time of the annealing treatment is greater than or equal to 4 h.
In the embodiment of the present application, the heating resistor layer 202, the temperature resistor layer 302, the first structural layer 201, and the second structural layer 203 are all formed by annealing, and then the heating resistor layer 202, the temperature resistor layer 302, the first structural layer 201, and the second structural layer 203 are all made of high temperature resistant materials, so as to adapt to the high temperature annealing process, and further enhance the stability of the gas sensor in detection in a high temperature environment.
S7: patterning and etching processes are performed on the protective layer to form the bridge structure 200.
S8: etching the area corresponding to the bridge structure 200 on the substrate 100 to form a heat dissipation cavity 101, so as to obtain the gas sensor for early warning of thermal runaway of the lithium battery; wherein, the bridge structure 200 is suspended at the opening of the cavity of the heat dissipation cavity 101.
In this embodiment of the application, the etching process may be a wet etching process or a dry etching process, specifically, first, a patterning process and an etching process are performed on the protection layer, then, a patterning process and an etching process are performed on the thermal insulation layer to form the bridge-type structure 200, and finally, an area on the substrate 100 corresponding to the bridge-type structure 200 is etched to obtain the heat dissipation cavity 101, so as to obtain the gas sensor for early warning of thermal runaway of the lithium battery.
According to the technical scheme of the embodiment of the application, the method has the following beneficial effects:
1. the gas sensor for the early warning of the thermal runaway of the lithium battery, which is prepared by the application, has the advantages of high response speed, high sensitivity, long service life, high anti-interference performance, low power consumption, small volume, simple and convenient preparation method and the like, and has higher application value.
2. A gas sensor for early warning of lithium cell thermal runaway in this application is through setting up heat dissipation chamber and unsettled bridge type structure that sets up on the heat dissipation chamber, so that the gas sensor who uses for the early warning of lithium cell thermal runaway has good adiabatic characteristic, reduce gas sensor's consumption, improve gas sensor's interference killing feature, and simultaneously, the detection face of the resistive heating layer of still being convenient for all exposes in the gaseous environment that awaits measuring, increase the contact range to hydrogen detection, so that resistive heating layer contacts hydrogen as far as, and then improve the sensitivity of the gas sensor who is used for the early warning of lithium cell thermal runaway.
3. The gas sensor prepared in the application has no chemical reaction process in the process of detecting gas, and can reach a thermal stable state in hundreds of milliseconds, so that the response speed of the gas sensor for the lithium battery thermal runaway early warning can be obviously improved.
4. A gas sensor for early warning of lithium cell thermal runaway in this application cooperates high accuracy measurement circuit, can detect out 0.05% concentration hydrogen at least, has broken through the limit that the gas sensor that the tradition was used for early warning of lithium cell thermal runaway detects hydrogen concentration, and then enlarges the scope value that detects hydrogen concentration to improve the detection precision of the gas sensor who is used for early warning of lithium cell thermal runaway, have wider application scene.
5. The gas sensor prepared in the application is utilized to detect gas, and materials which are easy to be poisoned or interfered by other gases such as catalysts, gas-sensitive materials and the like are not used, so that the service life of the gas sensor is effectively prolonged.
6. Utilize the gas sensor who prepares in this application to carry out the in-process that detects to gas, all not use consumptive material such as chemical reagent and chemical reaction material, have characteristics such as stable performance and long service life.
7. This application is through setting up first structural layer and second structural layer at heating resistor layer both ends face to and set up third structural layer and fourth structural layer at the both ends face of temperature resistance layer, with the stability of reinforcing heating resistor layer and temperature resistance layer, and then make gas sensor have anti-oxidant, anti sublimation and anti electron migration's characteristic.
8. The heating resistor layer, the temperature resistance layer, the first structural layer and the second structural layer which are arranged in the application are all formed through annealing treatment, and the heating resistor layer, the temperature resistance layer, the first structural layer and the second structural layer are made of high-temperature-resistant materials, so that the stability of detection of the gas sensor in a high-temperature environment is enhanced.
9. The preparation method of the gas sensor for the lithium battery thermal runaway early warning is simple to operate, low in cost and convenient for mass production.
With regard to the method for preparing the gas sensor for warning of thermal runaway of a lithium battery in the above embodiment, the details of the components, the positional relationship of the components, and the beneficial effects have been described in detail in the embodiment of the gas sensor for warning of thermal runaway of a lithium battery, and will not be described in detail here.
The above description is only for the specific embodiments of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present application, and shall be covered by the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. A gas sensor for early warning of thermal runaway of a lithium battery, comprising: a substrate (100) and a bridge structure (200);
a heat dissipation cavity (101) is arranged on the functional side of the substrate (100), and the bridge structure (200) is arranged in the range of a cavity opening of the heat dissipation cavity (101) in a suspended manner;
the bridge-type structure (200) comprises a first structural layer (201), a heating resistance layer (202) and a second structural layer (203) which are sequentially stacked and arranged in the direction away from the heat dissipation cavity (101), wherein the first structural layer (201) is close to the heat dissipation cavity (101).
2. The gas sensor for the warning of the thermal runaway of the lithium battery as claimed in claim 1, further comprising at least one ambient temperature sensing structure disposed on the substrate, the ambient temperature sensing structure being disposed adjacent to the bridge structure (200);
the environment temperature sensing structure comprises a third structure layer (301), a temperature resistance layer (302) and a fourth structure layer (303) which are sequentially stacked along the direction far away from the substrate (100).
3. The gas sensor for early warning of thermal runaway of a lithium battery as claimed in claim 2, wherein the ambient temperature sensing structure further comprises at least two pad structures (401), and both ends of the heating resistor layer (202) in the bridge structure (200) are respectively connected to the at least two pad structures (400);
the pad structure (400) is arranged on a side of the third structure layer (301) facing away from the substrate (100).
4. The gas sensor for the warning of the thermal runaway of the lithium battery as claimed in claim 3, wherein the pad structure (400) comprises a resistance pad layer (401) and a metal protection layer (402), the resistance pad layer (401) is disposed on the third structural layer (301), and the metal protection layer (402) is disposed on the resistance pad layer (401).
5. The gas sensor for warning of thermal runaway of a lithium battery as claimed in claim 4, wherein both ends of the temperature resistance layer (302) are connected to the at least two pad structures (400), respectively.
6. The gas sensor for warning of thermal runaway of a lithium battery as claimed in claim 1, wherein the heating resistor layer (202) is arranged in a serpentine on the first structural layer (201).
7. The gas sensor for the warning of the thermal runaway of the lithium battery as claimed in claim 1, wherein the thickness of the heating resistor layer (202) is 0.1um to 2 um.
8. The gas sensor for the warning of the thermal runaway of the lithium battery as recited in claim 4, wherein the material of the metal protection layer comprises at least one of gold, platinum, silver and aluminum.
9. The gas sensor for the warning of the thermal runaway of the lithium battery as claimed in claim 1, wherein the material of the first structural layer (201) comprises any one or more of silicon oxide, silicon nitride, aluminum oxide, phosphorosilicate glass and borosilicate glass.
10. A method for preparing the gas sensor for warning the thermal runaway of the lithium battery as claimed in any one of claims 1 to 9, which is characterized by comprising the following steps:
providing a substrate (100);
performing thin film deposition on the substrate (100) to form a heat insulating layer on the substrate (100);
depositing a metal film on one side of the heat-insulating layer far away from the substrate (100) to form a first metal film;
etching the first metal film, and forming a temperature resistance layer (302), a heating resistance layer (202) and a resistance pad layer on preset positions;
performing thin film deposition on the temperature resistance layer (302) and the heating resistance layer (202) at the side far away from the heat insulating layer to form a protective layer;
depositing a metal film on one side, far away from the heat-insulating layer, of the resistance pad layer 401 to form a second metal film;
carrying out patterning treatment and etching treatment on the protective layer to form a bridge type structure (200);
etching the area, corresponding to the bridge-type structure (200), on the substrate (100) to form a heat dissipation cavity (101) and obtain the gas sensor for early warning of thermal runaway of the lithium battery; the bridge-shaped structure (200) is arranged at the opening of the cavity of the heat dissipation cavity (101) in a suspending manner.
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| CN202210601086.8A CN115047030A (en) | 2022-05-30 | 2022-05-30 | Gas sensor for lithium battery thermal runaway early warning and preparation method thereof |
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| CN202210601086.8A CN115047030A (en) | 2022-05-30 | 2022-05-30 | Gas sensor for lithium battery thermal runaway early warning and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116759682A (en) * | 2023-08-24 | 2023-09-15 | 宁德时代新能源科技股份有限公司 | Battery, power utilization device and gas detection method of battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116759682A (en) * | 2023-08-24 | 2023-09-15 | 宁德时代新能源科技股份有限公司 | Battery, power utilization device and gas detection method of battery |
| CN116759682B (en) * | 2023-08-24 | 2024-02-27 | 宁德时代新能源科技股份有限公司 | Battery, power utilization device and gas detection method of battery |
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