CN113178606B - Flexible wearable composite energy collecting device and manufacturing method and application thereof - Google Patents
Flexible wearable composite energy collecting device and manufacturing method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N1/00—Electrostatic generators or motors using a solid moving electrostatic charge carrier
- H02N1/04—Friction generators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/40—Combination of fuel cells with other energy production systems
- H01M2250/402—Combination of fuel cell with other electric generators
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Abstract
The invention belongs to the technical field of flexible wearable electronic equipment, and particularly relates to a flexible wearable composite energy collecting device and a manufacturing method and application thereof, wherein the flexible wearable composite energy collecting device is formed by seamlessly assembling a flexible wearable friction nano generator and a flexible wearable lactate enzyme biofuel cell, the lactase biofuel cell belongs to one end close to human skin, and comprises a polydimethylsiloxane flexible shell, a lactase/three-dimensional multilevel structure graphene anode, a reduced oxygen precious metal/three-dimensional multilevel structure graphene cathode and a hydrogel electrolyte, the flexible wearable friction nano generator comprises a flexible polymer/nano carbon material composite electrode/flexible polymer composite film and a nano carbon material composite electrode/flexible polymer composite film with a supporting framework; the problem that sweat influences the performance of the wearable friction nanometer generator is solved by the flexible wearable combined type energy collecting device.
Description
Technical Field
The invention belongs to the technical field of flexible wearable electronic equipment, and particularly relates to a flexible wearable composite energy collecting device and a manufacturing method and application thereof.
Background
In recent years, electronic technologies gradually develop towards micro integration, function intellectualization, wireless mobility and full self-driving, the demand of people on wearable and ubiquitous intelligent equipment is continuously increased, and a large number of wearable electronic equipment is widely applied in the world. Generally, one of the most common methods of providing power to these electronic devices is to install a battery. However, batteries have a limited life span, and as the number of electronic devices increases, it becomes more difficult to replace, manage and/or recycle a large number of batteries, and in order to solve these problems, a triboelectric nano-generator (TENG) has come to be a device that can convert environmental mechanical energy into electrical energy. The working principle is based on the coupling effect of the triboelectric effect and the electrostatic induction effect. The emergence of TENG provides a new breakthrough for the development of wearable electronic equipment, so that the wearable electronic equipment obtains more stable, safe and high-conversion-efficiency energy, and very convenient experience is brought to the life and work of people.
The wearable friction nano-generator reported at present shows great application potential under experimental conditions, but some objective factors must be considered when facing practical application. For example, a healthy person may have a daily perspiration volume of about 600 ml without exercising. The perspiration amount of people who do strenuous exercise or work in a high-temperature environment for a long time can reach about 2000 ml per hour. A large amount of sweat forms a humid human environment, which reduces the friction effect and affects the generation of surface charges of the wearable friction nano-generator, thereby affecting the overall output performance of the device.
However, it is noteworthy that sweat itself is also a source of energy. For example, lactic acid, which is an organic substance having a large sweat content, can be used as a raw material for a biofuel cell to generate electricity. The biofuel cell is mainly composed of three parts: biological anode, biological cathode, electrolyte. At present, wearable biofuel cells which take lactic acid in sweat as raw materials are reported, the output of the wearable biofuel cells reaches 1.2mW/cm, and the wearable biofuel cells can provide energy for LED lamps and Bluetooth low-energy-consumption radios. The enzyme biofuel cell has the advantages of high catalytic efficiency on raw materials, good long-term working stability, environmental friendliness, good biocompatibility and the like.
Based on the principle of the biofuel cell, the sweat-free wearable friction nano-generator is expected to solve the problem that the performance of the wearable friction nano-generator is affected by sweat. Currently, there is no report on a composite energy collection device integrating a biofuel cell and a wearable friction nano-generator.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the flexible wearable composite energy collecting device and the manufacturing method thereof, the flexible wearable composite energy collecting device can simultaneously collect human body movement energy and sweat biological energy, the manufacturing method is simple and easy to operate, the problem that the sweat influences the performance of the wearable friction nano-generator is solved, and a new way is provided for solving the energy supply problem of the wearable electronic device.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a flexible wearable composite energy collecting device, which is formed by seamlessly assembling a flexible wearable friction nano-generator and a flexible wearable lactase biofuel cell.
Preferably, the lactase biofuel cell belongs to one end close to the skin of a human body, and comprises a polydimethylsiloxane flexible shell, a lactase/graphene anode with a three-dimensional multilevel structure, a reduced oxygen precious metal/graphene cathode with a three-dimensional multilevel structure and a hydrogel electrolyte, the polydimethylsiloxane flexible shell is provided with an accommodating cavity, the inner bottom surface of the polydimethylsiloxane flexible shell is provided with a groove, the lactase/three-dimensional multilevel structure graphene anode and the reduced oxygen precious metal/three-dimensional multilevel structure graphene cathode are symmetrically arranged in the groove, the groove is also filled with the hydrogel electrolyte, the top surface and the side surface of the polydimethylsiloxane flexible shell are both provided with a series of micropores, the side surface of the groove is provided with a micro-flow channel which communicates the side surface micropores with the groove;
the flexible wearable friction nano-generator belongs to the other end far away from the skin of a human body and comprises a flexible polymer/nano-carbon material composite electrode/flexible polymer composite film and a nano-carbon material composite electrode/flexible polymer composite film, wherein the nano-carbon material composite electrode/flexible polymer composite film is provided with a polydimethylsiloxane support framework, the polydimethylsiloxane support framework is a series of support blocks made of polydimethylsiloxane, the series of support blocks are connected end to end at the peripheral edge of one side face of the nano-carbon material composite electrode/flexible polymer composite film to form a uncovered cavity structure, and the face with the support framework in the nano-carbon material composite electrode/flexible polymer composite film is vertically connected with the flexible polymer/nano-carbon material composite electrode/flexible polymer composite film, the flexible wearable friction nanometer generator with the middle air layer is formed.
The flexible polymer/nano carbon material composite electrode/flexible polymer composite membrane end face of the flexible wearable friction nano generator and the end face of the flexible wearable enzyme biofuel cell without micropores are seamlessly assembled to form the flexible wearable composite energy collecting device.
Preferably, the microwells include top microwells and side microwells. The top micropores are used for collecting fresh sweat secreted by a human body, and the side micropores are used for discharging waste sweat used by the enzyme biofuel cell. In addition, the microfluidic channel is used for draining waste sweat out of the device.
The second purpose of the invention is to provide a manufacturing method of the flexible wearable composite energy collecting device, which comprises the following steps:
s1, spin-coating a layer of flexible polymer on the surface of the copper foil with the nano-carbon material, and etching the copper foil after curing; dispersing another nano carbon material on the nano carbon material to obtain a nano carbon material composite electrode, spin-coating a layer of flexible polymer on the surface of the nano carbon material composite electrode, and curing to obtain a flexible polymer/nano carbon material composite electrode/flexible polymer composite film;
s2, dispersing another nano carbon material on the surface of the copper foil with the nano carbon material growing on the surface, spin-coating a layer of flexible polymer, and etching the copper foil after curing to obtain the nano carbon material composite electrode/flexible polymer composite film;
s3, casting a polydimethylsiloxane support framework on the surface of the nano-carbon material composite electrode side of the nano-carbon material composite electrode/flexible polymer composite film in the step S2, wherein the support framework is a series of support blocks, the series of support blocks are connected end to end at the peripheral edge of one side face of the nano-carbon material composite electrode/flexible polymer composite film to form a uncovered cavity structure, and curing to obtain the nano-carbon material composite electrode/flexible polymer composite film with the polydimethylsiloxane support framework;
s4, assembling the flexible polymer/nano-carbon material composite electrode/flexible polymer composite film obtained in the step S1 and the side, provided with the supporting framework, of the nano-carbon material composite electrode/flexible polymer composite film provided with the polydimethylsiloxane supporting framework obtained in the step S3 through oxygen plasma auxiliary reaction to obtain a flexible wearable friction nano-generator;
s5, preparing the three-dimensional multilevel structure graphene electrode by using a plasma-assisted chemical vapor deposition method;
s6, preparing polydimethylsiloxane into a square structure with a containing cavity by a template method, preparing a series of micropores on the top surface and the side surfaces of the polydimethylsiloxane, forming a groove on the inner bottom surface of the polydimethylsiloxane, and arranging a microfluidic channel on the side surface of the groove, wherein the microfluidic channel connects the micropores on the side surface with the groove to obtain a polydimethylsiloxane flexible shell;
s7, dripping a suspension solution of carbon nanotubes and tetrathiafulvalene on the three-dimensional multi-level structure graphene electrode obtained in the step S5, drying in the air, dripping a lactic acid enzyme solution, drying in the air again, and covering a layer of highly crosslinked chitosan biopolymer to obtain a lactic acid enzyme/three-dimensional multi-level structure graphene anode;
s8, dropping and coating a suspension solution of carbon nanotubes and reduced oxygen precious metal powder on the three-dimensional multi-level structure graphene electrode in the step S5, airing, and then covering a layer of water-soluble perfluorosulfonic acid polymer to obtain a reduced oxygen precious metal/three-dimensional multi-level structure graphene cathode;
s9, placing the anode in the step S7 and the cathode in the step S8 into corresponding grooves of the lower surface component, and then injecting hydrogel electrolyte into the grooves to obtain the flexible wearable enzyme biofuel cell;
s10, seamlessly assembling the end face of the flexible polymer/nano carbon material composite electrode/flexible polymer composite membrane of the flexible wearable friction nano generator and the end face of the flexible wearable enzyme biofuel cell without micropores into a whole through oxygen plasma assisted reaction to obtain the flexible wearable composite energy collecting device.
The invention provides a flexible wearable composite energy collecting device based on a flexible wearable friction nano generator and a lactase biofuel cell, wherein a lactase biofuel cell component adopts self-supporting three-dimensional multilevel structure graphene as an electrode framework, and a carbon nano tube is attached to the framework; the friction nanometer generator part adopts a nanometer carbon material composite electrode which has the advantages of good flexibility, conductivity, chemical inertia, small thickness and the like, can meet the requirements of wearable devices, can ensure stable electric output of the generator, and can still keep high electric output under the actual application conditions of the generator such as human body sweating; meanwhile, the friction nanometer generator component adopts an auxiliary electrode vertical movement working mode which has higher electric output, and the generator component is of a closed hollow structure, so that the interference and influence of external conditions can be reduced as much as possible; the flexible wearable composite energy collecting device can collect human body movement energy and sweat biological energy at the same time, solves the problem that the sweat influences the performance of the wearable friction nano generator, provides a new way for solving the energy supply problem of the wearable electronic device, and can be applied to wearable electronic products.
Preferably, the nanocarbon materials of steps S1 and S2 include, but are not limited to, graphene, carbon nanotubes, bucky paper, carbon nanodots. Further, the nanocarbon material composite electrode described in steps S1 and S2 is a graphene and carbon nanotube composite electrode, bucky paper and carbon nanodot composite electrode.
Preferably, the flexible polymer in steps S1 and S2 includes, but is not limited to, Polydimethylsiloxane (PDMS), Polyurethane (PU), Ecolfelx. Further, the flexible polymer in steps S1 and S2 is PDMS or PU.
Preferably, the lactic acid enzyme in step S7 includes, but is not limited to, lactate oxidase, lactate dehydrogenase.
Preferably, the reduced oxygen precious metal of step S8 includes, but is not limited to, Pt, Pd, Ru, Ag, or oxides thereof. Further, the reduced oxygen precious metal in step S8 is silver oxide or platinum sheet.
Preferably, the hydrogel electrolyte (14) of step S9 includes, but is not limited to, a lactic acid solution. Further, the lactic acid solution had a molarity of 20 mM.
The third purpose of the invention is to provide the application of the flexible wearable composite energy collecting device in wearable electronic products.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a flexible wearable composite energy collecting device and a manufacturing method thereof, wherein the flexible wearable composite energy collecting device is formed by seamlessly assembling a flexible wearable friction nano generator and a flexible wearable lactic acid enzyme biofuel cell, wherein the lactic acid enzyme biofuel cell belongs to one end close to the skin of a human body; the flexible wearable composite energy collecting device is good in flexibility, light and thin in fit with skin, capable of adapting to skin strain of a human body, capable of keeping high electric output in a humid environment such as a sweat environment, and capable of supplying energy to a wearable electronic product by using collected electric energy (capable of collecting human motion energy and sweat bioenergy at the same time); the manufacturing method is simple and easy to operate, and not only solves the problem that sweat influences the performance of the wearable friction nano generator, but also provides a new way for solving the energy supply problem of wearable electronic devices.
Drawings
Fig. 1 is a schematic structural diagram of a flexible wearable composite energy harvesting device;
fig. 2 is a schematic structural diagram of a flexible wearable lactase biofuel cell;
FIG. 3 is a schematic structural diagram of a flexible wearable friction nano-generator;
fig. 4 is an open circuit voltage test chart of the flexible wearable composite energy collection device of example 1;
fig. 5 is a short circuit current test chart of the flexible wearable composite energy collection device of example 1;
fig. 6 is a power density versus open circuit voltage curve for the flexible wearable composite energy harvesting device of example 1.
In the figure, 1-flexible wearable lactase biofuel cell, 2-flexible wearable friction nano generator, 11-polydimethylsiloxane flexible shell, 12-lactate oxidase/three-dimensional multilevel structure graphene anode, 13-silver oxide/three-dimensional multilevel structure graphene cathode, 14-hydrogel electrolyte, 15-micropore, 21-polydimethylsiloxane/graphene and carbon nano tube composite electrode/polydimethylsiloxane composite membrane, and 22-graphene and carbon nano tube composite electrode/polydimethylsiloxane composite membrane with polydimethylsiloxane support framework.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
Embodiment 1A flexible wearable composite energy collection device and a manufacturing method thereof
The flexible wearable composite energy collecting device is formed by seamlessly assembling a flexible wearable friction nano-generator 2 and a flexible wearable lactase biofuel cell 1;
the lactate enzyme biofuel cell 1 belongs to one end close to human skin, the lactate enzyme biofuel cell 1 comprises a polydimethylsiloxane flexible shell 11, a lactate oxidase/three-dimensional multi-level structure graphene anode 12, a silver oxide/three-dimensional multi-level structure graphene cathode 13 and a hydrogel electrolyte 14(20mM lactic acid solution), a containing cavity (cuboid structure with the size of 8mM multiplied by 1mM and the wall thickness of 1mM) is formed in the polydimethylsiloxane flexible shell 11, a groove (cuboid structure with the size of 6mM multiplied by 1mM) is formed in the inner bottom surface of the polydimethylsiloxane flexible shell 11, the lactate oxidase/three-dimensional multi-level structure graphene anode 12 (with the size of 2mM multiplied by 6mM multiplied by 0.1mM) and the silver oxide/three-dimensional multi-level structure graphene cathode 13 (with the size of 2mM multiplied by 6mM multiplied by 0.1mM) are symmetrically placed in the groove, the grooves are also filled with the hydrogel electrolyte 14, and the top surface and the side surface of the polydimethylsiloxane flexible shell 11 are both provided with a series of micropores 15 (which are divided into top micropores and side micropores, and have a diameter of 0.5mm), wherein the top micropores are used for collecting sweat, and the side micropores are used for discharging waste liquid. Meanwhile, a micro-flow channel (with the diameter of 1mm) is further arranged in the polydimethylsiloxane flexible shell 11, and the micro-flow channel is communicated with the side micropores 15 and the grooves to help discharge waste liquid.
The flexible wearable friction nano-generator 2 belongs to the other end far away from the skin of a human body, the flexible wearable friction nano-generator 2 comprises a polydimethylsiloxane/graphene and carbon nano-tube composite electrode/polydimethylsiloxane composite film 21 (the thickness is 2mm) and a graphene and carbon nano-tube composite electrode/polydimethylsiloxane composite film 22 (the thickness is 1mm), the graphene and carbon nano-tube composite electrode/polydimethylsiloxane composite film 22 is provided with a polydimethylsiloxane supporting framework, the polydimethylsiloxane supporting framework is a series of supporting blocks, the series of supporting blocks are connected end to end at the peripheral edge of one side surface of the graphene and carbon nano-tube composite electrode/polydimethylsiloxane composite film 22 to form an uncovered cavity structure (cuboid structure), and the polydimethylsiloxane and carbon nano-tube composite electrode/polydimethylsiloxane composite film 22 is provided with a polydimethylsiloxane structure The side of the siloxane supporting framework is vertically connected with a polydimethylsiloxane/graphene and carbon nano tube composite electrode/polydimethylsiloxane composite membrane 21 to form a flexible wearable friction nano generator with an air layer supported by the polydimethylsiloxane supporting framework in the middle;
the end face of the polydimethylsiloxane/graphene and carbon nanotube composite electrode/polydimethylsiloxane composite membrane 21 of the flexible wearable friction nano generator 2 and the end face of the flexible wearable enzyme biofuel cell 1 without micropores are seamlessly assembled to form a flexible wearable composite energy collecting device.
The manufacturing method comprises the following steps:
(1) cutting a copper foil with the size of 10mm multiplied by 10mm and with graphene, spin-coating a layer of polydimethylsiloxane on the surface of the copper foil, standing for 1h at the temperature of 80 ℃, and etching the copper foil after the copper foil is solidified; dispersing 8mg of carbon nanotubes on the graphene to obtain a graphene/carbon nanotube composite electrode, spin-coating a layer of polydimethylsiloxane on the surface of the graphene/carbon nanotube composite electrode, standing for 1h at 80 ℃, and curing to obtain the polydimethylsiloxane/graphene and carbon nanotube composite electrode/polydimethylsiloxane composite membrane 21.
(2) Cutting a copper foil with the size of 10mm multiplied by 10mm and graphene growing on the copper foil, dispersing 8mg of carbon nano tubes on the surface of the copper foil, spin-coating a layer of polydimethylsiloxane, standing for 1h at 80 ℃, and etching away the copper foil after the copper foil is cured to obtain the graphene and carbon nano tube composite electrode/polydimethylsiloxane composite film 22.
(3) And (3) the surface of the graphene and carbon nanotube composite electrode/polydimethylsiloxane composite film 22 in the step (2) exposed out of the graphene/carbon nanotube electrode faces upwards, a polydimethylsiloxane support framework is poured (the polydimethylsiloxane support framework is a series of support blocks, and the series of support blocks are connected end to end at the peripheral edge of one side surface of the graphene and carbon nanotube composite electrode/polydimethylsiloxane composite film 22 to form an uncovered cuboid structure with the thickness of 1mm and the height of 2mm), and the graphene and carbon nanotube composite electrode/polydimethylsiloxane composite film 22 with the polydimethylsiloxane support framework is obtained by standing for 1h at 80 ℃.
(4) And (3) assembling the polydimethylsiloxane/graphene and carbon nanotube composite electrode/polydimethylsiloxane composite film 21 obtained in the step (1) and the graphene and carbon nanotube composite electrode/polydimethylsiloxane composite film 22 with the supporting framework obtained in the step (3) through oxygen plasma-assisted reaction to obtain the flexible wearable friction nano-generator 2.
The specific method of the assembly is as follows: and respectively sending the polydimethylsiloxane/graphene and carbon nano tube composite electrode/polydimethylsiloxane composite film 21 and the graphene and carbon nano tube composite electrode/polydimethylsiloxane composite film 22 with the supporting framework into a P15 plasma cleaning machine for treatment for 5-10min, performing oxygen plasma surface modification, and enabling the modified polydimethylsiloxane to become hydrophilic, so that the two layers of polydimethylsiloxane of the polydimethylsiloxane/graphene and carbon nano tube composite electrode/polydimethylsiloxane composite film 21 can be directly bonded with the polydimethylsiloxane supporting framework of the graphene and carbon nano tube composite electrode/polydimethylsiloxane composite film 22.
(5) And preparing the graphene electrode with the three-dimensional multilevel structure of 10mm multiplied by 10mm by using a plasma-assisted chemical vapor deposition method.
The preparation method comprises the following specific steps: cutting copper foil into 1 × 1cm2The method comprises the following steps of putting the uniform square blocks into beakers containing acetic acid solution, absolute ethyl alcohol solution and acetone solution, cleaning for 5min by ultrasonic waves (power 120W and frequency 40kHz) respectively, taking the blocks out by using tweezers, completely drying the surfaces of copper sheets by using an air gun, putting the copper sheets into a porcelain boat, sending the copper sheets into an auxiliary CVD (chemical vapor deposition) device, introducing argon inert gas to completely discharge air in a furnace body before introducing reaction gas, introducing argon and hydrogen, starting a program to heat up, starting to grow a graphene film after reaching 700 ℃, reacting for 180s to obtain the graphene film, and finally performing a traditional wet method (reference document): preparation of graphene [ D ] at low temperature by aid of Lihanyun plasma-assisted CVD (chemical vapor deposition) method]China university of Petroleum (Beijing) transfer exfoliated graphene to obtain a required graphene electrode of a three-dimensional multilevel structure.
(6) The polydimethylsiloxane is prepared into a square structure with a containing cavity by a template method, a series of micropores 15 are prepared on the top surface and the side surfaces of the polydimethylsiloxane, a groove is formed in the inner bottom surface of the polydimethylsiloxane, and a series of microflow channels communicated with the micropores 15 on the side surfaces of the groove are arranged on the side surfaces of the groove to obtain the polydimethylsiloxane flexible shell 11.
The preparation method comprises the following specific steps: a groove with the size of 10mm multiplied by 3mm is etched on an acrylic plate by adopting a laser cutting machine, a cuboid with the size of 8mm multiplied by 1mm is placed in the middle of the groove, a small cuboid with the size of 6mm multiplied by 1mm is placed on the cuboid, 25 silver needles with the diameter of 0.5mm (used for preparing top micropores) are vertically placed above the small cuboid, 4 silver needles with the diameter of 1mm (used for preparing micro-flow channels) are respectively and horizontally placed on four side faces of the small cuboid, the diameter of the silver needles is shrunk to 0.5mm (used for preparing side micropores) at the connecting part of the silver needles and the acrylic plate, and polydimethylsiloxane solution (SYLGARD 184SILICONE Elastomer Base, purchased from Shanghai Enlai trade Limited) and Curing Agent (SYLGARD SILICONE Elastomer Agent) are mixed according to 10: 1 into the template to fill the groove with the solution, then placing the solution into an oven to dry for one night at 40 ℃, taking out the solution and demoulding to obtain the square polydimethylsiloxane flexible shell 11 with the groove.
(7) Uniformly dripping a suspension solution of carbon nano Tubes and Tetrathiafulvalene (TTF) (60 mg of carbon nano tube powder is dissolved in 20mM tetrathiafulvalene solution to obtain the suspension solution) on the three-dimensional multi-stage structure graphene electrode in the step (1), after the suspension solution is dried in the air, uniformly dripping an lactate oxidase solution (25 mg of lactate oxidase is dissolved in 417 mu L of 0.01M phosphate solution, 6.25mg of bovine serum albumin is added to ensure the activity of the lactate oxidase, uniformly stirring to obtain 60mg/mL lactate oxidase solution), after the suspension solution is dried in the air, immersing the three-dimensional multi-stage structure graphene electrode into a chitosan solution (a solution is obtained after chitosan molecules are highly self-crosslinked by taking glutaraldehyde as a crosslinking agent), and specifically, the preparation method comprises the steps of uniformly mixing 0.01g of 1mL of 0.1M acetic acid solution of chitosan and 1mL of 1% glutaraldehyde solution to obtain the chitosan/mL of the three-dimensional multi-stage structure graphene electrode, and taking out and drying for 1h after 30s, so that a layer of highly crosslinked chitosan biopolymer is covered on the electrode attached with the enzyme, and obtaining the lactate oxidase/three-dimensional multi-level structure graphene anode 12.
(8) Uniformly dropping a suspension solution of carbon nanotubes and silver oxide powder on the three-dimensional multi-level structure graphene electrode obtained in the step (1) (40 mg of silver oxide powder and 20mg of carbon nanotube powder are dissolved in 2mL of 1% Nafion solution, stirring for 2h after ultrasonic treatment for 30min to obtain a required suspension solution), soaking the three-dimensional multi-level structure graphene electrode into 1% of perfluorosulfonic acid (Nafion) solution after the suspension solution is dried, taking out and drying for 1h after 30s, covering a layer of water-soluble Nafion polymer on the composite electrode, and obtaining the silver oxide/three-dimensional multi-level structure graphene cathode 13.
(9) And (3) placing the anode 12 in the step (7) and the cathode 13 in the step (8) into corresponding grooves of the polydimethylsiloxane flexible shell 11, and then injecting a 20mM lactic acid solution into the grooves to obtain the flexible wearable enzyme biofuel cell 1.
(10) And (3) seamlessly assembling the side of the polydimethylsiloxane/graphene and carbon nanotube composite electrode/polydimethylsiloxane composite membrane 21 of the flexible wearable friction nano generator 2 and the opening end face of the accommodating cavity of the flexible wearable enzyme biofuel cell 1 into a whole through oxygen plasma-assisted reaction to obtain the flexible wearable composite energy collecting device.
The seamless assembly specifically comprises: and respectively feeding the flexible wearable friction nano generator 2 and the flexible wearable enzyme biofuel cell 1 into a P15 plasma cleaning machine for treatment for 5-10min, carrying out oxygen plasma surface modification, and enabling the modified polydimethylsiloxane to become hydrophilic, so that the polydimethylsiloxane/graphene and carbon nano tube composite electrode/polydimethylsiloxane composite membrane 21 part of the flexible wearable friction nano generator 2 can be directly bonded with the opening end face of the accommodating cavity of the flexible wearable enzyme biofuel cell 1.
One end of a positive lead and a negative lead is inserted between the composite electrodes of the friction nano generator 2 of the flexible wearable composite energy collecting device, the other end of the positive lead and the negative lead is connected with an electrometer (Keithley 6514, KEITHLEY, Taeke science and technology (China) Co., Ltd.), certain frequency and pressure are applied to the friction nano generator 2 through flapping of human hands, generated electric signals are captured by the electrometer and an acquisition card, and then the electric signals are transmitted to a computer through a cable to obtain open-circuit voltage and output charge signals. As can be seen from fig. 4 and 5, the friction nanogenerator can output a voltage of 1.8V and an output charge of 1.3 nC.
The enzyme biofuel cell 1 of the flexible wearable composite energy collecting device is attached to the skin of a human body, one end of a positive lead and a negative lead is inserted between a positive electrode and a negative electrode of the enzyme biofuel cell, the other end of the positive lead and the negative lead is connected with an electrochemical workstation (MAC90304, Metrohm, Wantong China, Inc., Switzerland), under the condition that the human body sweats, sweat flows into the enzyme biofuel cell through micropores 15 to cause an electrochemical reaction, and the power density versus open-circuit voltage curve of the enzyme biofuel cell is measured by a linear scanning voltammetry. As can be seen from FIG. 6, the power generated by the enzyme biofuel cell was 42 mW.cm-3The voltage was 0.35V.
In conclusion, the electric energy collected by the friction nano generator and the enzyme biofuel cell of the flexible wearable composite energy collection device is respectively stored in the corresponding capacitors and is compounded through the rectifier, so that the power can be supplied to the small electronic equipment.
Embodiment 2A flexible wearable composite energy collecting device and a manufacturing method thereof
The structure and the preparation method are substantially the same as those of the embodiment 1, and the difference is that: structurally, the flexible wearable friction nano-generator 2 comprises a polyurethane/bucky paper and carbon nano-point composite electrode/polyurethane composite film 21 and a bucky paper and carbon nano-point composite electrode/polyurethane composite film 22 with a polydimethylsiloxane supporting framework; in terms of the preparation method, the graphene material in the step (1) and the step (2) of the embodiment 1 is changed into the bucky paper, the carbon nanotube material is changed into the carbon nanodots, and the polydimethylsiloxane is changed into the Polyurethane (PU).
Through detection, the friction nano generator and the enzyme biofuel cell of the flexible wearable composite energy collection device can collect electric energy.
Embodiment 3A flexible wearable composite energy collection device and a manufacturing method thereof
The structure and the preparation method are substantially the same as those of the embodiment 1, and the difference is that: structurally, the anode 12 is a lactate dehydrogenase/three-dimensional multi-level structure graphene anode, and the cathode 13 is a platinum/three-dimensional multi-level structure graphene cathode 13; in terms of the preparation method, lactate oxidase materials in the steps (7) and (8) of example 1 were changed to lactate dehydrogenase, and silver oxide materials were changed to platinum sheets (Pt).
Through detection, the friction nano generator and the enzyme biofuel cell of the flexible wearable composite energy collection device can collect electric energy.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (8)
1. A flexible wearable composite energy collection device is characterized in that the flexible wearable composite energy collection device is formed by seamlessly assembling a flexible wearable friction nano-generator (2) and a flexible wearable lactase biofuel cell (1);
the lactase biofuel cell (1) belongs to one end close to human skin, the lactase biofuel cell (1) comprises a polydimethylsiloxane flexible shell (11), a lactase/three-dimensional multi-level structure graphene anode (12), a reduced oxygen precious metal/three-dimensional multi-level structure graphene cathode (13) and a hydrogel electrolyte (14), the polydimethylsiloxane flexible shell (11) is of a square structure with a containing cavity, a groove is formed in the inner bottom surface of the polydimethylsiloxane flexible shell (11), the lactase/three-dimensional multi-level structure graphene anode (12) and the reduced oxygen precious metal/three-dimensional multi-level structure graphene cathode (13) are symmetrically arranged in the groove, the hydrogel electrolyte (14) is filled in the groove, and series of micropores (15) are formed in the top surface and the side surface of the polydimethylsiloxane flexible shell (11), the side surface of the groove is provided with a micro-flow channel which communicates the series of micropores (15) of the side surface with the groove;
the flexible wearable friction nano-generator (2) belongs to the other end far away from the skin of a human body, the flexible wearable friction nano-generator (2) comprises a flexible polymer/nano-carbon material composite electrode/flexible polymer composite film (21) and a nano-carbon material composite electrode/flexible polymer composite film (22), the nano-carbon material composite electrode/flexible polymer composite film (22) is provided with a polydimethylsiloxane supporting framework, the polydimethylsiloxane supporting framework is a series of supporting blocks made of polydimethylsiloxane materials, the series of supporting blocks are connected end to end at the peripheral edges of one side surface of the nano-carbon material composite electrode/flexible polymer composite film (22) to form a uncovered cavity structure, and the side with the supporting framework in the nano-carbon material composite electrode/flexible polymer composite film (22) and the flexible polymer/nano-carbon material composite electrode The flexible polymer composite films (21) are vertically connected to form a flexible wearable friction nano generator (2) with an air layer in the middle;
and (3) seamlessly assembling the side of the flexible polymer/nano carbon material composite electrode/flexible polymer composite membrane (21) of the flexible wearable friction nano generator (2) and the bottom surface without micropores of the flexible wearable enzyme biofuel cell (1) through oxygen plasma-assisted reaction to form the flexible wearable composite energy collecting device.
2. The method of making a flexible wearable composite energy harvesting device of claim 1, comprising the steps of:
s1, spin-coating a layer of flexible polymer on the surface of the copper foil with the nano-carbon material, and etching the copper foil after curing; dispersing another nano carbon material on the nano carbon material to obtain a nano carbon material composite electrode, spin-coating a layer of flexible polymer on the surface of the nano carbon material composite electrode, and curing to obtain a flexible polymer/nano carbon material composite electrode/flexible polymer composite film (21);
s2, dispersing another nano carbon material on the surface of the copper foil on which the nano carbon material grows, spin-coating a layer of flexible polymer, and etching away the copper foil after curing to obtain the nano carbon material composite electrode/flexible polymer composite film (22);
s3, casting polydimethylsiloxane support skeletons on the surface of the side, where the carbon nano-material composite electrode is located, of the carbon nano-material composite electrode/flexible polymer composite film (22) in the step S2, wherein the support skeletons are series support blocks, the series support blocks are connected end to end at the peripheral edges of one side face of the carbon nano-material composite electrode/flexible polymer composite film (22) to form a uncovered cavity structure, and curing to obtain the carbon nano-material composite electrode/flexible polymer composite film (22) with the polydimethylsiloxane support skeletons;
s4, assembling the flexible polymer/nano carbon material composite electrode/flexible polymer composite film (21) in the step S1 and the side, provided with the supporting framework, of the nano carbon material composite electrode/flexible polymer composite film (22) with the polydimethylsiloxane supporting framework in the step S3 through oxygen plasma auxiliary reaction to obtain a flexible wearable friction nano generator (2);
s5, preparing the three-dimensional multilevel structure graphene electrode by using a plasma-assisted chemical vapor deposition method;
s6, preparing polydimethylsiloxane into a square structure with a containing cavity by a template method, preparing a series of micropores (15) on the top surface and the side surface of the square structure, forming a groove on the inner bottom surface of the square structure, and arranging a microfluidic channel on the side surface of the groove, wherein the microfluidic channel connects the series of micropores (15) on the side surface with the groove to obtain a polydimethylsiloxane flexible shell (11);
s7, dripping a suspension solution of carbon nanotubes and tetrathiafulvalene on the three-dimensional multi-level structure graphene electrode obtained in the step S5, drying in the air, dripping a lactic acid enzyme solution, drying in the air again, and covering a layer of highly crosslinked chitosan biopolymer to obtain a lactic acid enzyme/three-dimensional multi-level structure graphene anode (12);
s8, dropping and coating a suspension solution of carbon nanotubes and reduced oxygen precious metal powder on the three-dimensional multi-level structure graphene electrode in the step S5, airing, and then covering a layer of water-soluble perfluorosulfonic acid polymer to obtain a reduced oxygen precious metal/three-dimensional multi-level structure graphene cathode (13);
s9, placing the anode (12) in the step S7 and the cathode (13) in the step S8 into a groove of the polydimethylsiloxane flexible shell (11), and then injecting a hydrogel electrolyte (14) into the groove to obtain the flexible wearable enzyme biofuel cell (1);
s10, seamlessly assembling the end face of the flexible polymer/nano carbon material composite electrode/flexible polymer composite membrane (21) of the flexible wearable friction nano generator (2) and the bottom surface of the flexible wearable enzyme biofuel cell (1) without micropores into a whole through oxygen plasma assisted reaction to obtain the flexible wearable composite energy collecting device.
3. The method of claim 2, wherein the nano-carbon materials of steps S1 and S2 include graphene, carbon nanotubes, bucky paper, and carbon nanodots.
4. The method of claim 2, wherein the flexible polymer of steps S1 and S2 comprises polydimethylsiloxane, polyurethane, Ecolfelx.
5. The method according to claim 2, wherein the lactic acid enzyme in step S7 comprises lactate oxidase or lactate dehydrogenase.
6. The method of claim 2, wherein the reduced oxygen precious metal of step S8 comprises Pt, Pd, Ru, Ag or an oxide thereof.
7. The method according to claim 2, wherein the hydrogel electrolyte (14) of step S9 includes a lactic acid solution.
8. Use of the flexible wearable composite energy harvesting device of claim 1 in wearable electronics.
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