Patent Application
20240027177
The present invention relates to the field of sensor device engineering, and in particular to a stretchable strain sensor based on vertical graphene and its application.
In the foreseeable future, the contact between the electronic equipment and human beings will become more and more frequent. The electronic equipment will get functions such as more advanced and convenient health detection, information acquisition and as a bridge between human beings and machines through more contact with human beings. Wearable devices represented by soft E-skin are emerging research hotspots in the electronic field such as electronic devices which can be directly contacted with human bodies and can be directly attached to the skins.
The traditional strain or pressure sensitive sensor is based on non-flexible materials such as piezoelectric ceramics, and the sensor cannot be stretched or compressed at will, so that it cannot be attached to the skin, and is limited in application. For example, to sense the joint movement locus of an animal or a robot, a sensor needs to be attached to a joint, and the sensor is stretched or compressed during the joint movement, in order to sense the amplitude and direction of the joint movement.
To create stretchable strain sensors, a stretchable elastic material, such as rubber, is required, but the sensitivity of the strain sensors which made of the material is limited, and the sensitivity factor (defined as the variation of the relative resistance divided by the relative deformation quantity, abbreviated as GF) is difficult to break through 100. In particular, since the Young's modulus of the elastic material is low, the natural frequency is low, and the natural frequency cannot follow the vibration frequency of the sound wave, so that the audio (or timbre) cannot be recognized, and only the intensity of the sound (volume) can be sensed at most, thereby limiting the application range.
Non-patent document 1 (Nature, 2014, 516, 222-226.doi:10.1038/nature14002) discloses a stretchable strain sensor prepared by plating a metal film on a stretchable elastic substrate (polydimethylsiloxane, PDMS), because the metal film forms many cracks during stretching, and the audio is sensed by the change of the cracks during vibration. However, the metal film is easy to completely break during the stretching process to cause failure, and the maximum stretching amount of the sensor is only 2%, so that the practical requirement of The stretchable strain sensor are difficult to meet.
Non-patent document 2 (ACS Appl. Mater. Interfaces 2019, 11, 1294-1302. DOI: 10.1021/acsami. 8b18210) discloses strain sensors made of graphene wall, the stretch ratio is 10%, but the sensor can only sense and cannot distinguish the sound timbres.
Non-patent document 3 (ACS Appl. Mater. Interfaces, 2018, 10, 36312-36322. DOI: 10. 1021/acsami. 8b15848) discloses stretchable strain sensors made from vertical graphene comprising a bottom plane layer containing zigzag cracks and a vertical layer. The cracks become widen during stretching, ande lengthening the current path and thus changing the resistance. However, such cracks are formed during the stretching process, having a low density of cracks (spacing between adjacent cracks is typically greater than 50 microns), and are directionally uniform, result in low sensitivity (maximum GF of 88.4) and are indistinguishable from the sound timbres.
Therefore, aiming at the defects in the prior art, it is necessary to provide a stretchable strain sensor with good performance and timbre recognition ability and its application to solve the defects in the prior art.
This invention aims to avoid the deficiencies of the prior art and provides a stretchable strain sensor based on vertical graphene which has high sensitivity, high natural frequency and timbre recognition ability.
The above object of the present invention is achieved by the following technical measures:
Preferably, the stretch ratio is greater than 70% and can recognize timbre.
Preferably, The stretchable strain sensor based on vertical graphene can recognize timbre that frequency greater than f hertz, f being 100, 800 or 2500.
Since the Young's modulus of the stretchable material is small and the natural frequency is low, the higher the acoustic frequency, the more difficult the stretchable strain sensor is to recognize. Therefore, the term “capable of recognizing timbre greater than a certain frequency” according to the present invention means: the highest-frequency timbre which can be recognized is greater than the frequency, and all timbre which are less than the frequency can be recognized; for example, “can recognize timbre that frequency greater than 100 Hz” means: the highest-frequency timbre that can be recognized is above 100 Hz and timbre less than 100 Hz can be recognized.
Generally, the frequency of drumming or plosive is below 100 Hz, the frequency of voice of human speaking is within the range of 100 Hz and 600 Hz, and the frequency of singing is below 1200 Hz. Therefore, the ability to recognize 100 Hz timbre means the ability to sense ambient vibrations, such as footsteps, car sounds, etc., which can be used to respond to changes in the ambient environment, as well as sense heartbeats; the ability to recognize 800 Hz timbre means the ability to identify voice of human speaking, which can be used to identify whose voice is and the spoken content; the ability to recognize 2500 Hz timbre means the ability to identify the voice of singing and the sounds produced by some instruments, which can be used to identify music.
Preferably, the above-mentioned stretchable strain sensors based on vertical graphene has a sensitivity factor greater than 100 at 50% stretch.
Preferably, the above-mentioned stretchable strain sensors based on vertical graphene has a sensitivity factor greater than 200 at 50% stretch.
Preferably, the above-mentioned stretchable strain sensor based on vertical grapheme, wherein the vertical graphene which the total thickness is 100 nanometers to 100 microns comprises a bottom plane layer and a vertical layer and contains high-density reticular cracks, the directions of the cracks comprise transverse, vertical and oblique directions, the reticular cracks divide the vertical graphene into a plurality of small blocks, and adjacent small blocks are electrically connected through the vertical layer; in the stretched state, the cracks widen, but still can be bridged by the vertical layer, the two sides of the cracks still remain electrically connected, the sensor remains effective.
Preferably, the average diameter range of the plane of each small block of the above-mentioned stretchable strain sensor based on vertical grapheme is between 5 and 20 microns.
The average diameter of the plane of the small block is defined as: the maximum length of the small block on a plane perpendicular to the thickness direction of the vertical graphene. The calculation formula of the natural frequency of the object is as follows:
More preferably, the average diameter range of the plane of each small block of the above-mentioned stretchable strain sensor based on vertical grapheme is between 6 and 10 microns.
Preferably, the vertical graphene of the above-mentioned stretchable strain sensor based on vertical grapheme is dissociated from the growth substrate by an ultrasonic dissociation method.
The vertical graphene of The stretchable strain sensor based on vertical grapheme is dissociated from the growth substrate by an ultrasonic dissociation method. During the ultrasonic dissociation process, high density cracks may be generated in the vertical graphene since bubble explosion may occur. The ultrasonic dissociation mode has the advantages of simplicity, high crack density and incomplete fracture. It should be noted that, in the existing dissociation method of graphene, ultrasonic wave is generally not used, because it is difficult to obtain complete graphene due to it that causes fragmentation of graphene; one of the creativity of the invention is that the ‘destruction’ effect of the ultrasonic wave on the graphene is just used to improve the stretch ratio, the sensitivity and the natural frequency.
It should be noted that the vertical graphene of The stretchable strain sensor based on vertical grapheme of the present invention is not limited to the preparation by the ultrasonic dissociation method, and other dissociation methods or dissociation subsequent treatments may also be suitable for preparation as long as the vertical graphene obtained can satisfy the above-mentioned crack shape and the size of the small block.
Application of The stretchable strain sensor based on vertical graphene of the present invention includes directly attaching to the skin of a pregnant woman for monitoring the heart rate of the pregnant woman or a fetus in real time. Because the heart beat of the fetus is weak and the heart beat signal needs to be transmitted outwards through the mother, sensor with high sensitivity and sound wave detection capability is needed to accurately record the state of the fetus. In addition, the sound wave detection function can also monitor states of fetal respiration, blood circulation, hiccup sounds and the like. Compared with the traditional table type fetal monitor, The stretchable strain sensor based on vertical graphene of the present invention can be directly attached to the skin of a pregnant woman, does not need to be coated with a couplant or detected by hands, and has the characteristics of convenience, comfort, continuous real-time monitoring and low cost. Signals detected by the stretchable strain sensor based on vertical graphene can also be transmitted to the mobile phone in real time, and the state of the fetus or the pregnant woman can be obtained through mobile phone program analysis. It has great help for pregnant women in late pregnancy, at high risk and with abnormal conditions. For example, if the fetus has more than three times of umbilical cord around the neck, the heart rate of the fetus needs to be measured every hour; if a table type fetal monitor is used for manual detection once every hour with the couplant coated every time, the sleep and other daily lives of the pregnant women will be seriously disturbed after 24 hours of a day; if The stretchable strain sensor based on vertical graphene is attached to the belly of a pregnant woman like a adhesive bandage, the sensor is automatically awakened to measure once every one hour without being torn off, so that the sensor is very convenient and does not disturb the pregnant woman.
The stretchable strain sensor based on vertical graphene of the present invention can be used for artificial eardrum and identifying timbre. The traditional sound sensor is rigid and stereoscopic and cannot be attached to a human body, and The stretchable strain sensor based on vertical graphene of the present invention is stretchable and elastic and is similar to an eardrum, so that The stretchable strain sensor is suitable for being used as an artificial eardrum.
The stretchable strain sensor based on vertical graphene of the present invention can be used for attaching to human skin for pulse and recognizing pulse conditions, or for sensing movement of human joints or muscles. An electronic bracelet capable of sensing pulse on the market can detect a complete pulse signal only when being worn tightly; some stretchable strain sensors also can detect complete pulse signals only when under a stretching state; since The stretchable strain sensor based on the vertical graphene of the present invention is high in sensitivity, it can detect a complete pulse signal by being attached to the wrist artery in a natural state.
The stretchable strain sensor based on vertical graphene of the present invention can be used for the skin of a robot, sensing contact or motion. The stretchable strain sensor based on vertical graphene of the present invention can be attached to a joint of a robot to sense joint movement; also can be made into gloves with touch function which can sense the contacted object and the contact pressure; also can be made into ‘clothes’, sensing the action, contact, sound, vibration and the like of each part of the robot.
The stretchable strain sensor based on vertical graphene of the present invention has the characteristics of high stretch ratio, high sensitivity and capability of recognizing timbre, and is wider in application compared with other stretchable strain sensors.
The invention is further illustrated by means of the attached drawings, the content of which do not constitute any limitation of the invention.
The technical solution of the present invention is further described in conjunction with the following embodiments.
A stretchable strain sensor based on vertical graphene, as shown in
Wherein the vertical graphene comprises a bottom plane layer and a vertical layer, and has a total thickness of 100 nanometers-100 microns, preferably a total thickness in the range of 500 nanometers-20 microns. The vertical graphene also contains high-density reticular cracks, and as shown in
The average diameter range of the plane of each small block is not more than 20 microns, preferably in the range of 5-20 microns, which can meet the performance requirements of the sensor of the invention with respect to timbre. More preferably, the average diameter is not more than 10 microns, with the average diameter ranging from 6 to 10 microns.
The average diameter of the plane of the small block is defined as: the maximum length of the small block on a plane perpendicular to the thickness direction of the vertical graphene. The smaller the area of the small block, the higher the natural frequency, so high-density crack is the key to form the small block that size is not more than 20 microns and one of the necessary conditions to be able to identify the timbre.
The vertical graphene of The stretchable strain sensor based on vertical grapheme of the present invention is dissociated from the growth substrate by an ultrasonic dissociation method. During the ultrasonic dissociation process, high density cracks may be generated in the vertical graphene since bubble explosion may occur as shown in
It should be noted that the specific process parameters adopted in the ultrasonic dissociation step are conventional ultrasonic dissociation processes, which can be obtained by those skilled in this art, and are not described herein again.
It should be further noted that the vertical graphene of The stretchable strain sensor based on vertical grapheme of the present invention is not limited to the preparation by the ultrasonic dissociation method, and other dissociation methods or dissociation subsequent treatments may also be suitable for preparation as long as the vertical graphene obtained can satisfy the above conditions of crack shape and size of the small block.
Experimental results prove that The stretchable strain sensor based on vertical graphene of the present invention does not lose effectiveness under the deformation condition that the stretch ratio is greater than 50%; more preferably, The stretchable strain sensor based on vertical graphene of the present invention does not lose effectiveness under the deformation condition that the stretch ratio is greater than 70%.
The stretchable strain sensor based on vertical graphene of the present invention can recognize the timbre with the frequency greater than 100 Hz; more preferably, timbre that frequency greater than 800 Hz can be recognized; still more preferably, timbre that frequency greater than 2500 Hz can be recognized.
The term “capable of recognizing timbre greater than a certain frequency” according to the present invention means: the highest-frequency timbre which can be recognized is greater than the frequency, and all timbre which are less than the frequency can be recognized; for example, “can recognize timbre that frequency greater than 100 Hz” means: the highest-frequency timbre that can be recognized is above 100 Hz and timbre less than 100 Hz can be recognized.
The stretchable strain sensor based on vertical graphene of the present invention has ultrahigh sensitivity, and the sensitivity factor is greater than 100 at 50% stretch; more preferably, the sensitivity factor can be greater than 200 at 50% stretch.
The stretchable strain sensor based on vertical graphene of the present invention can be directly attached to the skin of a pregnant woman for monitoring the heart rate of the pregnant woman or a fetus in real time. Compared with the traditional table type fetal monitor, The stretchable strain sensor based on vertical graphene of the present invention can be directly attached to the skin of a pregnant woman, does not need to be coated with a couplant or detected by hands, and has the characteristics of convenience, comfort, continuous real-time monitoring and low cost. Signals detected by The stretchable strain sensor based on vertical graphene can also be transmitted to the mobile phone in real time, and the state of the fetus or the pregnant woman can be obtained through mobile phone program analysis. It has great help for pregnant women in late pregnancy, at high risk and with abnormal conditions. For example, if the fetus has more than three times of umbilical cord around the neck, the heart rate of the fetus needs to be measured every hour; if a table type fetal monitor is used for manual detection once every hour with the couplant coated every time, the sleep and other daily lives of the pregnant women will be seriously disturbed after 24 hours of a day; if The stretchable strain sensor based on vertical graphene is attached to the belly of a pregnant woman like a adhesive bandage, the sensor is automatically awakened to measure once every one hour without being torn off, so that the sensor is very convenient and does not disturb the pregnant woman.
The stretchable strain sensor based on vertical graphene of the present invention can be used for artificial eardrum and identifying timbre. The traditional sound sensor is rigid and stereoscopic and cannot be attached to a human body, and The stretchable strain sensor based on vertical graphene of the present invention is stretchable and elastic and is similar to an eardrum, so that The stretchable strain sensor is suitable for being used as an artificial eardrum.
The stretchable strain sensor based on vertical graphene of the present invention can be used for attaching to human skin for pulse and recognizing pulse conditions, or for sensing movement of human joints or muscles. An electronic bracelet capable of sensing pulse on the market can detect a complete pulse signal only when being worn tightly; some stretchable strain sensors also can detect complete pulse signals only when under a stretching state; since The stretchable strain sensor based on the vertical graphene of the present invention is high in sensitivity, it can detect a complete pulse signal by being attached to the wrist artery in a natural state.
The stretchable strain sensor based on vertical graphene of the present invention can also be used for the skin of a robot, sensing contact or motion. The stretchable strain sensor based on vertical graphene of the present invention can be attached to a joint of a robot to sense joint movement; also can be made into gloves with touch function which can sense the contacted object and the contact pressure; also can be made into ‘clothes’, sensing the action, contact, sound, vibration and the like of each part of the robot.
Therefore, The stretchable strain sensor based on vertical graphene of the present invention has the characteristics of high stretch ratio, high sensitivity and timbre recognition ability, and is wider in application compared with other stretchable strain sensors.
A stretchable strain sensor based on vertical grapheme, the other structure being the same as that of embodiment 1 except that: as shown in
The preparation process of The stretchable strain sensor based on vertical grapheme comprises the following steps: firstly preparing vertical graphene 1 on a growth substrate such as a Si substrate and a Ni substrate, then pouring a stretchable material (such as PDMS) on the vertical graphene and curing the stretchable material to form a stretchable substrate 3, then placing the stretchable substrate 3/the vertical graphene 1 into an ultrasonic pool for ultrasonic dissociation, thus forming a double-layer stretchable device of the stretchable substrate 3/the vertical graphene 1, then preparing an extraction electrode 2 on one side of the vertical graphene 1 of the double-layer stretchable device of the stretchable substrate 3/the vertical graphene 1, and finally preparing a stretchable protective layer 4.
It should be noted that, in the actual preparation, the preparation steps may be adjusted according to actual requirements, for example, the extraction electrode 2 may be prepared on the vertical graphene 1 firstly, then the stretchable substrate 3 may be poured and cured, and then the ultrasonic dissociation may be performed; as another example, the device can be prepared by directly dissociating the vertical graphene 1 from the growth substrate without the stretchable substrate 3. The stretchable substrate 3 and the stretchable protective layer 4 are not essential layers of The stretchable strain sensor based on vertical grapheme of the present invention, and may be set according to the actual application requirements.
It should be further noted that the vertical graphene of The stretchable strain sensor based on vertical grapheme of the present invention is not limited to the preparation by the ultrasonic dissociation method, and other dissociation methods or dissociation subsequent treatments may also be suitable for preparation as long as the vertical graphene obtained can satisfy the above conditions of crack shape and size of the small block.
The extraction electrode 2 can be made of any conductive material and is used for connecting a power supply, the extraction electrode 2 can be bonded with the vertical graphene 1 by conductive silver paste and the like, and the electrode can be further fixed by a clamp.
The material of the stretchable substrate 3 and the stretchable protective layer 4 may be any stretchable insulating material such as polydimethylsiloxane (PDMS), hydrogenated styrene-butadiene block copolymer (SEBS), styrene-butadiene-styrene block copolymer (SBS), TPU, etc.
Experimental results prove that The stretchable strain sensor based on vertical graphene does not lose effectiveness under the deformation condition that the stretch ratio is greater than 50%; more preferably, The stretchable strain sensor based on vertical graphene does not lose effectiveness under the deformation condition that the stretch ratio is greater than 70%.
The stretchable strain sensor based on vertical graphene can recognize the timbre with the frequency greater than 100 Hz; more preferably, timbre that frequency greater than 800 Hz can be recognized; still more preferably, timbre that frequency greater than 2500 Hz can be recognized.
The stretchable strain sensor based on vertical graphene has ultrahigh sensitivity, and the sensitivity factor is greater than 100 at 50% stretch; more preferably, the sensitivity factor can be greater than 200 at 50% stretch.
The stretchable strain sensor based on vertical graphene can be directly attached to the skin of a pregnant woman for monitoring the heart rate of the pregnant woman or a fetus in real time; can be used for artificial eardrum and identifying timbre; can be used for attaching to human skin for pulse and recognizing pulse conditions, or for sensing movement of human joints or muscles; can be used for the skin of a robot, sensing contact or motion.
The stretchable strain sensor of the present embodiment has the characteristics of high stretch ratio, high sensitivity and capability of recognizing timbre, and is wider in application compared with other stretchable strain sensors.
A stretchable strain sensor based on vertical grapheme includes a vertical grapheme, an extraction electrode and a stretchable substrate.
The preparation process comprises the following steps: firstly preparing 1-micron-thick vertical graphene on a Si growth substrate by using a CVD method, then pouring a mixture of a prepolymer of PDMS and a curing agent on the vertical graphene and curing the mixture to form a stretchable substrate, then placing the stretchable substrate/the vertical graphene into an ultrasonic pool for ultrasonic dissociation (the ultrasonic frequency is 40 kHz and the power is 40 W), thus forming a double-layer stretchable device of the stretchable substrate/the vertical graphene, then preparing Cu on one side of the vertical graphene of the double-layer stretchable device of the stretchable substrate/the vertical grapheme to serve as an extraction electrode, and fixing the Cu by using conductive silver paste.
The vertical graphene contains high-density reticular cracks, the directions of the cracks comprise transverse, vertical and oblique directions, namely, the cracks exist in all directions, the staggered cracks form a plurality of small blocks, and the average diameter of the plane of each small block is 5-20 microns.
The experiment results of the prepared stretchable strain sensor based on vertical grapheme can identify the timbre are shown in
The stretch experiment results of The stretchable strain sensor based on vertical graphene of the present invention are shown in
The stretchable strain sensor based on vertical graphene of the present invention has ultrahigh sensitivity, and the sensitivity factor (GF) is about 300 at 50% stretch, as shown in
The stretchable strain sensor based on vertical graphene of the present invention is attached to human joints, can sense the movement of a human wrist joint, a human knee joint and a human finger joint, as shown in
The stretchable strain sensor based on vertical graphene of the present invention is attached to an artery, and can sense the complete pulse signal of a human body, as shown in
A stretchable strain sensor based on vertical grapheme, the other characteristic being the same as that of embodiment 1 except that: the vertical graphene 1 has a thickness of 10 microns and further includes a PDMS stretchable protective layer 4, as shown in
The stretchable strain sensor based on vertical graphene is attached to the skin of an arm, capable of sensing muscle contraction and transmitting signal to mobile phone, as shown in
The stretchable strain sensor based on vertical graphene of the present invention is attached to the belly of a pregnant woman for monitoring the heart rate of a fetus in real time, as shown in
Finally, it should be noted that the above embodiments are merely used for describing the technical scheme of the present invention, but not intended to limit the protection scope of the present invention. Although the present invention is described in detail according to preferable embodiments, those of ordinary skills in the art should understand that the technical schemes of the present invention may be modified or equivalently substituted without departing from the spirit and protection scope of the present invention.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2019/107326 | 9/23/2019 | WO |
