Patent Publication Number: US-2023135555-A1

Title: Flexible Sweat-Activated Graphene-Coated Ni foam-based Mg-O2 Battery for Stretchable Microelectronics for Continuous Biomarker Monitoring

Description:
TECHNICAL FIELD 
     The present invention is related to a flexible sweat-activated battery capable of powering an intelligent and flexible electronics for health monitoring purposes. 
     BACKGROUND 
     According to a statistics report, the wearable segment has projected revenue of US$17,834m in 2021, with an expected annual growth rate of 0.04%. The wearable segment includes devices equipped with sensors to track activity and health, which are explicitly intended for fitness. 
     There are many commercially available wearable devices, but most of them need a coin-cell or thin-film battery to power their system. These traditional batteries are classified as hazardous material, and there are certainly safety concerns for using them in contact with human skin. Additionally, they are not stretchable or flexible. 
     Certain academic publications introduce a biofluid-activated source of energy. While the choice of substrate varied, the reported batteries were flexible and biocompatible. The biofluids used for activation included sweat, blood, urine, saliva, and simulated body fluids, depending on whether the battery would be used to power external wearable electronics or implantable bioelectronics. 
     Among the reported batteries, the choice of anode, cathode, and electrolyte differed, leading to varying electrical performances. One of the batteries was sweat-activated with Mg anode, Ag/AgCl cathode, and an operating voltage of ˜1.6V. Another biofluid-activated micro battery reported 1.75V maximum output voltage, 7.17 μAh capacity, 46% maximum efficiency. An open circuit potential of 2.2V and 3.0 mW/cm 2  power density was reported in a paper-based galvanic cell with Mg foil anode and Ag foil cathode in cellulose chip. 
     Aside from biofluid-activated energy sources, other Mg-air batteries with various fabrication techniques and morphologies have also been reported. One Mg-air battery was made from a porous Mg thin film with an open-circuit voltage of 1.41V and a discharge capacity of 821 mA·h·g −1 . Another bioelectric thin-film battery with a silk fibroin-polypyrrole film cathode and Mg alloy anode in PBS electrolyte was reported to have a specific energy density of ˜4.70 mW·h·cm −2 . An Mg-air battery synthesized from Mg sea-urchin-like nanostructures had an energy density of 565 W·h·kg −1  at discharge current density 5 mA/cm 2  and an open-circuit voltage of 1.4V. However, the reported batteries still have many difficulties to apply to many wearable devices in the market in view of their energy sources, structures, materials used and/or limited output power. 
     A need therefore exists for an improved battery for wearable devices that eliminates or at least diminishes the disadvantages and problems described above. 
     SUMMARY 
     The present disclosure proposes a stretchable and flexible sweat-activated graphene-coated Ni foam-based Mg—O 2  battery capable of powering an intelligent and flexible electronics for health monitoring purposes with different biosensors. 
     The proposed battery in certain embodiments is based on the oxidation-reduction reaction (redox) between magnesium and oxygen. A thin layer of Mg and a nickel foam coated with graphene are working as the electrodes. Cotton with high absorption capabilities is placed between the Mg sheet and the skin, helping to absorb the sweat. Another cotton doped with KCl is placed between two electrodes. It works as the salt bridge and allows ion flow once it absorbs the sweat. A porous adhesive tape is a substrate for the battery parts while allowing the oxygen to pass through it easily. 
     Provided herein is a first fabric layer arranged to cover a skin of a user and used for absorbing sweat from the skin; a magnesium (Mg) sheet; a salt-doped fabric layer comprising a second fabric layer doped with particles of a potassium salt or a sodium salt, the Mg sheet being located between the first fabric layer and the salt-doped fabric layer, the first fabric layer and the salt-doped fabric layer being arranged to be partially overlapped for allowing the salt-doped fabric layer to absorb sweat from the first fabric layer; a graphene-coated Ni foam comprising a Ni foam and a graphene layer covering the Ni foam, the graphene layer being located between the Ni foam and the salt-doped fabric layer; and a porous tape covering the Ni foam and comprising pores for allowing oxygen from environment to flow into the Ni foam. 
     In certain embodiments, the first fabric layer comprises cotton, spandex, nylon or linen. 
     In certain embodiments, the second fabric layer comprises cotton, spandex, nylon or linen. 
     In certain embodiments, the potassium salt is potassium chloride (KCl). 
     In certain embodiments, the sodium salt is sodium chloride (NaCl). 
     In certain embodiments, the Mg sheet is connected to a first conductive wire; and the Ni foam is connected to a second conductive wire. 
     In certain embodiments, the porous tape further comprises a central portion and a peripheral portion, the central portion covering the Ni foam, the peripheral portion being arranged to be attached to the skin. 
     In certain embodiments, the porous tape further comprises an adhesive surface for attaching the porous tape to the Ni foam and the skin. 
     Provided herein is a wearable device for measuring one or more biomarkers comprising: one or more sensors for measuring the one or more biomarkers respectively; a microcontroller for collecting data of the one or more sensors; and one or more flexible sweat-activated batteries described above for powering the microcontroller. 
     In certain embodiments, the one or more biomarkers include body temperature, pulse rate (PR), exercise intensity, peripheral capillary oxygen saturation (SpO 2 ), or a combination thereof. 
     In certain embodiments, the one or more sensors include a temperature sensor, a PR sensor, an accelerometer, a SpO 2  sensor, or a combination thereof. 
     In certain embodiments, the wearable device further comprises: a voltage regulator connected to the one or more flexible sweat-activated batteries for providing a stable voltage to the microcontroller; a Bluetooth module for allowing the microcontroller to send the collected data to a user interface; and a flexible printed circuit board, on which the microcontroller, the voltage regulator, the Bluetooth module are mounted. 
     In certain embodiments, the one or more flexible sweat-activated batteries are configured to provide a voltage of 2.5V to 5.2V; and the voltage regulator is configured to provide the stable voltage with 3.3V. 
     In certain embodiments, the one or more flexible sweat-activated batteries include four flexible sweat-activated batteries. 
     In certain embodiments, the wearable device further comprises: a first flexible layer arranged to cover a skin of the user; and a second flexible layer, the flexible printed circuit board being located between the first flexible layer and the second flexible layer. 
     In certain embodiments, the first flexible layer comprises a hole accommodating the one or more sensors. 
     In certain embodiments, the wearable device further comprises: two conductive wires for connecting the one or more flexible sweat-activated batteries to the flexible printed circuit board; and a flexible substrate comprising one or more holes accommodating the one or more flexible sweat-activated batteries. 
     In certain embodiments, the user interface is a smartphone application contained in a smartphone. 
     This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter. Other aspects of the present invention are disclosed as illustrated by the embodiments hereinafter. 
    
    
     
       BRIEF DESCRIPTION OF DRAWINGS 
       The appended drawings, where like reference numerals refer to identical or functionally similar elements, contain figures of certain embodiments to further illustrate and clarify the above and other aspects, advantages and features of the present invention. It will be appreciated that these drawings depict embodiments of the invention and are not intended to limit its scope. The invention will be described and explained with additional specificity and detail through the use of the accompanying drawings in which: 
         FIG.  1 A  shows an exploded view of the layer-by-layer structure of a flexible sweat-activated battery (FSAB) according to certain embodiments; 
         FIG.  1 B  shows a flexible Ni foam covered by a layer of graphene; 
         FIG.  1 C  shows scanning electron microscope (SEM) images of a graphene layer on a Ni foam (left) and a Ni foam without graphene (right); 
         FIG.  1 D  shows the FSAB attached to the user&#39;s forearm; 
         FIG.  1 E  shows the working principle of the FSAB; 
         FIG.  2 A  shows the open-circuit output voltage of the FSABs with and without a graphene layer on a Ni foam; 
         FIG.  2 B  shows the open-circuit output voltage of the FSABs for Mg sheets with different thicknesses; 
         FIG.  2 C  shows the open-circuit output voltage of the FSABs for pieces of cotton with different thicknesses; 
         FIG.  2 D  shows the open-circuit output voltage of the FSAB as a proportion of its maximum output voltage by increasing the artificial sweat rate in a battery cell; 
         FIG.  2 E  shows the power density of the FSAB; 
         FIG.  2 F  shows the output voltage of the FSAB based on its discharging capacity; 
         FIG.  2 G  shows the output voltage of the FSAB during twisting cycles with different angles; 
         FIG.  2 H  shows the output voltage of the FSAB during bending cycles with different angles; 
         FIG.  2 I  shows the FSAB&#39;s capacity in different ambient temperatures; 
         FIG.  3 A  shows an exploded view of a wearable device represented layer by layer according to certain embodiments. 
         FIG.  3 B  shows four FSABs on a 8 cm×8 cm flexible substrate connected to a soft microelectronic patch with 3 cm×3 cm; 
         FIG.  3 C  shows the flexibility of the soft microelectronic patch under pressure; 
         FIG.  3 D  shows the diagram of the wearable device&#39;s working principle; 
         FIG.  3 E  shows output signals of the accelerometer sensor for different positions, including squatting, jumping, running, sitting, and walking, while the proposed wearable device is attached to three different places on the body; 
         FIG.  3 F  shows a comparison between the body temperature measured by the proposed wearable device and a commercial device; 
         FIG.  3 G  shows a comparison between user&#39;s pulse rate measured by the proposed wearable device and a commercial device; 
         FIG.  3 H  shows a comparison between user&#39;s SpO 2  measured by the proposed wearable device and a commercial device; 
         FIG.  4 A  shows a user wearing the proposed wearable device, connected to a smartphone through Bluetooth, while he is walking; 
         FIG.  4 B  shows output signals of the integrated sensors recorded by the proposed wearable device and transmitted to the smartphone during the user&#39;s exercise; and 
         FIG.  4 C  shows a measurement of different biomarkers by the proposed wearable device, at the beginning of exercise and one hour after it, in three different subjects. 
     
    
    
     Skilled artisans will appreciate that elements in the figures are illustrated for simplicity and clarity and have not necessarily been depicted to scale. 
     DETAILED DESCRIPTION OF THE INVENTION 
     It will be apparent to those skilled in the art that modifications, including additions and/or substitutions, may be made without departing from the scope and spirit of the invention. Specific details may be omitted so as not to obscure the invention; however, the disclosure is written to enable one skilled in the art to practice the teachings herein without undue experimentation. 
     The present disclosure proposes a flexible sweat-activated battery comprising highly biocompatible materials and flexible substrates. As a result, using this flexible sweat-activated battery does not have any safety concerns in contact with human skin. 
     The flexible sweat-activated battery is a graphene-paper based Mg—O 2  battery, which is sweat-activated and can power any skin-interfaced external wearables. The flexible sweat-activated battery uses an Mg sheet as the anode, oxygen as cathode, and graphene sheet as a catalyst. Two FSABs provide a voltage of 1.8-3V to power the stretchable microelectronic circuit. Problems like electrolyte leakage are mitigated due to the dry nature of the proposed FSAB. Also, they are flexible, stretchable, and biocompatible. Hence, they can conveniently power skin-interfaced wearable electronics. 
     Certain embodiments provide a first fabric layer arranged to cover a skin of a user and used for absorbing sweat from the skin; a Mg sheet; a salt-doped fabric layer comprising a second fabric layer doped with particles of a potassium salt or a sodium salt, the Mg sheet being located between the first fabric layer and the salt-doped fabric layer, the first fabric layer and the salt-doped fabric layer being arranged to be partially overlapped for allowing the salt-doped fabric layer to absorb sweat from the first fabric layer; a graphene-coated Ni foam comprising a Ni foam and a graphene layer covering the Ni foam, the graphene layer being located between the Ni foam and the salt-doped fabric layer; and a porous tape covering the Ni foam and comprising pores for allowing oxygen from environment to flow into the Ni foam. 
     In certain embodiments, the first fabric layer comprises cotton, spandex, nylon or linen, and the second fabric layer comprises cotton, spandex, nylon or linen. 
     In certain embodiments, the potassium salt is neutral and not irritating to the skin. Preferably, the potassium salt is potassium chloride. 
     In certain embodiments, the sodium salt is neutral and not irritating to the skin. Preferably, the sodium salt is sodium chloride. 
     Certain embodiments provide a flexible sweat-activated battery comprising: a first cotton layer arranged to cover on a skin of a user; a Mg sheet; a potassium chloride (KCl)-doped cotton layer comprising a second cotton layer doped with KCl particles, the Mg sheet being located between the first cotton layer and the KCl-doped cotton layer; a graphene-coated Ni foam comprising a Ni foam and a graphene layer covering the Ni foam, the graphene layer being located between the Ni foam and the KCl-doped cotton layer; and a porous tape covering the Ni foam and comprising pores for allowing oxygen from environment to flow into the Ni foam. 
     In certain embodiments, the Mg sheet is connected to a first conductive wire; and the Ni foam is connected to a second conductive wire. 
     In certain embodiments, the porous tape further comprises a central portion and a peripheral portion, the central portion covering the Ni foam, the peripheral portion being arranged to be attached to the skin. 
     In certain embodiments, the porous tape further comprises an adhesive surface for attaching the porous tape to the Ni foam and the skin. 
     The present disclosure further proposes a wearable device for measuring biomarkers comprising flexible sweat-activated batteries described above, biosensors and flexible electronics powered by the flexible sweat-activated batteries in order to monitor health. Through the biosensors, a lot of physiologically relevant information (e.g., sodium concentration of sweat, pH of sweat, skin impedance) can be gleaned through sweat analysis. An added advantage is that the collection is completely non-invasive and skin safe. Once the flexible sweat-activated batteries absorb sweat from the human body, they activate and power the flexible electronics in order to measure proper biomarkers. 
     Certain embodiments provide a wearable device for measuring one or more biomarkers comprising: one or more sensors for measuring the one or more biomarkers respectively; a microcontroller connected to the one or more sensors and used for collecting data of the one or more sensors; and one or more flexible sweat-activated batteries described above for powering the microcontroller. 
     In certain embodiments, the wearable device includes a stretchable microelectronic circuit fabricated on a soft substrate, containing different sensors to measure proper acceleration, peripheral capillary oxygen saturation, pulse rate, and body temperature, and sweat-activated batteries to provide power to the circuit. 
     In certain embodiments, the wearable device includes flexible smart electronics, four FSABs, an accelerometer, a SpO 2  sensor, a PR sensor and a temperature sensor. The wearable device monitors the subject&#39;s health using these sensors. It also contains a Bluetooth module, allowing the wearable device to communicate with a smartphone to display the collected data. 
     In certain embodiments, all parts of the wearable device, including FSABs, flexible electronic circuits, and sealing layers, are integrated into one patch, such that the user can conveniently use the wearable device during exercise or other physical activities. 
     As shown in  FIG.  1 A , a FSAB  100  according to certain embodiments is fabricated layer by layer. The FSAB  100  comprises a cotton layer  110 , a Mg sheet  120 , a KCl-doped cotton layer  130 , a graphene-coated nickel (Ni/G) foam  140  and a porous tape  150 , which are stacked together. The first layer that sits on a skin  160  is the cotton layer  110  (1 cm×3 cm) with high water absorption capability. The cotton layer  110  absorbs the secreted sweat on the skin  160 . The next layer is the Mg sheet  120  (slight less than 1 cm×3 cm) working as an anode. The KCl-doped cotton layer  130  covering the Mg sheet  120  is a layer of cotton  131  doped with KCl particles  132  (shown in the right inset of  FIG.  1 A ), which acts as the electrolyte layer and separator between anode and cathode. The KCl particles  132  are neutral salt particles with neutral character and not irritating to the skin as well as can provide better electrical performance than other salts. The areas of the cotton layer  110  and the KCl-doped cotton layer  130  are larger than that of the Mg sheet  120  such that the cotton layer  110  and the KCl-doped cotton layer  130  are partially overlapped at their periphery for allowing the KCl-doped cotton layer  130  to absorb the sweat from the cotton layer  110 . Once the absorbed sweat reaches the KCl-doped cotton layer  130 , the absorbed sweat allows ions (e.g., hydroxide ions) to flow between the Mg anode and oxygen cathode, functioning as an electrolyte. The next layer is the graphene-coated nickel foam  140  comprising a Ni foam  141  and a graphene layer  142  covering the Ni foam  141  (shown in the left inset of  FIG.  1 A ). The Ni foam  141  is open-celled and acts a current collector and a gas diffusion layer. The graphene layer  142  is located between the Ni foam  141  and the KCl-doped cotton layer  130 . The oxygen from the environment reduces in the graphene layer  142 , the graphene of which acts as a catalyzing agent. The porous structure of the Ni foam  141  results in a significantly increased contact area between graphene and oxygen. As a result, the FSAB  100  yields remarkably better performance. Finally, a porous tape  150  with pores  151  and an adhesive surface on its bottom side is used as the substrate to hold the battery parts together. The porosity of the porous tape  150  allows the flow of oxygen atoms from the environment to the Ni foam  141 . The porous tape  150  further comprises a central portion  152  and a peripheral portion  153 , the central portion  152  covers the Ni foam  141 , the peripheral portion  153  is attached to the skin  160 . 
     The total redox reaction between magnesium and oxygen is as follows: 
       2Mg(s)+O 2 (g)+2H 2 O( l )→2Mg(OH) 2 (aq)
 
     Magnesium oxidizes and loses two electrons, forming Mg 2+  ions. As a result, the oxidation half-reaction is as follows: 
       Mg(s)→Mg 2+ (aq)+2 e   − (Oxidation half-reaction)
 
     In Ni foam, oxygen atoms form hydroxide. As a result, oxygen reduces, and the reduction half-reaction is as follows: 
       O 2 (g)+2H 2 O( l )+4 e   − →4OH − (aq)(Reduction half-reaction)
 
     A nickel foam covered by graphene and its flexibility is demonstrated in  FIG.  1 B . SEM images of the graphene layer and Ni foam are shown in  FIG.  1 C . Optical images of a flexible sweat-activated battery while being used on the user&#39;s forearm are demonstrated in  FIG.  1 D . 
     The working principle of the flexible sweat-activated battery described above is shown in  FIG.  1 E . In step S1, the skin  160  secrete sweat  161 . In step S2, when the cotton layer  110  is in contact with the skin  160 , the cotton layer  110  absorbs the sweat  161 . In step S3, the KCl-doped cotton layer  130  absorbs the sweat  161  from the cotton layer  110 . In step S4, oxygen  170  from the environment flows into the Ni foam of the Ni/G foam  140  via the pores of the porous tape  150 . Then, the Mg sheet  120  oxidizes and release electrons and Mg 2+  ions, and the oxygen  170  in the Ni foam reduces under the assistance of the graphene layer of the Ni/G foam  140  and reacts with H 2 O to form OH −  ions such that a voltage is generated between the Mg sheet  120  and the oxygen  170  in the Ni foam. 
       FIGS.  2 A- 2 I  show the electrical performance of the flexible sweat-activated battery. The open-circuit output voltage of the battery is compared when the graphene covers the Ni foam and the graphene is not used.  FIG.  2 A  shows that the use of graphene results in a higher and more stable output voltage. The thickness of the Mg sheet directly influences the battery lifespan. The higher the Mg sheet thickness is, the longer battery can work as shown in  FIG.  2 B . The current measurements have been done while the battery is connected to a 2.5 resistance as the load. According to  FIG.  2 C , different layers of cotton with different thicknesses have been tested. With a thinner cotton layer, the battery works longer. As it is shown in  FIG.  2 D , once the sweat rate reaches 0.025 mL/cm 2 , the battery activates. The output voltage reaches its maximum when the secreted sweat is 0.1 mL/cm 2  or more. The battery&#39;s power density and discharging capacity have been tested and presented in  FIG.  2 E  and  FIG.  2 F , respectively. Accordingly, the maximum power density is 16.26 mW·cm −2 . The open-circuit output voltage of the battery has been measured through consecutive twisting cycles.  FIG.  2 G  shows the performance of the battery when it is twisted for 30°, 60°, and 90°. Twisting cycles and the recovery period are labeled in the graph, proving the reliable and stable performance of the battery under twisting.  FIG.  2 H  similarly shows the battery performance in different bending cycles when it is bent by different angles between 30° and 180°. The battery capacity has also been measured in different temperatures. In room temperature, the battery shows the best performance as shown in  FIG.  2 I . 
       FIGS.  3 A and  3 B  show a wearable device  300  for measuring biomarkers comprising a battery patch  310  and a soft microelectronic patch  320  with layer-by-layer structure according to certain embodiments. The battery patch  310  comprises a soft PDMS substrate  311  and four FSABs  312  accommodated in the holes of the soft PDMS substrate  311 , and the four FSABs  312  are connected to the soft microelectronic patch  320  through two thin wires  313  as shown in  FIG.  3 B . The battery patch  310  with four FSABs  312  is 8 cm×5 cm, and the soft microelectronic patch  320  occupies an area of 3 cm×3 cm. The soft microelectronic patch  320  comprises a flexible printed circuit board  321 , a microcontroller  322 , a voltage regulator  323 , a Bluetooth module  324 , an accelerometer  331 , a SpO 2  sensor  332 , a pulse rate sensor  333 , a temperature sensor  334 , a top PDMS layer  341  and a bottom PDMS layer  342 . The microcontroller  322 , the voltage regulator  323 , the Bluetooth module  324  and the accelerometer  331  are mounted on the flexible printed circuit board  321 , which is sandwiched by the top PDMS layer  341  and the bottom PDMS layer  342 . The SpO 2  sensor  332 , the pulse rate sensor  333 , the temperature sensor  334  are accommodated in a hole  343  of bottom PDMS layer  342  for being in contact with a skin to measure the biomarkers.  FIG.  3 C  shows the flexibility of the soft microelectronic patch. 
     The diagram in  FIG.  3 D  explains the working principle of the wearable device  300 . The FSABs  312  are connected to the voltage regulator  323  on the flexible printed circuit board  321  for providing a stable 3.3V voltage for the microcontroller  322 . The microcontroller  322  is connected to the aforesaid biosensors and collects the data. The microcontroller  322  sends the collected data through the Bluetooth module  324  to a user interface  350 , which is a smartphone app in this embodiment. 
       FIG.  3 E  shows the accelerometer&#39;s output signals for different positions while the wearable device is attached to three different places, including the back, leg, and arm. The body temperature measured by the proposed wearable device is compared to results from a commercial sensor.  FIG.  3 F  shows these temperature measurements, which evidence the excellent compatibility between the results. Pulse rate and SpO 2  have been measured simultaneously using the proposed wearable device and a commercial one. Results are reported in  FIG.  3 G  and  FIG.  3 H , respectively, showing the excellent performance of the proposed wearable device. 
     In order to show the performance of the proposed wearable device in a real-life situation, a user wear the proposed wearable device on his arm while walking as shown in  FIG.  4 A . A smartphone application is developed which is connected to the proposed wearable device and reads sensors&#39; data. The output signals of all sensors, including accelerometer, pulse rate, body temperature, and SpO 2 , are presented in  FIG.  4 B . Moreover, three different subjects used the proposed wearable device while exercising. They have self-reported their exercise intensity by a factor of 1. Sensors&#39; data are collected at the beginning and one hour after exercising. As it has been shown in  FIG.  4 C , the temperature and pulse rate of all subjects have increased after one hour of exercise. The percentage of oxygen saturation has also been measured and reported. 
     Thus, it can be seen that an improved battery and wearable device have been disclosed which eliminates or at least diminishes the disadvantages and problems associated with prior art devices. The proposed battery is a biocompatible and flexible sweat-activated battery that can be activated by the secreted sweat from the human body during any physical activities. Accordingly, the proposed battery has a wide variety of applications in wearable electronics. The flexible sweat-activated battery can power wearable microelectronics in order to measure biomarkers. The proposed flexible microelectronics can be used for monitoring acceleration, SpO 2 , PR and temperature for any individuals engaged in physical activities. Accordingly, the proposed wearable device can be used by any users working in healthcare facilities, sports centres, fitness rooms, and any other individual who has physical activities in their daily life. 
     Although the invention has been described in terms of certain embodiments, other embodiments apparent to those of ordinary skill in the art are also within the scope of this invention. Accordingly, the scope of the invention is intended to be defined only by the claims which follow.