CN108294747A - Aligned carbon nanotube adheres to dry electrode and its preparation process certainly - Google Patents
Aligned carbon nanotube adheres to dry electrode and its preparation process certainly Download PDFInfo
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- CN108294747A CN108294747A CN201810042398.3A CN201810042398A CN108294747A CN 108294747 A CN108294747 A CN 108294747A CN 201810042398 A CN201810042398 A CN 201810042398A CN 108294747 A CN108294747 A CN 108294747A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
- A61B5/25—Bioelectric electrodes therefor
- A61B5/279—Bioelectric electrodes therefor specially adapted for particular uses
- A61B5/291—Bioelectric electrodes therefor specially adapted for particular uses for electroencephalography [EEG]
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Abstract
The invention discloses a kind of aligned carbon nanotubes to adhere to dry electrode and its preparation process certainly.The dry electrode includes aligned carbon nanotube self-sticking layer, flexible support layers, Double-layer flexible conductive film and conducting wire.Present invention employs the modes of electrochemistry and micromachined to prepare dry electrode, such dry electrode has adhesiveness and flexibility, and Ultra light-weight, less than 20g, can stablize and skin contact simultaneously reduces motion artifacts, while enhancing the wearable comfort level of user, can be removed at any time after use, it will not remain, exempt cleaning.
Description
Technical field
The present invention relates to electricity physiological signal sensing acquisition technical fields, and in particular to aligned carbon nanotube adheres to dry electrode certainly
And its preparation process.
Background technology
It is important role that the monitoring and acquisition of electricity physiological signal, which play increasingly, especially around electrocardio and brain telecommunications
Number acquisition sensor greatly developed in recent years.Under normal conditions, after electrode is worn, in order to make between electrode and skin
Well stable electrical contact is formed, needs to inject comprising specific ion and conductive characteristic while having suitable to base part one by one
When the conductive paste of viscosity.Conductive paste overflows around in order to prevent, and general electrode is designed as tubbiness or bowl-shape, the electricity of injection
Pole cream is filled in scalp (skin) between electrode, plays wet skin and is electrically isolated caused by eliminating hair, is brain wave acquisition
One lower electrode/organizational interface is provided.Up to now, it is always to believe that this electrode structure and cooperation conductive paste, which place strategy,
A kind of best electricity physiological signal sampler of number quality.
Although taking advantage in terms of electrical signal collection quality, the shortcomings that this electrode, is primarily present three aspects：When
Long using time, it is difficult the independent wearing for completing electrode to need electrode injection conductive paste one by one, a people；Second be by
After examination person has used this electrode, hair and scalp sites have serious conductive glue residua, need hair washing that can remove, to use
Cause big inconvenience in family；Third is not to be suitable for long-term chronic electricity physiological signal monitoring.It is elapsed along with the time, conduction liquid
It can gradually volatilize, evaporate, increase skin electrode interface impedance.It is applied in terms of health supervision and brain-computer interface with brain electricity
It is unfolded and deeply, the deficiency of the mode of this electrode+conductive paste increasingly highlights.In these application scenarios, in order to which self is strong
Health is guarded or amusement, and user is difficult to tolerate with this operation mode that other people place, wash hair after.Some mechanisms research and develop thus
The dry electrode for having gone out not needing conductive paste, as M.A.Lopez-Gordo et al. is delivered for 2014 on SENSORS periodicals《Dry
EEG Electrodes》In one text, main dry electrode company and product in recent years are reviewed and are summarized, these dry electrodes
Device can not all be compared no matter in terms of usage comfort or in terms of signal quality with wet electrode.In order to eliminate hair
Barrier, dry electrode device mostly use pectinate texture, and hair is passed through using broach, while having lacked conductive paste buffering, broach
Smaller cross section is in direct contact scalp and itself has certain discomfort, while in order to keep contact more stable, often also needing to
Apply the pressure of bigger on the dry electrode of pectination.In terms of impedance and signal stabilization, due to lacking the buffering of conductive paste, dry electrode
Device is often very sensitive to motion artifacts, this is very unfavorable to the system required with wearing.It is ground simultaneously in long-term
Study carefully middle discovery, that there are hardness is really up to the mark by the dry electrode overwhelming majority that metal electrode or other polymeric materials are formed, and wears uncomfortable
Phenomena such as, when being especially for use in human brain experiment, a degree of feeling of pain is brought to subject.The dry electrode in fixed form
With need as wet electrode by cap or other special devices, using being inconvenient.
For the problem that above-mentioned electro physiology acquisition sensor there are the problem of, and exist in conjunction with some existing patents of invention
A kind of aligned carbon nanotube is proposed from adhering to dry electrode and its preparation process, this dry electrode of carbon nanotube have fluff structures
And adhesiveness, the process for eliminating injecting glue one by one after wearing electrode, it realizes to wear and use；Simultaneously using fexible film support knot
Structure so that device has flexible and ductility well, can closely be sticked with skin.Double-deck conductive film can be with flexibility
Supporting layer deformation and change, ensure stable electrical connection, reduce motion artifacts and noise.The wire quality of filamentary silver or spun gold is super
Gently, the quality that further reduced device entirety realizes frivolous theory, and helping device, inertia is small during exercise, equally subtracts
Small noise and artefact.Due to frivolous flexible structure and ultralight quality, which greatly improves wear comfort.
Invention content
(1) technical problems to be solved
For existing dry, wet electrode in wear comfort, Preparatory work of experiment overlong time, long term monitoring and skin electrode
The problems such as interface impedance is unstable, the main purpose of the present invention is to provide a kind of aligned carbon nanotube from adhere to dry electrode and its
Preparation process.Wherein designed aligned carbon nanotube has double-deck flexible structure from dry electrode is adhered to, can be according to skin arc
Degree carries out adaptability deformation and skin closely sticks.Simultaneously because aligned carbon nanotube can be adsorbed on skin from adhesion arrangement
Surface reduces the contact impedance of device.It is different by bulky cap and device fixation from conventional dry electrode and wet electrode needs,
The electrode quality is less than 20g, does not need foreign object and is auxiliarily fixed, greatly improves usage comfort.
(2) technical solution
In order to achieve the above objectives, on the one hand, the present invention proposes a kind of aligned carbon nanotube from adhering to dry electrode, including takes
To carbon nanotube self-sticking layer, flexible conductive film, flexible support layers and conducting wire, wherein the aligned carbon nanotube self-sticking layer
Be fixed in the flexible conductive film, be fixed in the flexible conductive film in the flexible support layers, the conducting wire with
The flexible conductive film connection.
Preferably, the flexible conductive film is Double-layer flexible conductive film, and upper layer is conducting polymer composite, and lower layer is
The thickness of conductive metal, the flexible conductive film is 50-500 μm.
Preferably, the conducting polymer composite is PEDOT or electric silica gel, and the conductive metal mixes for Ag/AgCl
Object or gold (Au).
Preferably, the material of the flexible support layers is selected from PDMS, PI, EVA or EPDM, the thickness of the flexible support layers
It is 20-300 μm.
On the one hand, the invention also provides a kind of aligned carbon nanotubes from the preparation process for adhering to dry electrode, including：
Flexible support layers are formed in substrate；
Flexible conductive film is formed in the flexible support layers；
Multiple carbon nanotubes are fixed in the flexible conductive film；
The substrate is removed, the connecting wire in the flexible conductive film.
Preferably, before forming the flexible support layers, the substrate is cleaned and is dried first.
Preferably, flexible support layers are formed by following steps：Conducting polymer composite and curing agent are uniformly mixed,
Even coating on the substrate, is then heating and curing, the mode of the coating is preferably spin coating.
Preferably, the flexible support layers are surface-treated, its surface is made to have hydrophily, the surface treatment is excellent
It is selected as oxygen plasma treatment.
Preferably, the flexible conductive film is formed by following steps：Be added in silver paste AgCl obtain Ag AgCl it is mixed
Close object, using Ag AgCl mixtures form conductive film, then the applying conductive polymer material layer on conductive film.
Preferably, multiple carbon nanotubes are made to be fixed in the flexible conductive film by being heating and curing.
Preferably, the substrate is selected from copper foil or aluminium foil, and the substrate is removed using corrosive liquid.
(3) advantageous effect
It can be seen from the above technical proposal that the present invention is using by based on a kind of flexible material, in combination with carbon
What nanotube conductive object was formed has the flexible dry electrode for being suitable for skin shape.It is formed by the dry electricity of layer flexible carbon nanotube
It is great to have good mechanical characteristic and comfort level, the feeling of pain for generating electrode compressing will not be made one and conduction liquid is largely remained and made
At sense of discomfort.Adaptability deformation along with flexible support layers to skin, maintains the stability of impedance between skin electrode,
The quality for greatly improving bio-electro-physiologic signal, conducive to being monitored for a long time to brain signal.Show in a large amount of experiment
The aligned carbon nanotube that the present invention is formed works well from dry electrode test is adhered to, and can reach acquisition similar with commercial electrode
Effect greatly improves comfort level, and reduces cost, it was demonstrated that the feasibility of the present invention.
Description of the drawings
Fig. 1 is that the aligned carbon nanotube of the embodiment of the present invention adheres to the structural schematic diagram of dry electrode certainly；
Fig. 2 is that the aligned carbon nanotube of the embodiment of the present invention adheres to the preparation process schematic diagram of dry electrode certainly.
Reference sign：
1- aligned carbon nanotube self-sticking layers；2- Double-layer flexible conductive films；3- flexible support layers；4- conducting wires.
Specific implementation mode
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in more detail.
Fig. 1 is that the aligned carbon nanotube of the embodiment of the present invention adheres to the structural schematic diagram of dry electrode certainly, as seen from the figure, is orientated
Carbon nanotube includes aligned carbon nanotube self-sticking layer 1, Double-layer flexible conductive film 2,3 and of flexible support layers from dry electrode is adhered to
Conducting wire 4.
Aligned carbon nanotube self-sticking layer 1 is longitudinal by the good multi wall of conductive characteristic, metallic conduction characteristic carbon nanotube
It arranges, carbon nanotube diameter (10 nanometers of representative diameter) between 8-15 nanometers, it is (typical highly between 0.5-3 millimeters
Highly 2 millimeters) proper alignment (bulk density 0.7mg/cm3).Aligned carbon nanotube self-sticking layer 1 has adsorptivity, can paste
It applies in skin surface, passes through the density and height of CVD Controllable growths.
The upper layer of Double-layer flexible conductive film 2 is conducting polymer composite, and lower layer is conductive metal.Wherein conducting polymer
Material can be PEDOT (poly- (3,4-ethylene dioxythiophene)), electric silica gel etc., and conductive metal can be Ag/AgCl mixtures
Or it is golden (Au).In this embodiment, Double-layer flexible conductive film 2 include Ag AgCl mixtures formed the first conductive layer, and
The second conductive layer that PEDOT is formed, Double-layer flexible conductive film 2 are prepared by MEMS technology and chemical etching technology, are had and are prolonged
Malleability and elasticity, 2 thickness of Double-layer flexible conductive film can be 50-500 μm.
The material of flexible support layers 3 can be selected from dimethyl silicone polymer (PDMS), polyimides (PI), ethylene-acetate
Vinyl ester copolymers (EVA), ethylene propylene diene rubber (EPDM) etc., in this embodiment, flexible support layers 3 pass through spin coating by PDMS
Mode formed, thickness is controllable, can be 20-300 μm.
Conducting wire 4 can be spun gold or filamentary silver.
As shown in Fig. 2, the preparation process of the aligned carbon nanotube of the present invention from the dry electrode of adherency includes：
Step 1：First, copper foil is cleaned in ethanol solution, and is put into ultrasonic device 10 minutes, washes the attachment on surface
Object.
Step 2：The copper foil cleaned up is placed in vacuum constant temperature drying box (50 DEG C), is toasted 20-30 minutes, it is completely dry
Until dry.
Step 3：On the sheet glass or silicon chip of 300um thickness, copper foil is fixed on silicon chip surface with high temperature gummed tape, with silicon
Piece surface closely sticks.
Step 4：PDMS solution is configured, is mixed with 10: 1 ratio of curing agent, and fix the silicon with copper foil on sol evenning machine
PDMS is uniformly spin-coated on using sol evenning machine on copper foil 6 by piece, is formed the PDMS film that thickness is 20-600 μm, is propped up as flexibility
Support layer 3.Then on hot plate 100 DEG C cure one hour.Preferably, the mixed solution of PDMS and curing agent is vacuumized, is gone
Bubble removing.
Step 5：The PDMS film piece being cured is put into plasma etching machine, oxygen plasma etching processing 2 minutes is right
PDMS film surface is handled, it is made to have certain hydrophily.
Step 6：High-purity silver paste is modulated, being less than 7: 3 according to proportioning is added a small amount of chlorination silver powder, forms Ag AgCl mixing
Object.
Step 7：Prolong a direction with scraper on PDMS film and the conductive silver paste modulated is uniformly spin-coated on film table
Face forms the first layer of fine and close bilayer conductive film 2.
Step 8：80 DEG C of hot plate toasts 1 hour, formed Ag AgCl mixture films, and the spin coating PEDOT on sol evenning machine
(poly- (3,4-ethylene dioxythiophene)) forms 2 second layer of bilayer conductive film.
Step 9：It will be in SiO2On with the good carbon nanotube 1 of CVD growth, along the sized divisions of scribing before growth, every piece
Length and width dimensions 2*2mm is clamped with tweezers and is disposed vertically on PEDOT conductive films.
Step 10：Electrode slice after transfer carbon nanotube is positioned in thermostatic drying chamber, side is vertical on the carbon nanotubes
Bloom pressing is put, 50 DEG C keep the second layer (PEDOT) solidification of 30 minutes carry out conductive films 2 and carbon nanotube 1 to fix.
Step 11：Corrode copper foil, discharges Thin Film Carbon Nanotube electrode.Copper foil is released from silicon chip, utilizes level
Porous is put into copper foil in corrosive liquid, it is allowed to float on corrosive liquid surface, and corrosive liquid cannot overflow across copper foil, avoids influencing upper table
The conductive film 2 and carbon nanotube 1 in face.
Step 12：Thin-film device is taken out after corrosion, is put into baking oven 20 minutes, it is to be packaged after taking-up etc..
Step 13：Packaging and testing are encapsulated with spun gold or 4 pressure welding of filamentary silver on pressure welding platform, enable the device to use and survey
Examination.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical solution and advantageous effect
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the protection of the present invention
Within the scope of.
Claims (10)
1. a kind of aligned carbon nanotube adheres to dry electrode, including aligned carbon nanotube self-sticking layer, flexible conductive film, flexibility certainly
Supporting layer and conducting wire, wherein the aligned carbon nanotube self-sticking layer is fixed in the flexible conductive film, the flexibility is led
It is fixed on conductive film in the flexible support layers, the conducting wire is connect with the flexible conductive film.
2. aligned carbon nanotube as described in claim 1 is from adhering to dry electrode, which is characterized in that the flexible conductive film is
Double-layer flexible conductive film, upper layer are conducting polymer composite, and lower layer is conductive metal, and the thickness of the flexible conductive film is
50-500 μm, it is preferable that the conducting polymer composite is PEDOT or electric silica gel, and the conductive metal mixes for Ag/AgCl
Object or gold (Au).
3. aligned carbon nanotube as described in claim 1 adheres to dry electrode certainly, which is characterized in that the material of the flexible support layers
Material is selected from PDMS, PI, EVA or EPDM, and the thickness of the flexible support layers is 20-300 μm.
4. a kind of any one of claim 1-3 aligned carbon nanotubes adhere to the preparation process of dry electrode certainly, including：
Flexible support layers are formed in substrate；
Flexible conductive film is formed in the flexible support layers；
Multiple carbon nanotubes are fixed in the flexible conductive film；
The substrate is removed, the connecting wire in the flexible conductive film.
5. preparation process as claimed in claim 4, which is characterized in that, first will be described before forming the flexible support layers
Substrate is cleaned and is dried.
6. preparation process as claimed in claim 4, which is characterized in that the flexible support layers are formed by following steps：It will
Conducting polymer composite and curing agent are uniformly mixed, and even spread on the substrate, is then heating and curing, the side of the coating
Formula is preferably spin coating.
7. preparation process as claimed in claim 4, which is characterized in that be surface-treated to the flexible support layers, make it
Surface has hydrophily, and the surface treatment is preferably oxygen plasma treatment.
8. preparation process as claimed in claim 4, which is characterized in that the flexible conductive film is formed by following steps：
In silver paste be added AgCl obtain Ag AgCl mixtures, using Ag AgCl mixtures formed conductive film, then in conductive thin
Applying conductive polymer material layer on film.
9. preparation process as claimed in claim 4, which is characterized in that so that multiple carbon nanotubes is fixed on institute by being heating and curing
It states in flexible conductive film.
10. preparation process as claimed in claim 4, which is characterized in that the substrate is selected from copper foil or aluminium foil, the substrate profit
It is removed with corrosive liquid.
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Cited By (5)
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| CN110063724A (en) * | 2019-04-26 | 2019-07-30 | 清华大学 | Flexible biological electrode and preparation method thereof |
| CN112587140A (en) * | 2020-12-09 | 2021-04-02 | 清华大学深圳国际研究生院 | Self-attaching bionic octopus sucking disc micro-nano structure dry electrode |
| CN112790776A (en) * | 2019-11-13 | 2021-05-14 | 中国科学院苏州纳米技术与纳米仿生研究所 | Self-adhesive surface myoelectricity dry electrode |
| CN113243921A (en) * | 2020-02-13 | 2021-08-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | Flexible bioelectricity dry electrode, manufacturing method thereof and manufacturing method of flexible substrate film |
| CN113855322A (en) * | 2021-09-22 | 2021-12-31 | 西安电子科技大学 | Wireless fully-integrated flexible stretchable artificial larynx based on mechanical acoustics and preparation method thereof |
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| CN113243921B (en) * | 2020-02-13 | 2023-02-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Flexible bioelectricity dry electrode, manufacturing method thereof and manufacturing method of flexible substrate film |
| CN112587140A (en) * | 2020-12-09 | 2021-04-02 | 清华大学深圳国际研究生院 | Self-attaching bionic octopus sucking disc micro-nano structure dry electrode |
| CN113855322A (en) * | 2021-09-22 | 2021-12-31 | 西安电子科技大学 | Wireless fully-integrated flexible stretchable artificial larynx based on mechanical acoustics and preparation method thereof |
| CN113855322B (en) * | 2021-09-22 | 2022-06-10 | 西安电子科技大学 | Wireless fully-integrated flexible stretchable artificial larynx based on mechanical acoustics and preparation method thereof |
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