Analyte sensing device

Abstract

A sensing device for detecting analytes within a package or container is disclosed. The sensing device can include a substrate, one or more electrodes, and an array of sensors disposed on the substrate. The array of sensors can include a plurality of carbon-based sensors coupled to the one or more electrodes. Each sensor can be configured to react with a unique set of analytes in response to an electromagnetic signal received from an external device. In some cases, a first sensor can be functionalized with a first material configured to detect the presence of each analyte of a first set of analytes, and a second sensor can be functionalized with a second material configured to detect the presence of each analyte of a second set of analytes. The second set of analytes can be a subset of the first set of analytes, and the second material can be different than the first material.

Description

Technical Field

[0001] This disclosure relates generally to the detection of analytes, and more specifically, to improving the accuracy of analyte sensing devices. Background Technology

[0002] Chemical sensors operate by generating a signal in response to the presence of a specific chemical substance. Conventional analyte sensors typically require relatively high-power energy sources to detect relatively low concentrations of analytes (such as less than one part per billion (ppb), making widespread adoption of such sensors impractical. Further improvements to chemical and vapor sensors are warranted. Summary of the Invention

[0003] This summary is provided to introduce a series of concepts in a simplified form, which will be further described in the following detailed description. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

[0004] One innovative aspect of the subject matter described in this disclosure can be implemented as a sensing device for detecting analytes. The sensing device may include a substrate and a sensor array. The sensor array may be arranged on the substrate and may include a plurality of carbon-based sensors. In some implementations, a first carbon-based sensor disposed between a first pair of electrodes may be configured to detect the presence of each analyte in a first group of analytes, and a second carbon-based sensor disposed between a second pair of electrodes may be configured to detect the presence of each analyte in a second group of analytes, wherein the second group of analytes is a subset of the first group of analytes. In some cases, the first group of analytes may include at least twice the number of different analytes as the second group of analytes. In some implementations, the first carbon-based sensor may be configured to generate a first output signal in response to detecting the presence of one or more analytes in the first group of analytes, and the second carbon-based sensor may be configured to generate a second output signal in response to confirming the presence of one or more analytes detected by the first carbon-based sensor. In one implementation, the first and second output signals may be currents at least partially based on alternating currents applied to the first and second carbon-based sensors. In some cases, the ratio of the current to the alternating current of the first output signal can indicate the concentration of at least one of the detected analytes, and the ratio of the current to the alternating current of the second output signal can indicate the concentration of at least one of the confirmed analytes.

[0005] In other implementations, the first and second output signals may respectively indicate the impedance of the first and second carbon-based sensors. In some aspects, the first output signal may indicate the impedance change of the first carbon-based sensor due to exposure to one or more analytes from the first analyte group, and the second output signal may indicate the impedance change of the second carbon-based sensor due to exposure to one or more analytes from the second analyte group. In some other implementations, the first and second output signals may respectively indicate the frequency response of the first and second carbon-based sensors. In some cases, the frequency response of the first carbon-based sensor may indicate the presence or absence of each analyte from the first analyte group, and the frequency response of the second carbon-based sensor may indicate the presence or absence of each analyte from the second analyte group. The frequency response may be sensed based on electrochemical impedance spectroscopy (EIS) or resonant impedance spectroscopy (RIS).

[0006] In various implementations, a first carbon-based sensor may be functionalized with a first material configured to react with each analyte in a first analyte group, and a second carbon-based sensor may be functionalized with a second material configured to react only with analytes in a second analyte group. In some cases, the first material may be a cobalt-decorated carbon nanotube onion (CNO) configured to detect the presence of one or more of triacetone triperoxide (TATP), toluene, ammonia, or hydrogen sulfide (H2S), and the second material may be an iron-decorated three-dimensional (3D) graphene structure configured to confirm the presence of toluene.

[0007] The substrate can be paper, a flexible polymer, or other suitable material. In some implementations, the substrate and sensor array can be integrated within a label configured to be removably printed onto the surface of packaging or a container. In some aspects, each of the carbon-based sensors can be printed on the substrate using a different carbon-based ink, and the electrode pairs can be printed on the substrate using ohmic-based ink. In some cases, the first and second carbon-based sensors can be stacked on top of each other. In other cases, the first and second carbon-based sensors can be arranged adjacent to each other.

[0008] In some implementations, each of the carbon-based sensors may include a variety of different graphene allotropes. In some aspects, the different graphene allotropes of a given carbon-based sensor may include one or more microporous or mesoporous pathways. Each of the carbon-based sensors may include a polymer configured to bind the various different graphene allotropes together. The polymer may include a wetting agent configured to reduce the susceptibility of the given carbon-based sensor to humidity.

[0009] Another innovative aspect of the subject matter described in this disclosure can be implemented as a sensing device for detecting analytes within packaging or containers. In various implementations, the sensing device may include a substrate, one or more electrodes, and a sensor array. The sensor array may be disposed on the substrate and may include multiple carbon-based sensors coupled to one or more electrodes. In some implementations, the carbon-based sensors may be configured to react to a unique set of analytes in response to an electromagnetic signal received from an external device. In some cases, the carbon-based sensors may be configured to resonate at different frequencies in response to an electromagnetic signal. Each of the one or more electrodes may be configured to provide an output signal indicating whether the corresponding carbon-based sensor has detected one or more analytes from a corresponding group of the unique set of analytes. In some cases, each output signal may indicate the impedance or reactance of the corresponding carbon-based sensor.

[0010] Alternatively, a first frequency response of the first carbon-based sensor to an electromagnetic signal may indicate the presence or absence of analytes from the first analyte group in the packaging or container, and a second frequency response of the second carbon-based sensor to an electromagnetic signal may indicate the presence or absence of analytes from the second analyte group in the packaging or container. In some cases, the first frequency response may be based at least in part on the first carbon-based sensor being exposed to an electromagnetic signal for a first time period, and the second frequency response may be based at least in part on the second carbon-based sensor being exposed to an electromagnetic signal for a second time period longer than the first time period. In some cases, the length of the second time period is at least twice the length of the first time period. The first and second frequency responses may be sensed based on resonant impedance spectroscopy (RIS).

[0011] In various implementations, a first carbon-based sensor may be functionalized with a first material configured to detect the presence of each analyte in a first analyte group, and a second carbon-based sensor may be functionalized with a second material configured to detect the presence of each analyte in a second analyte group. The second analyte group may be a subset of the first analyte group, and the second material may differ from the first material. In some aspects, the first analyte group may include at least twice the number of different analytes as the second analyte group. In some cases, the first material may be a cobalt-decorated carbon nanotube onion (CNO) configured to detect the presence of one or more of triacetone triperoxide (TATP), toluene, ammonia, or hydrogen sulfide (H2S), and the second material may be an iron-decorated three-dimensional (3D) graphene structure configured to confirm the presence of toluene. In various implementations, a third carbon-based sensor may be functionalized with a third material configured to detect the presence of each analyte in a third analyte group, wherein the third analyte group may be another subset of the first analyte group, and the third material may differ from the first and second materials.

[0012] In some implementations, at least two of the carbon-based sensors may be planar and disposed on a substrate. In other implementations, the carbon-based sensors may be vertically stacked on top of each other. For example, in one implementation, the carbon-based sensors may form a dielectric constant gradient. In some aspects, a single electrode may be configured to provide an output signal indicating whether the stacked carbon-based sensors have detected one or more analytes. A single electrode may also be configured to provide an output signal to an external device.

[0013] The substrate can be paper, a flexible polymer, or other suitable material. In some implementations, the substrate and sensor array can be integrated within a label, which can be removably printed onto the surface of packaging or a container. In some aspects, each of the carbon-based sensors can be printed on the substrate using different carbon-based inks, and one or more electrodes can be printed on the substrate using ohmic inks. In some implementations, each of the carbon-based sensors can include a variety of different graphene allotropes. In some aspects, the different graphene allotropes of a given carbon-based sensor can include one or more microporous or mesoporous pathways. Each of the carbon-based sensors can include a polymer configured to bond the various different graphene allotropes together. The polymer can include a wetting agent configured to reduce the susceptibility of the given carbon-based sensor to humidity.

[0014] Another innovative aspect of the subject matter described in this disclosure can be implemented as a sensing device for monitoring a battery pack. The sensing device may include a substrate and a plurality of carbon-based sensors disposed on the substrate. Each of the carbon-based sensors may be coupled between a corresponding electrode pair. In some implementations, the 3D graphene-based sensing material of the first carbon-based sensor may be functionalized with a first material configured to detect the presence of each analyte in a first analyte group, and the 3D graphene-based sensing material of the second carbon-based sensor may be functionalized with a second material configured to detect the presence of each analyte in a second analyte group. In some aspects, the second analyte group is a subset of the first analyte group, and the analyte group may include at least twice the number of different analytes as the second analyte group. In some cases, the first and second carbon-based sensors may be stacked on top of each other. In other cases, the first and second carbon-based sensors may be disposed adjacent to each other. In some implementations, the carbon-based sensors may be carbon-based ink printed on a substrate. In some cases, the first carbon-based sensor may be a first carbon-based ink, and the second carbon-based sensor may be a second carbon-based ink different from the first carbon-based ink.

[0015] A first carbon-based sensor may be configured to generate a first output signal in response to detecting the presence of one or more analytes from a first group of analytes, and a second carbon-based sensor may be configured to generate a second output signal in response to confirming the presence of one or more analytes detected by the first carbon-based sensor. In some implementations, the sensing device may include an input terminal for receiving alternating current, and the first and second output signals may be currents at least partially based on the alternating current. In some cases, a first difference between the alternating current and the first output signal may indicate the presence or absence of one or more analytes from the first group of analytes, and a second difference between the alternating current and the second output signal may indicate the presence or absence of one or more analytes from the second group of analytes.

[0016] In other implementations, a first output signal may indicate an impedance change in a first carbon-based sensor due to exposure to one or more analytes from a first analyte group, and a second output signal may indicate an impedance change in a second carbon-based sensor due to exposure to one or more analytes from a second analyte group. In some cases, a relatively small impedance change in a corresponding carbon-based sensor may indicate the absence of the corresponding analyte group, and a relatively large impedance change in a corresponding carbon-based sensor may indicate the presence of the corresponding analyte group.

[0017] In some other implementations, the sensing device may include an antenna configured to receive electromagnetic signals from an external device, and the first and second output signals may be the frequency responses of the 3D graphene-based sensing materials of the first and second carbon-based sensors to the electromagnetic signals, respectively. For example, the frequency response of the 3D graphene-based sensing material of the first carbon-based sensor may indicate the presence or absence of one or more analytes from a first analyte group, and the frequency response of the 3D graphene-based sensing material of the second carbon-based sensor may indicate the presence or absence of one or more analytes from a second analyte group. In some aspects, the frequency response may be sensed based on resonant impedance spectroscopy (RIS).

[0018] In various implementations, at least one of the output signals can indicate the operating mode of the battery pack. In some implementations, at least one output signal can indicate a normal mode based on the absence of analytes from the first analyte group, a maintenance mode based on the presence of one or more analytes from the first analyte group not exceeding a threshold level, or an emergency mode based on the presence of one or more analytes from the first analyte group exceeding a threshold level. Furthermore, or in alternatives, the first output signal can indicate the concentration level of one or more analytes from the first analyte group, and the second output signal can indicate the concentration level of one or more analytes from the second analyte group.

[0019] In some implementations, the analytes in the first and second analyte groups may include one or more volatile organic compounds (VOCs). One or more VOCs include any one or more of the following: carbon dioxide (CO2); carbon monoxide (CO); nitrogen dioxide (NO2); one or more hydrocarbons, including methane (CH4), ethylene (C2H4), ethane (C2H6), or propane (C3H8); one or more acids, including hydrochloric acid (HCl) or hydrofluoric acid (HF); one or more fluorinated hydrocarbons, including phosphorus oxyfluoride; hydrogen cyanide (HCN); one or more aromatic compounds, including benzene (C6H6), toluene (C7H8); ethanol (C2H5OH); hydrogen; carbonate-based electrolytes, including ethylene carbonate (C3H4O3), dimethyl carbonate (C3H6O3), propylene carbonate (C4H3O3); or one or more reduced sulfur compounds, including thiols in the R-SH form. In some aspects, each of the 3D graphene-based sensing materials can be configured to adsorb VOCs. In some respects, each of the carbon-based sensors may include a variety of different graphene allotropes. The various graphene allotropes of a corresponding carbon-based sensor may include one or more microporous or mesoporous pathways.

[0020] Another innovative aspect of the subject matter described in this disclosure can be implemented as a container for storing one or more articles. The container may include a surface defining a container volume and a label printed on the container. In various implementations, the label may include a substrate, a plurality of carbon-based sensors printed on the substrate, and one or more electrodes printed on the substrate. The carbon-based sensors may be collectively configured to detect the presence of one or more analytes within the container. In some implementations, each of the carbon-based sensors may be configured to react with a unique set of analytes in response to an electromagnetic signal received from an external device. One or more electrodes may be coupled to at least some of the carbon-based sensors and may be configured to provide one or more output signals indicating the presence or absence of one or more analytes in the container. In some implementations, a first electrode coupled to a first carbon-based sensor may be configured to indicate the presence of one or more analytes from a first set of analytes, and a second electrode coupled to a second carbon-based sensor may be configured to confirm the presence of an analyte detected by the first carbon-based sensor. In some aspects, the carbon-based sensors may be configured to resonate at different frequencies in response to an electromagnetic signal.

[0021] In some implementations, a first carbon-based sensor may be functionalized with a first material configured to detect the presence of each analyte in a first analyte group, and a second carbon-based sensor may be functionalized with a second material configured to detect the presence of each analyte in a second analyte group, wherein the second analyte group may be a subset of the first analyte group. In some aspects, the first analyte group may include at least twice the number of different analytes as the second analyte group. The second material may differ from the first material. For example, in one implementation, the first material may be cobalt-decorated carbon nanotubes (CNO) configured to detect the presence of one or more of triacetone triperoxide (TATP), toluene, ammonia, or hydrogen sulfide (H2S), and the second material may be an iron-decorated three-dimensional (3D) graphene structure configured to confirm the presence of toluene. As another example, a third carbon-based sensor may be functionalized with a third material configured to detect the presence of each analyte in a third analyte group, wherein the third analyte group is another subset of the first analyte group, and the third material differs from both the first and second materials.

[0022] In some implementations, each output signal may indicate the frequency response of the corresponding carbon-based sensor to an electromagnetic signal. In some cases, a first frequency response of the first carbon-based sensor to an electromagnetic signal may indicate the presence or absence of analytes from a first analyte group in the container, and a second frequency response of the second carbon-based sensor to an electromagnetic signal may indicate the presence or absence of analytes from a second analyte group in the container. The first frequency response may be based at least in part on the first carbon-based sensor being exposed to an electromagnetic signal for a first time period, and the second frequency response may be based at least in part on the second carbon-based sensor being exposed to an electromagnetic signal for a second time period longer than the first time period. In some aspects, the length of the second time period is at least twice the length of the first time period. The first and second frequency responses may be sensed based on resonant impedance spectroscopy (RIS).

[0023] In various implementations, the antenna can be printed on a substrate and configured to drive current through the carbon-based sensor in response to an electromagnetic signal. In some aspects, each output signal can indicate the impedance or reactance of the corresponding carbon-based sensor to the current. The impedance or reactance of the carbon-based sensor can indicate the presence or absence of one or more analytes in the container. For example, the impedance or reactance of the first carbon-based sensor can indicate the presence or absence of analytes in a first group of analytes, and the impedance or reactance of the second carbon-based sensor can indicate the presence or absence of analytes in a second group of analytes. In some cases, at least two of the carbon-based sensors are arranged in a planar manner and disposed on a substrate. In other cases, the carbon-based sensors are stacked on top of each other. In some aspects, the carbon-based sensors can form a dielectric constant gradient.

[0024] In some implementations, each of the carbon-based sensing materials may include multiple different graphene allotropes. In some aspects, the different graphene allotropes of a given carbon-based sensor may include one or more microporous or mesoporous pathways. Each of the carbon-based sensors may include a polymer configured to bind multiple different graphene allotropes together. The polymer may include a wetting agent configured to reduce the susceptibility of the given carbon-based sensor to humidity.

[0025] Details of one or more implementations of the subject matter described herein are set forth in the accompanying drawings and description below. Other features, aspects, and advantages will become apparent from the description, drawings, and claims. It should be noted that the relative dimensions in the following figures may not be drawn to scale. Attached Figure Description

[0026] Figure 1 An exemplary sensing device is shown that is configured to detect analytes according to some implementation.

[0027] Figure 2 It describes the coupling to the receiver according to some implementation method. Figure 1 Illustration of the sensing device.

[0028] Figure 3 It describes the analysis of the battery pack by being configured according to some implementation method. Figure 1 Illustration of the sensing device.

[0029] Figure 4 It describes the analysis of the battery pack by being configured according to some implementation method. Figure 1 Illustration of the sensing device.

[0030] Figure 5 It describes one or more analytes based on some implementation methods and Figure 1 A diagram illustrating the interaction between sensing devices.

[0031] Figure 6 It is based on some implementation methods, including Figure 1 Block diagram of an analyte detection system with a sensing device.

[0032] Figures 7A-7E The diagram illustrates sensor arrays configured to detect analytes according to various implementation methods.

[0033] Figure 8 A flowchart is shown illustrating exemplary operation for manufacturing at least some of the sensing devices disclosed herein, according to some implementation methods.

[0034] Figure 9 Another sensor array is shown, based on some implementation methods.

[0035] Figure 10A Exemplary sensor configurations are shown according to some implementation methods.

[0036] Figure 10B Exemplary sensor configurations based on other implementations are shown.

[0037] Figure 11A-11G Illustrations show various structured carbon materials that can be used in the sensing devices disclosed herein, according to some implementation methods.

[0038] Figure 12A-12F Exemplary frequency responses of resonant impedance sensors to various analytes are shown according to some implementations.

[0039] Figure 13A The real (Z′) impedance component of an exemplary frequency response of an electrochemical impedance sensor according to some implementations is shown.

[0040] Figure 13B The virtual (Z”) impedance component of the exemplary frequency response of an electrochemical impedance sensor according to some implementations is shown.

[0041] Figure 14A Exemplary baseline frequency responses and exemplary frequency responses to hydrogen peroxide are shown according to some implementations.

[0042] Figure 14B Exemplary frequency responses to acetone and water are shown according to some implementations.

[0043] Figure 14C Exemplary frequency responses to ethanol and ammonia are shown according to some implementations.

[0044] The same reference numerals and names in the various figures indicate the same elements. Detailed Implementation

[0045] For the purpose of describing the innovative aspects of this disclosure, the following description pertains to a number of exemplary implementations. However, those skilled in the art will readily recognize that the teachings herein can be applied in a wide variety of different ways. The described implementations can be implemented in any environment to detect the presence of a variety of different analytes within or near any device, battery pack, packaging, container, structure, or system that may be susceptible to the analyte. Furthermore, implementations of the subject matter disclosed herein can be used to detect the presence of any harmful or hazardous chemical substance, gas, or vapor. Therefore, the disclosed implementations are not limited to the examples provided herein but cover all implementations contemplated by the appended claims. Additionally, well-known elements of this disclosure will not be described in detail or will be omitted to avoid obscuring the relevant details.

[0046] Batteries typically comprise multiple electrochemical cells and can power a wide variety of devices, including mobile phones, laptops, electric vehicles (EVs), factories, and buildings. When batteries are exposed to harsh environmental conditions or become damaged, toxic chemicals and vapors within the electrochemical cells can leak from the battery casing, posing serious health and safety risks. When released from the battery, these toxic chemicals and vapors can cause respiratory problems, allergic reactions, and may even explode. Chemicals commonly used in lithium-ion battery cells can be particularly dangerous due to their high reactivity and potential for explosion if accidentally released from the battery casing. Therefore, there is a need for rapid and accurate determination of whether a particular battery or battery pack is leaking such toxic chemicals or vapors. Furthermore, when the presence of one or more analytes (or other toxic chemicals or vapors) is detected, it is desirable to determine the concentration of such analytes. It is also desirable to predict battery failure and / or determine the operational integrity of such batteries.

[0047] Various aspects of the subject matter disclosed herein relate to the detection of the presence of one or more analytes in the environment. According to various implementations of the subject matter disclosed herein, sensing devices may include multiple carbon-based sensors configured to detect the presence of a variety of different analytes. In some implementations, at least some of the carbon-based sensors may include different types of three-dimensional (3D) graphene-based sensing materials configured to react with different analytes or groups of analytes. In some aspects, the sensing materials of different sensors may be functionalized with different materials, for example, to improve the sensitivity of each sensor to one or more corresponding analytes.

[0048] In some implementations, impedance changes of the sensor can be used to determine the presence of one or more analytes near the sensing device. In other implementations, current changes of the sensor can be used to determine the presence of one or more analytes near the sensing device. In still other implementations, the frequency response of the sensor can be used to determine the presence of one or more analytes near the sensing device. In some aspects, the frequency response of the sensor can be compared with one or more reference frequency responses corresponding to one or more analytes to identify which analytes are present in the environment. In this way, the sensor system disclosed herein can accurately detect the presence of a variety of different analytes in a given environment.

[0049] In one implementation, a first sensor may be configured to detect the presence of a relatively large number of different analytes, and one or more second sensors may be configured to confirm the presence of one or more analytes detected by the first sensor. Specifically, the first sensor may be configured to react to each analyte in a first analyte group, and one or more second sensors may be configured to react to a corresponding second analyte group, which is a unique subset of the first analyte group. In some cases, the first sensor may be exposed to the surrounding environment for a relatively short period of time to provide an initial coarse indication of the presence of analytes in the first analyte group, and each of the second sensors may be exposed to the surrounding environment for a relatively long period of time to provide a fine indication of the presence of any analyte in the corresponding second analyte group. For example, while the first sensor may be able to detect a larger number of analytes than any one of the second sensors, configuring each of the second sensors to detect only one or two different analytes increases the sensitivity of the second sensor to its corresponding “target” analyte, thereby improving the accuracy of the sensing device in detecting the presence of a variety of analytes. Therefore, when the indication provided by the second sensor is used to confirm the indication provided by the first sensor, the number of false positive indications is reduced, which in turn improves the overall accuracy of the sensing device.

[0050] Specific implementations of the subject matter described herein can be implemented to achieve one or more of the following potential advantages. In some implementations, the sensing device disclosed herein can not only detect the presence of multiple analytes and other hazardous chemicals and gases, but also reduce the incidence of false positives. Specifically, by rapidly detecting the presence of one or more analytes in an analyte group using a first sensor and confirming the presence of the analytes detected by the first sensor using one or more second sensors, aspects of this disclosure can reduce the number of false positives indicated by the sensing device. This contrasts with conventional analyte sensors that may not only be insensitive to differences between different analytes in an analyte group and / or do not employ multilayer analyte detection systems.

[0051] Figure 1 An exemplary sensing device 100 configured to detect an analyte according to some implementations is shown. The sensing device 100 may include an array 110 of carbon-based sensors 120 disposed on a substrate 130. In some aspects, each of the carbon-based sensors 120 may include a carbon-based sensing material 125 disposed between corresponding electrode pairs 121-122, for example, such as... Figure 1As shown. In other respects, the carbon-based sensor 120 may be coupled to only one electrode. The carbon-based sensor 120, and their corresponding carbon-based sensing material 125, may be formed of any suitable material that reacts with a variety of different analytes or can be configured to react with a variety of different analytes. The reactions between the carbon-based sensor 120 and the various analytes can be used to detect the presence of a specific analyte or a specific group of analytes. For example, the reaction may result in a change in current through one or more carbon-based sensors 120, a change in impedance or reactance of one or more carbon-based sensors 120, a unique or different frequency response in one or more carbon-based sensors 120, or any combination thereof.

[0052] exist Figure 1 In this example, multiple different analytes 151-155 are present in the sensing device 100. Although Figure 1 Only five analytes 151-155 are shown, but the sensing device 100 can detect a much larger number of different analytes. In some aspects, analytes 151-155 may comprise any vapor phase and / or fluid composition containing one or more volatile organic compounds (VOCs) such as (but not limited to) carbon dioxide (CO2); carbon monoxide (CO); nitrogen dioxide (NO2); one or more hydrocarbons, including methane (CH4), ethylene (C2H4), ethane (C2H6), or propane (C3H8); one or more acids, including hydrochloric acid (HCl) or hydrofluoric acid (HF); one or more fluorinated hydrocarbons, including phosphorus oxyfluoride; hydrogen cyanide (HCN); one or more aromatic compounds, including benzene (C6H6), toluene (C7H8); ethanol (C2H5OH); hydrogen; or one or more reduced sulfur compounds, including thiols in the R-SH form.

[0053] In some implementations, the carbon-based sensor 120 may include carbon particles or 3D graphene structures that react with (or can be configured to react with) analytes associated with the battery, for example, to determine whether a particular battery is leaking potentially harmful or hazardous analytes. In other implementations, the carbon-based sensor 120 may include carbon particles or 3D graphene structures that react with (or can be configured to react with) groups of analytes that are considered harmful or hazardous, individually or in combination with each other. For example, the carbon-based sensor 120 may be configured to produce a detectable reaction upon exposure to acetone and hydrogen peroxide to detect the presence of acetone peroxide (which is highly explosive). In another example, one or more of the carbon-based sensors 120 may be configured to detect the presence of triacetone triperoxide (TATP) or tricyclic acetone peroxide (TCAP) (which is a trimer of acetone peroxide).

[0054] In some implementations, each of the sensors 120 can be configured to react to a unique set of analytes. In some aspects, the sensors 120 can be configured to detect different material functionalizations of different analytes or different sets of analytes. In one implementation, a first sensor of the sensor array 110 can be configured to detect a first material functionalization present in a first set of analytes, and one or more second sensors of the sensor array 110 can be configured to detect a second material functionalization present in one or more corresponding second sets of analytes, wherein the second materials are different from each other and different from the first materials, and the second set of analytes is a unique subset of the first set of analytes. For example, the first sensor can be configured to detect each of five analytes 151-155, while each of the second sensors can be configured to detect only one of the five analytes 151-155. The first sensor can sense the environment for a relatively short period of time to provide a coarse detection of any one of the analytes 151-155, and each of the second sensors can sense the environment for a relatively long period of time to confirm the presence of a corresponding analyte among the five analytes 151-155. In this way, one or more second sensors 120 can be used to verify the detection of various analytes by the first sensor 120, thereby reducing or even eliminating false positives.

[0055] In other implementations, sensor 120 may be configured to react with overlapping analyte groups. In some other implementations, sensor 120 may be configured to react with the same or similar analyte groups.

[0056] The substrate 130 can be any suitable material. In some cases, the substrate can be paper or a flexible polymer. In other cases, the substrate 130 can be a rigid or semi-rigid material, such as a printed circuit board.

[0057] Figure 2 It describes the coupling to receiver 180 according to some implementation methods. Figure 1The figure 200 shows the sensing device 100. The receiver 180 can be any suitable device, component, or mechanism capable of collecting, guiding, or directing analytes 151-155 present in the surrounding environment toward the sensing device 100. As shown, the receiver 180 includes an inlet 182 and a plurality of outlets 184. The inlet 182 can be configured to receive or attract analytes 151-155 into the receiver 180, and the outlets 184 can be configured to guide analytes 151-155 toward one or more exposed surfaces of the sensing device 100. In some implementations, each of the outlets 184 of the receiver 180 can be aligned with a corresponding sensor 120, for example, such that analytes 151-155 entering the receiver 180 can be released and exposed to each of the sensors 120 in the array 110. In this way, the receiver 180 can concentrate analytes 151-155 onto or near the corresponding sensing material 125 of the array 110, thereby increasing the likelihood of detection by the sensing device 100. For example, if the sensing device 100 is printed on the surface of the shipping packaging, a portion of the shipping packaging (e.g., a foldable flap) can be used as the receiver 180.

[0058] Figure 3 It describes a configuration based on some implementation method to detect the presence of analytes within or near the battery pack 310. Figure 1 The figure 300 shows a sensing device 100. A battery pack 310 is shown comprising a plurality of battery cells 320 arranged as a planar array on a substrate 312. One or more sensing devices 100 may be positioned around or coupled to a corresponding number of battery cells 320 in the battery pack 310. In some implementations, a subset of the battery cells 320 may be associated with sensing devices 100 such that the number of sensing devices 100 is less than the number of battery cells 320, for example, as shown in Figure 300. Figure 3 As depicted in the examples. In other implementations, each of the battery cells 320 may be associated with or coupled to a corresponding sensing device 100. In some cases, the sensors 120 of the corresponding sensing devices 100 may be stacked on top of each other (e.g., arranged vertically). In other cases, the sensors 120 of the corresponding sensing devices 100 may be arranged adjacent to each other (e.g., arranged planarly).

[0059] The sensing device 100 can be configured to function similarly to the description above. Figure 1 The described method detects the presence of analyte 340 leaking from one or more battery cells 320 of the battery pack 310. Specifically, each of the sensors 120 may be coupled between a corresponding electrode pair 121-122 and may include components configured to detect certain analytes (such as... Figure 1The presence of analytes 151-155) is detected by various 3D graphene-based sensing materials 125. In some implementations, sensing materials 125 within different sensors 120 may be configured to detect the presence of different analytes or different groups of analytes. For example, in some cases, the sensing material 125 of the first sensor 1201 may be functionalized with a first material configured to detect the presence of each analyte in the first analyte group, and the sensing material 125 of the second sensor 1202 may be functionalized with a second material configured to detect the presence of each analyte in the second analyte group, wherein the second analyte group is a subset of the first analyte group. In other implementations, sensing materials 125 within different sensors 120 may be configured to detect the presence of the same analyte or the same group of analytes.

[0060] In various implementations, each of the sensors 120 within the corresponding sensing device 100 may be configured to provide an output signal in response to the detection of the presence of one or more analytes. In some implementations, the output signal may be a current generated in response to an alternating current supplied to the corresponding sensor 120. In some cases, the difference between the alternating current and the output signal may indicate the presence or absence of one or more analytes from the first analyte group. In other implementations, the output signal may indicate an impedance change in the corresponding sensor 120 due to exposure to one or more analytes. In some cases, a relatively small impedance change in the sensor 120 may indicate the absence of one or more analytes, and a relatively large impedance change in the sensor 120 may indicate the presence of one or more analytes.

[0061] In some other implementations, one or more of the sensing devices 100 may include an antenna (not shown for simplicity) configured to receive electromagnetic signals from an external device, and the output signal may be the frequency response of the sensing material 125 to the electromagnetic signal. For example, the frequency response of the sensing material 125 of the first sensor 1201 may indicate the presence or absence of a first analyte group, and the frequency response of the sensing material 125 of the second sensor 1202 may indicate the presence or absence of a second analyte group. In some aspects, the frequency response may be sensed based on resonant impedance spectroscopy (RIS).

[0062] In various implementations, the output signal generated by each sensing device 100 can indicate the operating mode of the corresponding battery cell 320 of the battery pack 310. In some implementations, the output signal can indicate a normal mode of the corresponding battery cell 320 based on the absence of an analyte, a maintenance mode of the corresponding battery cell 320 based on the presence of an analyte not exceeding a threshold level, or an emergency mode of the corresponding battery cell 320 based on the presence of an analyte exceeding a threshold level. The output signal can also indicate the concentration level of each analyte detected by the sensing device 100.

[0063] Figure 4 It describes a configuration based on some implementation method for detecting analytes in shipping packaging 410. Figure 1 The figure 400 shows the sensing device 100. The shipping package 410 is shown as including a surface 412 that defines a volume therein capable of accommodating one or more items (not shown for simplicity). The defined volume of the shipping package 410 also includes various analytes 414, which may be, for example... Figure 1 One or more of the analytes 151-155. As shown, the sensing device 100 may be a label 430 printed on the surface 412 of the shipping package 410. In various implementations, the label 430 may include a substrate 432, a plurality of carbon-based sensors 434 printed on the substrate, and one or more electrodes 436 printed on the substrate. Figure 1 The carbon-based sensor 120 and sensor 434 can be configured together to detect the presence of analyte 414 within shipping package 410.

[0064] In some implementations, each of the sensors 434 may be configured to react with a unique set of analytes in response to an electromagnetic signal 442 received from an external device 440. For example, a first sensor 4341 may be configured to detect the presence of a first set of analytes, and a second sensor 4342 may be configured to detect the presence of a second set of analytes, which is a first subset of the first set of analytes. In one implementation, a third sensor 4343 may be configured to detect the presence of a third set of analytes, which is a second subset of the first set of analytes. As discussed, the first sensor 4341 may be functionalized with a first material configured to react with the first set of analytes, the second sensor 4342 may be functionalized with a second material configured to react with the second set of analytes, and the third sensor 4343 may be functionalized with a third material configured to react with the third set of analytes. In this way, the second sensor 4342 may be used to confirm the detection of the first subset of analytes by the first sensor 4341, and the third sensor 4343 may be used to confirm the detection of the second subset of analytes by the first sensor 4341. In other implementations, one or more sets of sensors 434 may be configured to react with an overlapping set of analytes in response to an electromagnetic signal 442.

[0065] It can be Figure 1 In examples of electrodes 121-122, electrode 436 may be coupled to sensor 434. In some implementations, each sensor 434 may be coupled between corresponding electrode pairs 436. The first electrode 436 of each electrode pair may be configured to receive electromagnetic signal 442, and the second electrode 436 of each electrode pair may be configured to provide an output signal indicating whether the corresponding sensor 434 has detected the presence of an analyte.

[0066] In some implementations, each output signal may indicate the frequency response of the corresponding sensor 434 to the electromagnetic signal 442. For example, the frequency response of the first sensor 4341 may indicate the presence (or absence) of a first analyte group within the shipping package 410, the frequency response of the second sensor 4342 may confirm the presence (or absence) of a second analyte group, and the frequency response of the third sensor 4343 may confirm the presence (or absence) of a third analyte group. In some cases, the first sensor 4341 may be exposed to the electromagnetic signal 442 for a relatively short period to provide a coarse indication of the presence or absence of the analyte in the first analyte group, while the second and third sensors 4342 and 4343 may be exposed to the electromagnetic signal 442 for a relatively long period to confirm the indication of the first sensor 4341 regarding the presence of the second and third corresponding analyte groups. In this way, sensors 4341-4343 may collectively reduce the number of false positives indicated by the sensing device 100.

[0067] In at least some implementations, an antenna (not shown for simplicity) may be printed on substrate 432 and configured to drive an alternating current through sensor 434 in response to electromagnetic signal 442. Because sensor 434 can be functionalized with different materials that can have different electrical and / or chemical characteristics, the resulting sensor output current can indicate the presence (or absence) of different analytes. For example, in some cases, each output signal can indicate the impedance or reactance of the corresponding sensor 434 to the alternating current. The impedance or reactance of each sensor 434 can be measured and compared with a reference impedance or reactance to determine the presence of one or more analytes associated with sensor 434 in shipping package 410. In some cases, the reference impedance or reactance can be determined by driving an alternating current through sensor 434 when all analytes are absent and measuring the impedance or reactance of the output signal from sensor 434.

[0068] In some implementations, sensor 434 may be planar and disposed on substrate 432. In other implementations, sensor 434 may be vertically arranged and stacked on top of each other. In some implementations, sensor 434 may form a dielectric constant gradient.

[0069] As discussed, the analyte sensing devices disclosed herein can be integrated into products or packaging, such as cardboard boxes or food packaging. The analyte sensing devices disclosed herein can be placed near the product or packaging and can detect analytes on or within the product or packaging. For example, the analyte sensing device can be integrated into or placed near a scale used for weighing shipping containers, and the analyte sensing device can be used to detect analytes on or within any shipping package weighed by the scale. As another example, the analyte sensing device can be integrated into or placed near a component of a vehicle used for transporting shipping containers, such as inside a mail truck, and the analyte sensing device can be used to detect analytes on or within any shipping package being transported by the vehicle. As a further example, the analyte sensing device can be integrated into a conveyor belt or mounted on a part of a mechanical conveyor. Alternatively or additionally, the analyte sensing device can be integrated into handling equipment, such as a robotic arm, or handling apparel, such as gloves, and the analyte sensing device can be used to detect analytes on or within any shipping package being conveyed or handled.

[0070] In one implementation, a fan or suction device, such as a vacuum pump, can be used to direct ambient gas (which may include one or more analytes) toward and / or into a housing containing the analyte sensing device. For example, the analyte sensing device can be placed within the housing, and a fan or vacuum pump can draw ambient gas into the housing, exposing any analytes present in the ambient gas to the analyte sensing device. In another instance, the analyte sensing device can be placed near a set of objects, such as shipping packaging, mouse pads, or other products, and can monitor the presence of one or more analytes.

[0071] Figure 5 It describes one or more analytes based on some implementation methods and Figure 1 The illustration 500 shows an exemplary reaction between sensors 120. As discussed, sensor 120 may include a 3D graphene-based sensing material 125 disposed on a substrate 130, and sensing material 125 may be functionalized with material 126 configured to detect the presence of analytes 151-152. In some implementations, sensing material 125 may include a variety of different graphene allotropes having one or more microporous or mesoporous pathways. Although not shown for simplicity, polymers may combine a variety of different graphene allotropes with each other. In some cases, the polymer may include a wetting agent configured to reduce the susceptibility of the carbon-based sensor to humidity.

[0072] As shown in the figure, analytes 151-152 can permeate and react with sensing material 125 via various pathways. Specifically, illustration 510 depicts analytes 151-152 adsorbed on various exposed surfaces of functionalized material 126 and / or sensing material 125. Illustration 520 depicts carbon particles 522 that can form sensing material 125. In some cases, reactive chemical additives (such as salts dissolved in a carrier solvent) can be deposited on and within the exposed surfaces, pores, and / or pathways of the particulate carbon 522. In some cases, reactive chemical additives can be incorporated into the particulate carbon 522 to increase the sensitivity of sensor 120 to one or more specific analytes.

[0073] Figure 6 This is a block diagram of an analyte detection system 600 according to some implementations. The analyte detection system 600 is shown as including an input circuit 610, a sensor array 620, a measurement circuit 630, and a controller 640. The input circuit 610 is coupled to the controller 640 and the sensor array 620, and provides an interface through which current, voltage, and electromagnetic signals can be applied to the sensor array 620. It may be... Figure 1 An example of the sensor array 110, sensor array 620, is shown comprising eight carbon-based sensors 1201-1208 coupled between corresponding electrode pairs 1211 and 1221 to 1218 and 1228. In some cases, each of the first electrodes 1211-1218 may be coupled to a corresponding terminal of input circuit 610, and each of the second electrodes 1221-1228 may be coupled to a corresponding terminal of measurement circuit 630. In other cases, each terminal of input circuit 610 may be coupled to a corresponding sensor group 1201-1208.

[0074] The controller 640 can generate an excitation signal or field, which can be used by the measurement circuit 630 to measure or determine the carbon-based sensor 1201-120. nThe current level, voltage level, impedance, and / or frequency response. For example, in some implementations, controller 640 may be a current source configured to drive direct current or alternating current through each of sensors 1201-1208. In other implementations, controller 640 may be a voltage source that can apply various voltages to sensors 1201-1208 via corresponding electrodes 121 and 122. In some cases, controller 640 can adjust the sensitivity of a respective sensor 120 to a particular analyte by changing the voltage applied across the respective sensor 120. For example, controller 640 can increase the sensitivity of a respective sensor 120 by decreasing the applied voltage and decrease the sensitivity of a respective sensor 120 by increasing the applied voltage. In some other implementations, an antenna (not shown for simplicity) coupled to sensor array 620 can receive one or more electromagnetic signals from an external device. In some aspects, first electrodes 1211-121 R It can be configured to receive electromagnetic signals.

[0075] As discussed, sensors 1201-1208 may include corresponding sensing materials 1251-1258, which can be functionalized with different materials configured to react with and / or detect different analytes or groups of analytes. In some implementations, sensors 1201-1208 may include cobalt in particulate form, and sensing materials 1251-1258 may include carbon nanotubes (CNO). Specifically, in some aspects, the active sites on the exposed surface of CNO may be solid-phase cobalt (Co). (S) Functionalization (such as with Co particles) and / or cobalt oxide (Co2O3) (such as through surface modification) with available carbon on the exposed surface of CNO. For example, the chemical reaction associated with the detection of the presence of hydrogen peroxide (H2O2) using cobalt oxide can be represented as follows:

[0076]

[0077]

[0078] H2O2→2H + +O2+2e - (Overall reaction) (Equation 3)

[0079] Alternatively, cobalt-based functionalization can be used to detect TATP based on the following chemical reactions:

[0080] TATP+H + →3(CH3)2 CO+3H2O2 (Equation 4)

[0081] In other implementations, the presence of TATP can be detected based on the following steps or operations:

[0082] • Adsorb TATP (50 ppb) onto exposed carbon surfaces (300-700 μm) 2 On a carbon surface (C), an acid (such as HCl at a concentration level of approximately 0.1 mg) is added to make it acidic. An exemplary acid treatment level includes 10 mg of carbon (C) corresponding to 100 mg of HCl diluted in a suitable carrier solvent at a concentration of 0.1 mg. Over time, the adsorbed HCl evaporates and protonates the hydroxyl and / or carboxyl groups on the exposed carbon surface, making such surfaces relatively acidic.

[0083] TATP hydrolyzes into acetone and peroxide;

[0084] • Perform peroxide oxidation as shown in equations (1)-(3) above; and

[0085] • Observable changes that generate free electrons and one or more electrical or chemical characteristics of the sensing device.

[0086] In some implementations, cobalt-decorated CNO provides the most selective and sensitive response to triacetone triperoxide (TATP) compared to other types of 3D graphene-based sensing materials. The applicant notes that because hydrogen peroxide has a somewhat similar chemical structure to triacetone triperoxide (TATP) or tricycloacetone peroxide (TCAP), sensing devices configured to detect the presence of hydrogen peroxide can also be used to detect the presence of TATP.

[0087] The exact chemical reactivity and / or interaction between the analyte and the exposed carbon surface of materials 1251-1258 may depend on the type of analyte and the structure or organization of the corresponding materials 1251-1258. For example, some analytes, such as hydrogen peroxide (H2O2) and TATP, can be detected by one or more redox (“reduction”) type chemical reactions with metals decorated to the exposed carbon surface of sensing materials 1251-1258. In some implementations, some of the sensing materials 1251-1258 may be prepared or generated as including free amines that can react with electronically defective nitroaromatic analytes such as TNT and DNT.

[0088] Measurement circuit 630 measures the output signals provided by sensors 1201-1208 to determine the presence of certain analytes in the surrounding environment. For example, when sensor array 120 is subjected to electromagnetic signals (e.g., from sources such as...) Figure 4When an external device (receiving) a ping signal from the device 440, the measurement circuit can measure the frequency response of sensors 1201-1208 and compare the measured frequency response with one or more reference frequency responses. If the measured frequency response of sensor 120 matches a specific reference frequency response, the measurement circuit 630 can indicate the presence of an analyte associated with that specific reference frequency response. Conversely, if the measured frequency response of sensor 120 does not match any of the reference frequency responses, the measurement circuit 630 can indicate the absence of an analyte associated with that specific reference frequency response.

[0089] In another example, applying an alternating current to the sensor array 120 can cause one or more electrical and / or chemical characteristics of sensors 1201-1208 to change (e.g., increase or decrease). Measurement circuitry 630 can detect the resulting changes in the electrical and / or chemical characteristics of sensors 1201-1208 and can determine the presence of certain analytes based on these changes. In some implementations, measurement circuitry 630 can measure the output current of sensors 1201-1208 caused by the alternating current and can compare the measured output current with one or more reference currents to determine the presence of certain analytes. Specifically, if the measured output current of sensor 120 matches a particular reference current, measurement circuitry 630 can indicate the presence of an analyte associated with that particular reference current. Conversely, if the measured output current of sensor 120 does not match any of the reference currents, measurement circuitry 630 can indicate the absence of an analyte associated with that particular reference current.

[0090] In other implementations, measurement circuit 630 can measure the impedance or reactance of sensors 1201-1208 to alternating current and compare the measured impedance or reactance with one or more reference impedances or reactances to determine the presence of certain analytes. Specifically, if the measured impedance or reactance of sensor 120 matches a reference impedance or reactance, measurement circuit 630 can indicate the presence of an analyte associated with the reference impedance or reactance. Conversely, if the measured impedance or reactance of sensor 120 does not match any of the reference impedances or reactances, measurement circuit 630 can indicate the absence of an analyte associated with the reference impedance or reactance.

[0091] Figure 7A Another sensor array 700A according to some implementations is shown. As shown, the sensor array 700A includes a plurality of sensors 701-704 arranged in a planar manner, wherein each of the sensors 701-704 includes a different carbon-based sensing material. In some aspects, the sensors 701-704 may be Figure 1-3 and Figure 5-6An example of sensor 120. In other respects, sensors 701-704 may be... Figure 4 An example of sensor 434. Although Figure 7A Example 700A shows four sensors 701-704 arranged in a 2-row x 2-column array, but in other implementations, other numbers of sensors can be arranged in other suitable configurations.

[0092] Sensors 701-704 may include routing channels between various deposits of the carbon-based sensing material. These routing channels provide a path through which electrons can flow through sensors 701-704. The current generated by sensors 701-704 can be measured by ohmic contact with corresponding electrode pairs E1-E4. For example, the measurement value M1 of the first sensor 701 can be obtained through electrode pair E1, the measurement value M2 of the second sensor 702 can be obtained through electrode pair E2, the measurement value M3 of the third sensor 703 can be obtained through electrode pair E3, and the measurement value M4 of the fourth carbon-based sensor 704 can be obtained through electrode pair E4.

[0093] In various implementations, each of sensors 701-704 can be configured to react with and / or detect a corresponding analyte or group of analytes. For example, a first sensor 701 can be configured to react with or detect a first group of analytes in a coarse-grained manner, and a second sensor 702 can be configured to react with or detect a subset of the first group of analytes in a fine-grained manner. In some cases, sensors 701-704 can be printed onto a substrate using different carbon-based inks. Ohmic contacts can be used to capture measurements M1-M4 simultaneously or sequentially.

[0094] Figure 7B Another sensor array 700B is shown according to some implementations. Sensor array 700B includes multiple carbon-based sensors 701-704 arranged vertically or stacked on top of each other. In some aspects, sensors 701-704 may be... Figure 1-3 and Figure 5-6 An example of sensor 120. In other respects, sensors 701-704 may be... Figure 4 An example of sensor 434. Sensors 701-704 (and their corresponding sensing materials) may be sequentially deposited on each other to form a stacked array. In some cases, spacers (not shown for simplicity) may be provided between sensors 701-704. As discussed, sensors 701-704 may be functionalized with different materials and / or may comprise different types of carbon-based sensing materials, which may be printed onto a substrate or label in the form of continuous layers.

[0095] With the increasing demand for low-cost analyte sensors, reducing or even eliminating the need for electronic components in analyte sensors has become increasingly important. For example, the high cost of electronic components commonly found in conventional analyte sensors makes their widespread deployment in shipping containers, packaging, and envelopes impractical. Therefore, some implementations of the subjects disclosed herein can provide cost-effective solutions to the problem of monitoring the long-term presence of hazardous chemicals and gases (e.g., the various analytes described herein) in large quantities of shipping containers, packaging, and envelopes.

[0096] Figure 7C This is illustration 700C, depicting the printing of various sensing devices disclosed herein onto the surface of shipping containers, packages, or envelopes using an inkjet or bubble printhead 720 according to some implementations. Specifically, illustration 700C depicts a process that can be used to print multiple layers of different carbon-based sensing materials 711-714 onto a substrate 710. As shown, the printhead 720 can use a first carbon-based ink 721 to print a first layer 711 of the carbon-based sensing material onto the substrate 710, a second carbon-based ink 722 to print a second layer 712 of the carbon-based sensing material onto the substrate 710, a third carbon-based ink 723 to print a third layer 713 of the carbon-based sensing material onto the substrate 710, and a fourth carbon-based ink 724 to print a fourth layer 714 of the carbon-based sensing material onto the substrate 710. In some cases, the carbon-based inks 721-724 may be different from each other, for example, such that the resulting sensing material layers 711-714 are configured to react with and / or detect different analytes or different groups of analytes. The printhead 720 may also use ohmic ink 725 to print electrodes E1-E4 for the different sensing material layers 711-714 separately. Ohmic contacts can be printed onto the substrate 710 and / or portions of the sensing material layers 711-714 by multiple passes through the multi-nozzle printhead 720. In some implementations, the sensing device may include through-holes through which the resulting electrodes E1-E4 are accessible. In other implementations, other suitable mechanisms may be used to provide ohmic contacts for the electrodes E1-E4.

[0097] Figure 7DThis is illustration 700D depicting the printing of various sensing devices disclosed herein onto the surface of a shipping container, package, or envelope using a printhead 720 according to other implementations. Specifically, illustration 700D depicts a process that can be used to print multiple layers of different carbon-based sensing materials 711-714 arranged in a pyramidal configuration onto a substrate 710. Illustration 700D also depicts ohmic contacts 705 printed on the sensing material layers 711-714 using ohmic ink 725. In some aspects, different sizes and different exposed surface areas of the sensing material layers 711-714 can result in corresponding sensors having different electrical and / or chemical characteristics, which in turn can configure the corresponding sensors to react with and / or detect different types of analytes.

[0098] Additional details relating to the various carbon-based sensing materials, adjustment and calibration techniques that can be used to form the carbon-based sensors disclosed herein are summarized in Table 1 below.

[0099]

[0100] Table 1

[0101] As discussed, different materials can resonate at different frequencies, and many materials can resonate at different frequencies, depending on the presence of one or more analytes. In some implementations, the dielectric constant of the carbon-based sensing material described herein can be altered by exposing the material to ultraviolet (UV) radiation.

[0102] Figure 7E This is illustration 700E depicting ultraviolet radiation emitted towards sensor 701. As shown, an ultraviolet beam source 753 can be used to spray ultraviolet radiation towards sensor 701. The power and wavelength of the ultraviolet radiation can be controlled by a power control unit 751 and a wavelength control unit 752, respectively. In some implementations, adjusting the power level and / or wavelength of the ultraviolet radiation can change the dielectric constant of each of the sensing material layers 711-714. That is, after being bombarded with ultraviolet radiation, each of the sensing material layers 711-714 can resonate at a different frequency. In some aspects, the different dielectric constants of the sensing material layers 711-714 can be collectively referred to as dielectric constant gradient 725. Dielectric constant gradient 725 can correspond to a step gradient 761, a linear gradient 762, or a curved gradient 763.

[0103] Figure 8A flowchart 800 is shown depicting exemplary operation for manufacturing at least some of the sensing devices disclosed herein, according to several implementations. In various implementations, the dielectric constant of the carbon-based sensing material can be varied to induce a specific resonance signature in the carbon-based sensing material when it is exposed to certain analytes. In some cases, different portions of the carbon-based sensing material can be configured to have different dielectric constant values ​​specifically selected to induce specific resonant frequencies and / or resonant signatures. In particular, it is sometimes desirable for a first portion of the carbon-containing material to have a first dielectric constant that is tuned to resonate with a specific resonance signature when the first portion of the carbon-containing material absorbs a first target analyte, while a second portion of the carbon-containing material has a second dielectric constant that is tuned to resonate with a specific resonance signature when the second portion of the carbon-containing material absorbs a second target analyte.

[0104] The formation of different portions of a carbon-containing material with different dielectric constant values ​​can be accomplished using a combination of masking and ultraviolet (UV) treatment. At box 802, the carbon-containing material is deposited onto a substrate or electrode 811. At box 804, a UV-blocking mask is deposited or printed on top of the carbon-containing material. At box 806, the carbon-containing material is activated, for example, by bombardment with UV photons. This results in a first portion 8121 of the carbon-containing material having a first dielectric constant and a second portion 8122 of the carbon-containing material having a second dielectric constant different from the first dielectric constant. At box 808, the mask can be washed away, ablated, or otherwise removed. Two or more of the resulting analyte sensing devices can be used as multi-element, multi-analyte sensors and / or as highly sensitive analyte sensors. Furthermore, or alternatively, the resulting analyte sensing devices can be exposed to additional UV photon bombardment at box 810, for example, to further alter the portion of the carbon-containing material previously under the UV-blocking mask.

[0105] Some exemplary alternative implementations are summarized in Table 2 below:

[0106]

[0107]

[0108] Table 2

[0109] Figure 9Another sensor array 900 according to some implementations is shown. Sensor array 900 includes multiple layers 911-914 of individually functionalized carbon-containing materials. As shown, layers 911-914 are arranged sequentially to form a layer stack, with the first layer 911 disposed on a substrate 910. Each layer is formed by a corresponding individually functionalized carbon-containing matrix (such as carbon matrix 1, carbon matrix 2, carbon matrix 3, carbon matrix 4), wherein each individually functionalized carbon-containing matrix includes a corresponding additive (AD). The combination of carbon-containing matrix and additives can be selected based on the sensitivity of a specific target analyte to a particular combination.

[0110] When forming the analyte sensor array, different layers can be deposited using any known technique. Furthermore, each of the different layers can be configured to have a specific thickness. Strictly speaking, and as illustrated, the first deposited layer can have a first thickness 924 within a first range (such as 10 nm–100 nm), while another deposited layer can have a thickness within a different range (such as 500 nm–1,000 nm), and so on. The specific thickness of a particular layer can be selected based on any combination of the following:

[0111] • The characteristics of the additives in the specific layer, and / or

[0112] • Characteristics of the target analyte, and / or

[0113] • The components of the layer and their inherent binary-ternary interactions.

[0114] In some implementations, the open-pore structure of the carbon-based sensing materials disclosed herein allows certain analytes to more easily permeate the material and / or interact more easily with the carbon matrix within the material. Therefore, these openings can increase the sensitivity of the sensors disclosed herein to analytes compared to conventional analyte detection systems.

[0115] Figure 10A An exemplary sensor configuration 1000A is shown according to some implementations. According to some implementations, the sensor configuration 1000A includes a mapping between the sensors of an analyte detection system and various analytes. For example, Figure 1The 3D graphene-based sensing material of the carbon-based sensor 120 may be or include the carbon recipe shown in sensor configuration 1000A. That is, in a configuration where sensor array 120 includes eight carbon-based sensors 120, each sensor may have a corresponding carbon recipe, as shown in exemplary sensor configuration 1000A. For example, the first sensor may be CNO decorated with cobalt oxide (Co2O3) and produce a percentage change in current (%ΔI) and / or an increase in measured impedance of 9.26244% relative to an initial current (I0), etc. In this way, the carbon recipe of sensor configuration 1000A can be used to configure carbon-based sensors to detect and identify different analytes (such as TATP, DNT, H2S, etc.) based on the corresponding chemical fingerprint of the analyte, even at relatively low concentration levels. Therefore, the sensing device disclosed herein can be able to detect relatively low concentrations of analytes and / or other chemical threats, even in the presence of common interfering agents.

[0116] Figure 10B Another exemplary sensor configuration 1000B is shown, based on some implementation methods. Sensor configuration 1000B can be similar to... Figure 10A The sensor is configured as 1000A, for example, such that:

[0117] Sensor #1: Carbon #29, corresponding to carbon nano-onion (CNO) oxide produced in the thermal reactor; Cobalt(II) acetate (C4H6CoO4), the cobalt salt of acetate (commonly found as tetrahydrate Co(CH3CO2)2·4H2O, abbreviated as Co(OAc)2·4H2O), flows into the thermal reactor at a rate of approximately 59.60 wt%, corresponding to 40.40 wt% carbon (referring to carbon in the form of CNO), resulting in cobalt functionalization of active sites on the CNO oxide, as shown at 15,000x and 100,000x levels, respectively; A suitable gas mixture for producing carbon #29 and / or cobalt-decorated CNO may include the following steps:

[0118] • Ar purging at 0.75 standard cubic feet per minute (scfm) for 30 minutes;

[0119] • Runtime Ar purge changed to 0.25 scfm;

[0120] • Heating: 25°C to 300°C, 20 minutes; and

[0121] • Heating: 300℃-500℃, 15 minutes.

[0122] Sensor #2: Corresponds to TG JM (thermal graphene jet milling; thermal reactor carbon unfunctionalized), such as Figure 11A As shown.

[0123] Sensor #3: Carbon #19, corresponding to "DXR" (such as...) generated in a microwave reactor (e.g., a reactor coupled to a microwave source, allowing microwave energy to propagate through the reactor, thereby exciting carbon-containing gases and / or plasma inside the reactor). Figure 5 Carbon of type or configuration (characterized by A and / or 5B); silver acetate (CH3CO2Ag), a white crystalline solid particulate matter suspended in a carrier gas to produce silver acetate vapor, flows into the microwave reactor at a rate of approximately 58.18 wt%, corresponding to 41.82 wt% carbon (referring to carbon in DXR form), resulting in silver functionalization of active sites on the DXR-configured carbon, such as... Figure 11D (undecorated form) and / or Figure 11G (This is essentially shown in the illustration of actual decoration using cobalt instead of silver.) Used to produce... Figure 11D and 11G The exemplary gas mixture of carbon #19 and / or silver-decorated DXR carbon shown in the figure may include the following steps:

[0124] • The carrier gas flowed on the DXR carbon structure at a volume ratio of 6.7% H2 / 93.3% Ar for approximately 1 minute and 8 seconds.

[0125] Sensor #4: CNO (carbon nano-onion; unfunctionalized carbon in thermal reactor), such as Figure 11B As shown.

[0126] Sensor #5: Carbon #16, corresponding to "DXR" generated in the microwave reactor (e.g., Figure 5 Carbon of type or configuration (characterized by A and / or 5B); ferric acetate (II), a white solid particulate matter suspended in a carrier gas to produce ferric acetate vapor, flows into the microwave reactor at a rate of approximately 65.17 wt%, corresponding to 34.83 wt% carbon (referring to carbon in DXR form), resulting in silver functionalization of active sites on the DXR-configured carbon, such as... Figure 11D (undecorated form) and / or Figure 11G (This is essentially shown in the illustration of actual decoration using cobalt instead of iron.) Used to produce... Figure 11D and 11G The exemplary gas mixture of carbon #16 and / or iron-decorated DXR carbon shown in the figure may include the following steps:

[0127] • The carrier gas flowed on the DXR carbon structure at a volume ratio of 6.7% H2 / 93.3% Ar for approximately 1 minute and 13 seconds.

[0128] Sensor #6: Carbon #1, corresponding to the "Anvel" produced in the microwave reactor (e.g., ... Figure 7CThe carbon of the type or configuration characterized; bis(acetylacetone)platinum(II), a coordination compound having the formula Pt(O2C5H7)2, abbreviated as Pt2, flows as particulates dispersed in a carrier gas to generate bis(acetylacetone)platinum(II) vapor, which flows into the microwave reactor at a ratio of approximately 76.62 wt%, corresponding to 23.38 wt% carbon (referring to carbon in the Anvel configuration), resulting in the platinum functionalization of the active sites on the Anvel configuration carbon, such as Figure 11C (Undecorated form) is basically shown; used to produce in Figure 11C A suitable gas mixture of carbon #1 and / or undecorated Anvel carbon, substantially as shown in the figure, may include the following steps:

[0129] • The carrier gas flowed over the Anvel carbon structure at a volume ratio of 6.7% H2 / 93.3% Ar for approximately 15 minutes.

[0130] Sensor #7: Carbon #6, corresponding to the "Anvel" produced in the microwave reactor (e.g., ...). Figure 7C Carbon of the type or configuration characterized by; palladium(II) acetate, a carbon derived by the formula [Pd(O2CCH3)2] n The chemical compound describing palladium is abbreviated as [Pd(OAc)2]. n As particulate matter dispersed in a carrier gas, it flows to generate palladium(II) acetate vapor, which flows into the microwave reactor at a rate of approximately 65.17 wt%, corresponding to 34.83 wt% carbon (referring to carbon in the Anvel configuration), resulting in platinum functionalization of the active sites on the Anvel-configured carbon, such as... Figure 11C (Undecorated form) is basically shown. Used to produce in Figure 11C An exemplary gas mixture of carbon #6 and / or palladium-decorated Anvel carbon, substantially as shown in the figure, may include the following steps:

[0131] • The carrier gas flowed over the Anvel carbon structure at a volume ratio of 6.7% H2 / 93.3% Ar for approximately 15 minutes.

[0132] Sensor No. 8: 1,3-diaminonaphthalene composite with TG-JM, such as Figure 11A As shown, this is to produce organically modified carbon.

[0133] Figure 11A-11G Illustrations show various structured carbon materials that can be used in the sensing devices disclosed herein, according to some implementation methods. For example, Figure 11A Photographs 1100A of thermogravimetric (TG) carbon according to various implementation methods are shown. Figure 11B Photograph 1100B of an undecorated CNO according to various implementations is shown. Figure 11C Photographs of Anvel carbon 1100C are shown according to various implementations. Figure 11D The image shows a 1100D photomicrograph of DXR carbon according to various implementations. Figure 11E Photograph 1100E of CNO with cobalt decoration according to various implementations is shown at a magnification level of 15,000x. Figure 11F Photomicrograph 1100F of CNO with cobalt decoration according to various implementations is shown at a magnification level of 100,000x. Figure 11G Micrographs of DXR carbon with cobalt decoration according to various implementations are shown. (1100G)

[0134] Compared to conventional 2D graphene materials, the 3D graphene sensing material disclosed in this invention can be designed with a convolutional 3D structure to prevent graphene recombination, thereby avoiding several drawbacks of using 2D graphene as a sensing material. This process also increases the areal density of the material, generating more analyte adsorption sites per unit area, thus improving chemical sensitivity. This can be achieved through a library of carbon allotropes used to customize the sensor array disclosed herein for chemical fingerprinting of leaked analytes for a variety of applications.

[0135] Figure 11A-11G The structured carbon materials shown can be produced using a flow-through microwave plasma reactor configured to continuously produce pristine 3D graphene particles from hydrocarbon gases under near-atmospheric pressure conditions. Operationally, as hydrocarbons flow through the relatively hot zone of the plasma reactor, free carbon radicals are formed. These radicals flow further down the length of the reactor into a growth zone, where 3D carbon particles (based on multiple interconnected 2D graphene particles) are formed and collected as fine powder. The density and composition of the gaseous class of free radical carbon can be tuned via gas chemistry and microwave (MW) power levels. By controlling reactor process parameters, these reactors can produce carbon with a wide but tunable range of morphologies, crystallization sequences, and sizes (and distributions). For example, possible sizes and distributions can range from flakes (hundreds of nanometers to micrometers wide and a few nanometers thin) to spherical particles (tens of nanometers in diameter) to graphene clusters (tens of micrometers). The 3D nature of the material effectively prevents agglomeration, allowing the material to disperse as unagglomerated particles. Therefore, highly responsive and selective sensing materials can be produced. Graphene, an atomically thin two-dimensional (2D) material, has many advantageous properties for sensing, including excellent chemical and mechanical strength, high carrier mobility, high electrical conductivity, high surface area, and gate-tunable carrier density.

[0136] To improve chemoselectivity, the 3D graphene disclosed in this invention can be functionalized with various reactive materials in ways that optimize the binding of target molecules and carbon. This functionalization step, along with the ability to measure the complex impedance of the exposed sensor, can be crucial for the efficient and selective detection of analytes. For example, different metal nanoparticles or metal oxide nanoparticles can be decorated on the surface of the 3D graphene to selectively detect hydrogen peroxide (a TATP degradation product), since peroxides are known to react with different metals. Furthermore, the nanoparticle-decorated graphene structures can synergistically provide desired and advantageous properties for sensing applications.

[0137] Figure 12A-12F Exemplary frequency responses of resonant impedance sensors to various analytes are shown according to some implementations. Specifically, Figure 12A An exemplary frequency response 1200A of sensor 120 and a baseline or reference frequency response are shown. Specifically, Figure 12A An exemplary frequency response 1200A of sensor 120 to acetone and a baseline or reference frequency response are shown. Figure 12B An exemplary frequency response 1200B of sensor 120 to acetonitrile and a baseline or reference frequency response are shown. Figure 12C An exemplary frequency response 1200C of sensor 120 to ethanol and a baseline or reference frequency response are shown. Figure 12D An exemplary frequency response 1200A of sensor 120 to isopropanol and a baseline or reference frequency response are shown. Figure 12E An exemplary frequency response 1200E of the sensor 120 to water and a baseline or reference frequency response are shown. Figure 12F An exemplary frequency response 1200F of the sensor 120 to xylene and a baseline or reference frequency response are shown.

[0138] Figure 13A Figure 1300A depicts the real (Z′) impedance components of the exemplary frequency response of sensor 120 to acetone, ethanol (EtOH), water, and hydrogen peroxide (H2O2) and the baseline or reference frequency response, according to some implementations. Figure 13B Figure 1300B depicts the exemplary frequency response of sensor 120 to acetone, ethanol (EtOH), water, and hydrogen peroxide (H2O2), as well as the virtual (Z”) impedance component of the baseline or reference frequency response, according to some implementations.

[0139] Figure 14A Exemplary frequency responses of sensor 120 to hydrogen peroxide, as well as baseline or reference frequency responses, are shown according to some implementations. Figure 14B The following illustrates an exemplary frequency response of sensor 120 to acetone and water, according to some implementations. Figure 14CExemplary frequency responses to ethanol and ammonia are shown according to some implementations.

[0140] As used herein, the terms “at least one” or “one or more” in the list of references refer to any combination of those items, including a single member. For example, “at least one of a, b, or c” is intended to cover the following possibilities: only a, only b, only c, a combination of a and b, a combination of a and c, a combination of b and c, and a combination of a, b, and c.

[0141] The various illustrative components, logic, logic blocks, modules, circuits, operations, and algorithmic processes described in conjunction with the implementation methods disclosed herein can be implemented as electronic hardware, firmware, software, or a combination of hardware, firmware, or software, including the structures disclosed in this specification and their structural equivalents. The interchangeability of hardware, firmware, and software has been generally described in terms of functionality, and has been illustrated in the various illustrative components, blocks, modules, circuits, and processes described above. Whether this functionality is implemented in hardware, firmware, or software depends on the application and the design constraints imposed on the system as a whole.

[0142] Various modifications to the implementations described herein will be readily apparent to those skilled in the art, and the general principles defined herein can be applied to other implementations without departing from the spirit and scope of this disclosure. Therefore, the claims are not intended to be limited to the implementations shown herein, but rather to be made within the broadest scope consistent with the disclosure, principles, and novel features disclosed herein.

[0143] Furthermore, the various features described in this specification in the context of independent implementations can also be implemented in combination in a single implementation. Conversely, the various features described in the context of a single implementation can also be implemented individually or in any suitable sub-combination in multiple implementations. Therefore, although features may be described above as combinations of each other, and even initially claimed in this way, in some cases, one or more features from the claimed combination may be removed from said combination, and the claimed combination may be for sub-combinations or variations thereof.

[0144] Similarly, although the operations are depicted in a specific order in the accompanying drawings, this should not be construed as requiring such operations to be performed in the specific order shown or sequentially, or that all shown operations be performed to achieve the desired result. Furthermore, the drawings may schematically depict another exemplary process in the form of a flowchart or diagram. However, other operations not depicted may be incorporated into the schematically illustrated exemplary process. For example, one or more additional operations may be performed before, after, simultaneously with, or between any of the illustrated operations. In some cases, multitasking and parallel processing may be advantageous. Moreover, the separation of various system components in the above implementations should not be construed as requiring such separation in all implementations, and it should be understood that the described program components and systems can generally be integrated together in a single software product or packaged into multiple software products.

Claims

1. A container for storing one or more items, the container comprising: The surface that defines the volume of the container; and A label printed on the container, the label comprising: substrate; Multiple carbon-based sensors, printed on the substrate and configured to detect the presence of one or more analytes within the container, each configured to react with a unique set of analytes in response to an electromagnetic signal received from an external device, wherein the carbon-based sensors are functionalized with carbon materials configured to detect the presence of the analytes; and One or more electrodes, printed on the substrate and coupled to at least some of the carbon-based sensor, are configured to provide one or more output signals indicating the presence or absence of the one or more analytes in the container. in, The first carbon-based sensor is functionalized with a first material configured to detect the presence of each analyte in the first analyte group; and The second carbon-based sensor is functionalized with a second material configured to detect the presence of each analyte in a second analyte group, wherein the second analyte group comprises a subset of the first analyte group, and the second material is different from the first material.

2. The container of claim 1, wherein the carbon-based sensor is configured to resonate at different frequencies in response to the electromagnetic signal.

3. The container of claim 1, wherein each output signal includes the frequency response of a corresponding carbon-based sensor to the electromagnetic signal.

4. The container of claim 1, further comprising an antenna printed on the substrate, the antenna being configured to drive current through the carbon-based sensor in response to the electromagnetic signal.

5. The container of claim 4, wherein each output signal indicates the impedance or reactance of the corresponding carbon-based sensor to the current, the impedance or reactance indicating the presence or absence of at least one analyte from the corresponding unique analyte group.

6. The container of claim 1, wherein the first analyte group comprises at least twice the number of different analytes as the second analyte group.

7. The container of claim 1, wherein the first material comprises cobalt-decorated carbon nanotubes configured to detect the presence of one or more of triacetone triperoxide, toluene, ammonia, or hydrogen sulfide; and the second material comprises an iron-decorated three-dimensional graphene structure configured to confirm the presence of toluene.

8. The container of claim 1, wherein the third carbon-based sensor is functionalized with a third material configured to detect the presence of each analyte in the third analyte group, wherein the third analyte group comprises another subset of the first analyte group, and the third material is different from the first material and the second material.

9. The container as claimed in claim 1, wherein: The first carbon-based sensor's first frequency response to the electromagnetic signal indicates the presence or absence of the analytes from the first analyte group within the container; and The second carbon-based sensor's second frequency response to the electromagnetic signal indicates whether the analytes of the second analyte group are present or absent in the container.

10. The container of claim 9, wherein the first frequency response is based at least in part on the first carbon-based sensor being exposed to the electromagnetic signal for a continuous first time period, and the second frequency response is based at least in part on the second carbon-based sensor being exposed to the electromagnetic signal for a continuous second time period longer than the first time period.

11. The container of claim 10, wherein the length of the second time period is at least twice that of the first time period.

12. The container of claim 10, wherein the one or more electrodes comprise: A first electrode, coupled to the first carbon-based sensor and configured to indicate the presence of one or more analytes from the first analyte group; as well as A second electrode is coupled to the second carbon-based sensor and configured to confirm the presence of an analyte detected by the first carbon-based sensor.

13. The container of claim 1, wherein the first carbon-based sensor and the second carbon-based sensor form a dielectric constant gradient.

14. The container of claim 1, wherein the substrate comprises paper or a flexible polymer.

15. The container of claim 1, wherein each of the carbon-based sensors comprises a different carbon-based ink printed on the substrate.

16. The container of claim 1, wherein each of the carbon-based sensors comprises a plurality of different graphene allotropes.

17. The container of claim 16, wherein the various graphene allotropes of the respective carbon-based sensors include one or more microporous or mesoporous pathways.

18. The container of claim 16, wherein each of the carbon-based sensors comprises a polymer configured to bond the various graphene allotropes to one another.

19. The container of claim 18, wherein the plurality of different graphene allotropes include at least one of graphene sheets or carbon nanotubes.

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