CN110391768B - Mechanical energy harvester for carbon nanotube yarn based on vacuum high-temperature annealing treatment - Google Patents
Mechanical energy harvester for carbon nanotube yarn based on vacuum high-temperature annealing treatment Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N2/00—Electric machines in general using piezoelectric effect, electrostriction or magnetostriction
- H02N2/18—Electric machines in general using piezoelectric effect, electrostriction or magnetostriction producing electrical output from mechanical input, e.g. generators
- H02N2/186—Vibration harvesters
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2101/00—Inorganic fibres
- D10B2101/10—Inorganic fibres based on non-oxides other than metals
- D10B2101/12—Carbon; Pitch
Abstract
The invention belongs to the field of energy conversion and application, and particularly relates to a mechanical energy capturer of carbon nanotube yarns based on high-vacuum high-temperature treatment. The carbon nanotube yarn is prepared by twisting and natural untwisting a carbon nanotube array capable of spinning, and then is heated to 2000 ℃ by a vacuum electrifying device. During the heating process, the carbon nanotube yarn needs to exert a tensile tension at break of 40%. After vacuum high-temperature treatment, the yarn is taken out and twisted continuously to be made into a spiral structure. Then the carbon nanotube yarn is used as a working electrode to be placed in an electrochemical system of a three-electrode system, and mechanical energy is converted into voltage output of the working electrode and a reference electrode through a mechanical stretching device, so that mechanical vibration energy is converted into electric energy.
Description
Technical Field
The invention belongs to the field of energy conversion and application, and particularly relates to a mechanical energy capturer of carbon nanotube yarns based on high-vacuum high-temperature treatment.
Background
Energy and environment are the two most important topics of human concern in the 21 st century. With the development of economy, fossil energy resources such as coal and petroleum are increasingly reduced due to continuous consumption, and various renewable energy sources are vigorously developed in various countries in the world, so that it is desired to collect and convert energy which can be recycled in the environment. On the one hand, the quality requirement of people on energy sources is continuously improved; on the other hand, people's awareness of environmental protection is increasingly strengthened, and a series of environmental problems caused by long-term use of fossil energy are increasingly prominent, so that research and utilization of clean, environment-friendly, reliable and cheap new energy becomes a hotspot.
The mechanical vibration energy capturing device is a functional device capable of converting mechanical energy into electric energy, and is widely applied to self-powered wireless sensors, human health monitoring, motion energy capturing and sea wave vibration energy recovery. The devices mainly used in the method can convert mechanical vibration energy with high frequency and low deformation into electric energy, but the devices are not greatly deformed and are rigid in material, so that the devices are generally only used as sensors. The other piezoelectric nano generator can also well convert mechanical energy in the forms of friction, vibration and the like into electric energy output at high voltage, but the output energy density and the output power density are both small. Therefore, how to design a functional material which can effectively output mechanical vibration energy with high output power density and high output energy density and has better flexibility, stretchability and reuse rate is a technical difficulty in recent years.
Disclosure of Invention
The invention aims to provide a mechanical energy converter based on high-vacuum high-temperature processing carbon nanotube yarns, so as to overcome the difficulties in the prior art. The carbon nanotube yarn is prepared by twisting and natural untwisting a carbon nanotube array capable of spinning, and then is heated to 2000 ℃ by a vacuum electrifying device. During the heating process, tension is required to be applied to the carbon nanotube yarn, and the tension is 40% of the breaking tensile tension. After vacuum high-temperature treatment, the yarn is taken out and twisted continuously to be made into a spiral structure. Then, the carbon nano tube yarn is used as a working electrode and placed in a three-electrode electrochemical system, and the mechanical stretching device is used for converting the reciprocating stretching mechanical energy into the relative change voltage output of the working electrode and the reference electrode, so that the aim of converting the mechanical vibration energy into the electrical energy is fulfilled.
In order to achieve the purpose, the invention adopts the following technical scheme:
the mechanical energy harvester for the carbon nanotube yarn based on the vacuum high-temperature annealing treatment is characterized by comprising the carbon nanotube yarn which is arranged in a three-electrode electrochemical system and is used as a working electrode and has a spiral structure after the vacuum high-temperature treatment, wherein the carbon nanotube yarn is mechanically stretched, and the mechanical energy obtained by the mechanical stretching is converted into the relative change voltage output of the working electrode and a reference electrode, so that the aim of converting the mechanical vibration energy into the electric energy is fulfilled.
Further, in the three-electrode electrochemical system, a counter electrode and an Ag/AgCl reference electrode which are made of Pt meshes and graphene oxide are used for carrying out three-electrode electrochemical performance test.
The specific preparation steps of the counter electrode are as follows: pt foil net with the area of 50mm multiplied by 50mm is coated with the weight of 3g and the specific surface area of 2630m 2 And g, graphene oxide, and making a counter electrode, and then folding the foil net in half so that the graphene oxide is placed inside the foil net. Graphene oxide is purchased from AlPHA Nanoteh.
Further, the preparation method of the carbon nanotube yarn with the spiral structure after vacuum high-temperature treatment comprises the following steps:
the method comprises the following steps: firstly, preparing a spinnable multi-walled carbon nanotube array by a chemical vapor deposition growth method, wherein the specific preparation method comprises the following steps: acetylene gas diluted in argon is used as a carbon source, iron with the thickness of 2nm is used as a catalyst through electron beam physical vapor deposition, the temperature of catalytic reaction is 690 ℃, and the multi-walled carbon nanotube array is prepared, wherein the number of the tube walls is 6-9.
Step two: preparing carbon nanotube (MWNT) yarn by a motor; drawing 5 layers of carbon nanotube yarns with the width of 6-10 mm and the length of 20cm from the multi-wall carbon nanotube array; then at 500rpm -1 The twist of (a) twists it as shown in figure 1. The weight applied during twisting was 10 g. The density of the yarn obtained after twisting may vary for different applied weights. The invention adopts 10g weight to pretension the carbon nanotube yarn and simultaneously prevents untwisting at two ends. After the yarn is twisted to 500turns m -1 After the twisting degree is reached, the moment limitation on the carbon nano tube yarn is removed, the carbon nano tube yarn is freely untwisted, and the carbon nano tube yarn with the removed twisting degree is obtained after stabilization.
Step three: and carrying out high-temperature annealing treatment on the carbon nanotube yarn with the twist removed. The invention relates to a high-temperature vacuum annealing device. The method is characterized in that voltage is applied to the yarn, and the carbon nanotube yarn has good conductivity, so that a large amount of Joule heat is generated and the temperature is increased, and the operation process is shown in the attached figure 2. And cutting the carbon nanotube yarn which is 15cm in length and is freely untwisted, and respectively clamping two ends of the yarn through clamps. And (3) connecting the carbon nanotube yarn by using a TR-3000110V single-phase alternating current voltage regulator, and forming a passage. After the lines are connected, a weight needs to be applied to the carbon nanotube yarn, and the size of the weight is 40% of the breaking tensile strength of the yarn. And then, slowly increasing the voltage of the voltage regulator, finding that the carbon nanotube yarn slowly heats and turns red, continuously increasing the voltage of the voltage regulator until the carbon nanotube yarn emits bright white light, and obtaining the temperature of the carbon nanotube yarn to be 2000 ℃ by comparing spectra. The voltage applied at this time was 105V, and the voltage per unit length of yarn was set to 70V/cm depending on the length of yarn. The time of the yarn being treated by high temperature vacuum annealing is 2 min.
Step four: and (4) twisting the yarn subjected to the high-temperature vacuum annealing treatment in the fourth step again until the carbon nanotube yarn with the spiral structure is formed, wherein the weight applied in the twisting is 10g as in the second step.
The high-temperature vacuum annealing device is a quartz glass tube electrifying device, and is shown in an attached figure 2. The method specifically comprises the following steps: the model is PFEIFFER Vacuum equipment, a quartz tube with the diameter of 5cm, a TR-3000110V pressure regulator and a Vacuum power supply lead with the model of 9422013-18001. The specific assembly relationship is shown in fig. 2. The bottom of the vertical quartz tube is connected with a vacuum device, and the top of the vertical quartz tube is led out with 2 wires through a vacuum power lead and connected into a voltage regulator. The output voltage is changed through the voltage regulator, and the electric energy input to the yarns can be changed, so that the actual temperature of the yarns is changed, and the purpose of vacuum annealing treatment is achieved.
Step five: the counter electrode of the above three electrodes has a sufficiently high capacitance with respect to the working electrode, and the battery capacitance is largely determined by the capacitance of the working electrode. The Open Circuit Voltage (OCV) between the working electrode and the reference electrode was measured using a Gamry potentiostat. Short Circuit Current (SCC) was measured between the working and counter electrodes by maintaining the voltage between the electrodes at zero volts (i.e., shorting the electrodes) and recording the resulting current. When a resistive load is applied to measure the power output of the collector, the current is measured by either an online current measurement of a potentiostat or by measuring the load voltage and calculating the current as I ═ V/R, where V is the voltage through the load and R is the resistance of the load.
Step six: the average and peak output electrical power and the output energy per cycle were measured by connecting an external load resistor between the carbon nanotube yarn working and counter electrodes and recording the resulting voltage during tensile deformation. The average output power and the peak output power are optimized by changing the load resistance.
Step seven: unless otherwise stated, electrode capacitance was measured by Cyclic Voltammetry (CV) over a small potential range, meaning no redox processes were induced, 0.3 to 0.6V versus Ag/AgCl, and a potential scan rate of 50 mV/s.
Step eight: by connecting an external load resistor between the carbon nanotube yarn working and counter electrodes and recording the resulting voltage during tensile deformation. Fixing the stretching frequency to be 1Hz, and obtaining the relation between different deformation quantities and output voltage through the deformation quantity of the carbon nano tube with the spiral structure; the relation between the output voltage and the load resistance can be obtained by changing different load resistances with fixed deformation quantity, so that the optimal load resistance is obtained. Using the formula P ═ U 2 the/R is used to calculate the peak power of the output, the average output electrical power, and the output energy per cycle. Wherein, P is output peak power, U is output voltage, and R is load resistance. The average output power and the peak output power are optimized by changing the load resistance.
The invention innovatively provides that the vertical and electrified vacuum quartz tube is adopted to carry out high-temperature annealing treatment on the carbon nanotube yarn. The advantages are that: 1. the problem that the high-temperature tube furnace consumes long time for vacuum annealing treatment is solved, the high-temperature vacuum treatment device provided by the invention can carry out rapid high-temperature vacuum treatment on the fiber in a short time (such as 2 minutes), and the treatment efficiency is improved. 2. The invention can pre-apply adjustable tension to the carbon nano tube fiber and pre-stretch the fiber, thereby overcoming the defect that a horizontal tube furnace is difficult to pre-apply tension to the fiber. 3. The method for processing the carbon nanotube fiber by high-temperature vacuum can improve the energy density, the power density and the like of the carbon nanotube fiber output by an energy capture device, and the output energy density and the power density are about 3 times. 4. The invention can carry out rapid carbonization treatment on the non-conductive fiber to prepare the carbon material with high specific surface area, so that the carbon material has the performances of electrochemical capacitance and mechanical vibration energy capture, and can prepare the material which is cheaper and easier to commercialize than the carbon nano tube. 5. The invention can measure the temperature of the surface of the fiber and feed back the temperature to the voltage regulator, and can reach the required set vacuum treatment temperature by changing the output voltage of the voltage regulator, has the characteristics of simple operation, accurate measurement and the like, and is also used for other forms of rapid high-temperature vacuum treatment equipment.
Drawings
FIG. 1 is a schematic view of a carbon nanotube yarn twisted in substance to enlarge;
1, twisting the untreated carbon nanotube yarn; 2. twisting the carbon nanotube yarn subjected to high-temperature vacuum treatment; 3. the carbon nanotube yarn with the spiral structure is not subjected to vacuum high-temperature treatment. 4. Spiral-structured carbon nanotube yarn subjected to vacuum high-temperature treatment
FIG. 2 is a quartz glass tube energization apparatus;
wherein, 5, ammeter; 6. a quartz tube; 7. carbon nanotube yarn.
FIG. 3 a twisted carbon nanotube yarn in a vacuum high temperature process;
FIG. 4 is a schematic diagram of a three-electrode electrochemical system mechanical tensile testing apparatus with helical carbon nanotube yarn as a working electrode;
wherein, 8, Ag/AgCl reference electrode; 9. a Pt/graphene oxide counter electrode; 10. a helical-structured carbon nanotube working electrode.
Fig. 5 is a comparison between the output open circuit voltages of the carbon nanotube yarn of the helical structure without vacuum high-temperature treatment and the carbon nanotube yarn of the helical structure with high-temperature vacuum treatment during the drawing process.
Fig. 6 is a comparison between output short-circuit currents of a carbon nanotube yarn of a helical structure without vacuum high-temperature treatment and a carbon nanotube yarn of a helical structure with high-temperature vacuum treatment during drawing.
FIG. 7 comparison of output power densities of a helical-structured carbon nanotube yarn without vacuum high-temperature treatment and a helical-structured carbon nanotube yarn with high-temperature vacuum treatment during drawing
The invention converts tensile vibration mechanical energy commonly used in life into electric energy through an electrochemical method to output, and can be used for capturing endless vibration energy of low-frequency waves. The mechanical energy capturer with high power output density is prepared by twisting carbon nanotube yarn with high conductivity, low density and high mechanical strength as a raw material through high-temperature vacuum treatment. It can be used in human activity monitoring and seismic prediction. Because it does not need external bias voltage, it does not need to consume extra electric energy when using.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings:
with reference to fig. 1 and 2, a mechanical energy harvester for carbon nanotube yarn based on vacuum high-temperature annealing treatment includes a carbon nanotube array capable of being spun, the carbon nanotube array is spun to form twisted carbon nanotube yarn 1, the carbon nanotube yarn 1 is subjected to high-temperature treatment by a vacuum energization annealing device to form carbon nanotube yarn 2 with higher mechanical strength, and the carbon nanotube yarn 2 with high mechanical strength is twisted to form carbon nanotube yarn 4 with a spiral structure. The carbon nano tube yarn 4 with the spiral structure is used as a working electrode of a three-electrode electrochemical system to be repeatedly stretched mechanically, so that voltage which changes relatively to a reference electrode can be continuously generated, and the voltage can output electric energy through an external resistor.
1. The preparation process of the carbon nanotube yarn with the spiral structure, which is used as the working electrode and is subjected to vacuum high-temperature treatment, comprises the following steps:
the method comprises the following steps: firstly, a spinnable multi-walled carbon nanotube array is prepared by a chemical vapor deposition growth method. The manufacturing method comprises the following steps: acetylene gas diluted in argon is used as a carbon source, iron with the thickness of 2nm is used as a catalyst for carrying out acetylene reduction catalytic reaction on a silicon wafer through electron beam physical vapor deposition, and the reaction temperature is 690 ℃. After the reaction is finished, a multiwall carbon nanotube array with the height of 100-300 mu m grows on the surface of the silicon wafer, and the number of tube walls is generally 6-9.
Step two: carbon nanotube (MWNT) yarns were prepared by a motor. 5 layers of carbon nanotube yarns with the width of 6-10 mm and the length of 20cm are pulled out from the multi-wall carbon nanotube array; then turn at 500turns m -1 The twist is twisted as shown in fig. 1. The weight applied during twisting was 10 g. The density of the yarn obtained after twisting may vary for different weights applied. The carbon nanotube yarn was pretensioned with a 10g weight while preventing untwisting at both ends. After the yarn is twisted to 500turns m -1 After the twisting degree is reached, the torque limitation on the carbon nano tube yarn is removed, the carbon nano tube yarn is allowed to untwist freely, and the carbon nano tube yarn with the removed twisting degree is obtained after the twisting degree is stabilized.
Step three: and carrying out high-temperature annealing treatment on the carbon nanotube yarn with the twist removed. Because the carbon nanotube yarn has good conductivity, a large amount of joule heat is generated after the carbon nanotube yarn is electrified, so that the temperature of the carbon nanotube yarn is increased, and the operation process is as follows: and (3) cutting the carbon nanotube yarn with the length of 15cm and the twist removed, and respectively clamping two ends of the yarn through metal screws. A weight is applied to the carbon nanotube yarn, the weight having a size of 40% of the tensile strength at break of the yarn, here 10 g. And connecting the carbon nanotube yarns by using a TR-3000110V single-phase alternating current voltage regulator to form a passage. And slowly increasing the voltage regulator voltage, slowly heating the carbon nano tube yarn and emitting red light, continuously increasing the voltage regulator voltage until the carbon nano tube yarn emits bright white light, and measuring the temperature of the carbon nano tube yarn to be 2000 ℃ by comparing spectra or a thermocouple. The voltage applied at this time was recorded to be 105V. And then setting the voltage applied to the unit length to be 70V/cm according to the lengths of different yarns, and setting the time of the carbon nano tube yarn subjected to high-temperature vacuum annealing treatment to be 2 min.
Step four: and twisting the yarn subjected to the high-temperature vacuum annealing treatment in the third step until the carbon nanotube yarn with a spiral structure is formed, wherein the weight applied in twisting is 10g which is the same as that in the second step.
2. With reference to fig. 4, a mechanical energy harvester for carbon nanotube yarn based on vacuum high temperature annealing treatment includes that carbon nanotube yarn 4 with a spiral structure is used as a working electrode of a three-electrode electrochemical system to perform mechanical repeated stretching, so as to continuously generate a voltage relatively changing with respect to a reference electrode, and the voltage can output electric energy through an external resistor. The operation process of continuously outputting electric energy by mechanically and repeatedly stretching the carbon nanotube yarn with the spiral structure as the working electrode through a three-electrode electrochemical system is as follows:
step five: the counter electrode of the three electrodes has a sufficiently high capacitance with respect to the working electrode, and the capacitance of the capacitor is largely determined by the capacitance of the working electrode. The Open Circuit Voltage (OCV) between the working electrode and the reference electrode was measured using a Gamry potentiostat. Short Circuit Current (SCC) was measured between the working and counter electrodes by maintaining the voltage between the electrodes at zero volts (i.e., shorting the electrodes) and recording the resulting current. When a resistive load is applied to measure the power output of the collector, the current is measured by either an online current measurement by a potentiostat or by measuring the load voltage and calculating the current as I ═ V/R.
Step six: the average and peak output electrical power and the output energy per cycle were measured by connecting an external load resistor between the carbon nanotube yarn working and counter electrodes and recording the resulting voltage during tensile deformation. The average output power and the peak output power are optimized by changing the load resistance.
Step seven: unless otherwise stated, the electrode capacitance was measured by Cyclic Voltammetry (CV) over a small potential range, meaning no redox process was induced, 0.3 to 0.6V versus Ag/AgCl, and a scan rate of 50 mV/s. Unless otherwise stated, three-electrode electrochemical experiments were performed using carbon nanotube yarn before and after high temperature treatment with a helical structure as the working electrode, a counter electrode made of Pt mesh and carbon with high surface area (CNT or graphene) and an Ag/AgCl reference electrode. The pair of electrodes has a sufficiently high capacitance with respect to the double electrode, and the cell capacitance is largely determined by the capacitance of the double electrode. Open Circuit Voltage (OCV) between the two electrodes and the counter electrode.
Step eight: by operating electricity on carbon nanotube yarnsAn external load resistor was connected between the pole and counter electrode and the resulting voltage was recorded during the tensile deformation. Fixing the stretching frequency to be 1Hz, and obtaining the relation between different deformation quantities and output voltage through the deformation quantity of the carbon nano tube with the spiral structure; the relation between the output voltage and the load resistance can be obtained by changing different load resistances with fixed deformation quantity, so that the optimal load resistance is obtained. Using the formula P ═ U 2 the/R is used for calculating the peak power of the output, the average output electric power and the output energy per period. The average output power and the peak output power are optimized by changing the load resistance.
3. With reference to fig. 5, a comparison between the output open-circuit voltage of the spiral-structure carbon nanotube fiber energy harvester based on the vacuum high-temperature annealing treatment and the output open-circuit voltage of the spiral-structure carbon nanotube energy harvester without the vacuum high-temperature annealing treatment in the stretching process is specifically shown. The curve shows the variation of the open-circuit voltage and the tensile strain output by the carbon nanotube fiber energy harvester with a helical structure having a diameter of 132 μm and a length of 10.2mm under different tensile strains. As can be seen, the yarn without vacuum high temperature annealing had an output voltage of 83mV at 30% tensile strain, whereas the yarn with vacuum high temperature annealing had an output voltage of 109mV at 30% tensile strain, which is 20% higher than the yarn without vacuum high temperature annealing. On the other hand, the tensile strength of the yarn subjected to the high-temperature vacuum annealing treatment reached 50%, and the output open circuit voltage at this time was 280 mV. Therefore, the yarn subjected to the high-temperature vacuum annealing treatment has a larger tensile strain, and the open circuit voltage of the yarn is more than 3 times that of the yarn not subjected to the high-temperature vacuum annealing treatment.
4. With reference to fig. 6, a comparison between the peak value of the output short-circuit current of the spiral-structure carbon nanotube fiber energy harvester based on the vacuum high-temperature annealing treatment and the peak value of the output short-circuit current of the spiral-structure carbon nanotube energy harvester without the vacuum high-temperature annealing treatment in the stretching process is specifically shown. The curve shows the variation relationship between the peak-to-peak value of the output short-circuit current and the tensile strain of the carbon nanotube fiber energy harvester with the spiral structure and the diameter of 132 μm and the length of 10.2mm under different tensile strains. As can be seen, the yarn without vacuum high temperature annealing treatment has an output short circuit current peak value of 250 μ A at 30% tensile strain, while the yarn with vacuum high temperature annealing treatment has an output short circuit current peak value of 150 μ A at 30% tensile strain, which is 50% lower than that of the yarn without vacuum high temperature annealing treatment. On the other hand, the tensile strength of the yarn subjected to the high-temperature vacuum annealing treatment reached 55%, and the peak value of the output short-circuit current at this time was 310 μ a.
5. With reference to fig. 7, a comparison between the output peak power density of the spiral-structure carbon nanotube fiber energy harvester based on the vacuum high-temperature annealing treatment and the output peak power density of the spiral-structure carbon nanotube energy harvester without the vacuum high-temperature annealing treatment during the stretching process is specifically shown. The curve shows the variation of the output peak power density and tensile strain of the carbon nanotube fiber energy harvester with a spiral structure with the diameter of 132 μm and the length of 10.2mm under different tensile strains. As can be seen, the peak power density at 25% tensile strain of the yarn without vacuum annealing was 50W/kg, while the peak power density at 30% tensile strain of the yarn with vacuum annealing was 43W/kg, which is lower than that of the yarn without vacuum annealing. However, the tensile strength of the yarn subjected to the high-temperature vacuum annealing treatment reaches 55%, so that the output power density of the yarn reaches 160W/kg, which is 3 times of that of the yarn subjected to the high-temperature vacuum annealing treatment. Therefore, the spiral-structure carbon nanotube fiber energy harvester subjected to the vacuum high-temperature annealing treatment can improve the output power density and broaden the use strain range, and is a simple and efficient energy harvester.
Claims (10)
1. The mechanical energy harvester for the carbon nanotube yarn based on the vacuum high-temperature annealing treatment is characterized by comprising the carbon nanotube yarn which is arranged in a three-electrode electrochemical system and is used as a working electrode and has a spiral structure after the vacuum high-temperature treatment, wherein the carbon nanotube yarn is mechanically stretched, and the mechanical energy obtained by the mechanical stretching is converted into the relative change voltage of the working electrode and the reference electrode to be output, so that the aim of converting the mechanical vibration energy into electric energy is fulfilled;
the preparation method of the carbon nanotube yarn with the spiral structure after vacuum high-temperature treatment comprises the following steps:
the method comprises the following steps: firstly, preparing a spinnable multi-walled carbon nanotube array by a chemical vapor deposition growth method;
step two: preparing carbon nanotube yarn by a motor; drawing out carbon nanotube yarns from the multi-wall carbon nanotube array; then 500turns m -1 Twisting the fiber by the twist degree of the fiber, and applying a heavy object during twisting; pre-tensioning the carbon nanotube yarn while preventing untwisting of both ends; after the yarn is twisted to 500turns m -1 After the twist is finished, removing the torque limitation on the carbon nano tube yarn, allowing the carbon nano tube yarn to be freely untwisted, and obtaining the carbon nano tube yarn with the removed twist after stabilization;
step three: carrying out high-temperature annealing treatment on the carbon nanotube yarn with the twist removed; applying voltage to the yarns by using a high-temperature vacuum annealing device until the carbon nano tube yarns emit bright white light, and keeping for 2 min;
step four: and (4) twisting the yarn subjected to the high-temperature vacuum annealing treatment in the third step again until the carbon nanotube yarn with the spiral structure is formed.
2. The mechanical energy harvester for carbon nanotube yarn based on vacuum high temperature annealing process according to claim 1, wherein in the three-electrode electrochemical system, a counter electrode made of Pt mesh and graphene oxide and an Ag/AgCl reference electrode are used for three-electrode electrochemical performance test.
3. The mechanical energy harvester for carbon nanotube yarn based on vacuum high temperature annealing treatment according to claim 2, wherein the counter electrode is prepared by the following steps: pt foil net with the area of 50mm multiplied by 50mm is coated with the weight of 3g and the specific surface area of 2630m 2 And g, graphene oxide, and making a counter electrode, and then folding the foil net in half so that the graphene oxide is placed inside the foil net.
4. The mechanical energy harvester for carbon nanotube yarns based on vacuum high temperature annealing treatment as claimed in claim 1, wherein in the first step, the specific preparation method of the multi-walled carbon nanotube array comprises: acetylene gas diluted in argon is used as a carbon source, iron with the thickness of 2nm is used as a catalyst through electron beam physical vapor deposition, the temperature of catalytic reaction is 690 ℃, and the multi-walled carbon nanotube array is prepared, wherein the number of the tube walls is 6-9.
5. The mechanical energy harvester for carbon nanotube yarns based on vacuum high temperature annealing treatment as claimed in claim 1, wherein in the second step, 5 layers of carbon nanotube yarns with the width of 6-10 mm and the length of 20cm are drawn from the multi-wall carbon nanotube array; the weight applied during twisting was 10 g.
6. The mechanical energy harvester based on vacuum high temperature annealing treatment for carbon nanotube yarn according to claim 1, wherein in the third step, the high temperature vacuum annealing device is a quartz glass tube electrifying device, and the device comprises: PFEIFFER Vacuum equipment, a vertical quartz tube with the diameter of 5cm, a TR-3000110V pressure regulator and a Vacuum power supply lead wire with the model of 9422013-18001; the bottom of the vertical quartz tube is connected with vacuum equipment, and 2 electric wires are led out from the top of the quartz tube through a vacuum power supply lead and connected into a voltage regulator; change the voltage of output through the voltage regulator, can change the electric energy of inputing to the yarn to change the actual temperature of yarn, reach the purpose of vacuum annealing treatment, specifically do: cutting out carbon nanotube yarn with the length of 15cm and free untwisting, and respectively clamping two ends of the yarn through clamps; connecting the carbon nano tube yarn by using a TR-3000110V single-phase alternating current voltage regulator, and forming a passage; after the lines are connected, a weight needs to be applied to the carbon nano tube yarn, and the size of the weight is 40% of the breaking tensile strength of the yarn; then, slowly increasing the voltage of the voltage regulator, and when the carbon nanotube yarn is found to slowly heat and turn red, continuously increasing the voltage of the voltage regulator until the carbon nanotube yarn emits bright white light, and obtaining the temperature of the carbon nanotube yarn to be 2000 ℃ by comparing spectra; the voltage applied at this time was 105V; setting the voltage applied to the unit length to be 70V/cm according to the lengths of different yarns; the time of the yarn being treated by high temperature vacuum annealing is 2 min.
7. The mechanical energy harvester for carbon nanotube yarn based on vacuum high temperature annealing process of claim 1, wherein in the fourth step, the weight applied by twisting is 10g same as that in the second step.
8. The mechanical energy harvester based on vacuum high temperature annealed carbon nanotube yarn of claim 1, wherein said three-electrode electrochemical system uses a Gamry potentiostat to measure the open circuit voltage between the working electrode relative to the reference electrode; measuring a short circuit current between the working electrode and the counter electrode by maintaining the voltage between the electrodes at zero volts and recording the resulting current; when a resistive load is applied to measure the power output of the collector, the current is measured by either an online current measurement of a potentiostat or by measuring the load voltage and calculating the current as I ═ V/R, where V is the voltage through the load and R is the resistance of the load.
9. The vacuum high temperature anneal-based mechanical energy harvester for carbon nanotube yarn of claim 1, wherein the three-electrode electrochemical system measures electrode capacitance by cyclic voltammetry within a small potential range, which does not induce redox processes, of 0.3 to 0.6V versus Ag/AgCl and has a potential scan rate of 50 mV/s.
10. The vacuum high temperature annealing process-based mechanical energy harvester for carbon nanotube yarn of claim 1, wherein the voltage obtained is recorded during the tensile deformation by connecting an external load resistor between the working electrode and the counter electrode of carbon nanotube yarn; fixing the stretching frequency to be 1Hz, and obtaining the relation between different deformation quantities and output voltage through the deformation quantity of the carbon nano tube with the spiral structure; the relation between the output voltage and the load resistance can be obtained by changing different load resistances by fixing the deformation quantity to obtainObtaining the optimal load resistance; using the formula P ═ U 2 The peak power, the average output electric power and the output energy per period of the output are calculated by the/R; wherein, P is output peak power, U is output voltage, and R is load resistance; the average output power and the peak output power are optimized by changing the load resistance.
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