CN107800323A - A kind of full degradable nano generator of natural material - Google Patents
A kind of full degradable nano generator of natural material Download PDFInfo
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- CN107800323A CN107800323A CN201610808735.6A CN201610808735A CN107800323A CN 107800323 A CN107800323 A CN 107800323A CN 201610808735 A CN201610808735 A CN 201610808735A CN 107800323 A CN107800323 A CN 107800323A
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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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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
- A61N1/00—Electrotherapy; Circuits therefor
- A61N1/18—Applying electric currents by contact electrodes
- A61N1/32—Applying electric currents by contact electrodes alternating or intermittent currents
- A61N1/36—Applying electric currents by contact electrodes alternating or intermittent currents for stimulation
Abstract
The medical implantable devices field of the present invention, disclose a kind of full degradable nano generator of natural material, characterized in that, the nano generator, which includes friction electric generator and the encapsulating structure for encapsulating the friction electric generator, the friction electric generator, includes polymeric layer；The polymeric layer and the encapsulating structure are formed by natural degradable material；The natural degradable material is the one or more in fibroin albumen, soybean protein, egg white, cellulose, lignin, chitin, starch, rice paper, PHA and Glucomannan.The full degradable nano generator obtained according to the present invention, it is simple in construction, securely and reliably, there is good encapsulation, and its treatment time and degradation time are controllable, have a good application prospect.
Description
Technical field
The present invention relates to medical implantable devices field, in particular it relates to which a kind of full degradable nano of natural material generates electricity
Machine.
Background technology
In recent years, implantable medical device growth momentum of new generation is swift and violent, and compared to conventional portable Medical Devices, it has
Have the advantages that volume is dexterous, easy to use and quick, so as to cause people's extensive concern.It has been widely used in medical science now
Diagnosis and therapy field.But implantable medical device is in external form and size, energy consumption, selection and biocompatibility and degraded simultaneously
Etc. be faced with stern challenge.
Georgia ,U.S.A Institute of Technology professor Wang Zhonglin etc. has invented nano generator, and the nano generator is available to rub
Wipe when the material that position is different in potential sequence (Triboelectricity series) contacts with each other and/or rubbed and electricity occurs
Son is shifted so as to export electric energy.And nano generator has the characteristics that small volume, light weight, it is very suitable for driving implantation
Formula, portable and small-sized self-driving type electronic equipment.
There is the relevant report that nano generator is applied to implantable medical device field at present, such as will can receive
Rice generator is as degradable doctors such as osteoblastic proliferation and differential stimulus device, pacemaker and degradable implantable sensors
Treat the energy supply source of device.In order to which nano generator is fabricated into implantable medical device, it is necessary to consider the size of device
The problems such as with size, device biocompatibility in itself and the security of encapsulation, also needed to if being related to device degradability
The problems such as considering encapsulated layer and device inside degradation time and security.Most implantable medical devices are in vivo all now
It is nondegradable, can only be taken out from the method removed in vivo by performing the operation.Can thus make medical expense increase and meanwhile it is heavier
What is wanted is the pain that it can make patient experience operation again.If implanted equipment is designed to be able to by metabolism certainly
So removed naturally after degraded and/or dissolving, by the very big quality of life for improving implanted equipment user, reduce pain and operation
Spend.
Now, energy shortage and people's extensive and strong concern is caused the problems such as environmental pollution.Exploration and research can be again
Production-goods source and environmentally friendly material, to alleviate lack of energy and environmental crisis, turn into survival and development of mankind important topic it
One.So sight is gradually transferred to based on renewable animal and plant resource, biodegradable, environmentally friendly day by many researchers
In the research of right high polymer material.Natural macromolecular material be it is a kind of without by artificial synthesized, be naturally occurring in animals and plants and
Macromolecular organic compound in microbial body.Compared with traditional artificial synthesized high polymer material, it has inexhaustible and used
The advantage such as inexhaustible, thus as the focus of people's research.
One kind is proposed in the prior art to punch on encapsulated layer, then is controlled by the scheme in the magnetic plug hole
The working time of medical embedded equipment.This scheme is based on control body fluid and passes through encapsulated layer, once body fluid will through encapsulated layer
Influence and destroy internal generator work.So magnetic plug is actually the working time for controlling generator, and equipment is in body
Interior degradation time is simultaneously uncontrolled.And the program needs equipment complete when terminating treatment task, by applying strong magnetic in vitro
, magnetic plug is sucked out, adds the program of equipment degraded, therefore there is certain limitation.
Secondly, the constituent material of used implanted nanometer generating machine equipment such as condensing model, PLA in the prior art
All it is artificial synthesized high polymer material with polycaprolactone etc..It is compared with natural macromolecular material, it is necessary to by raw material-urge
It is combined to-the production stage such as machine-shaping.First, it does not have the cheap natural polymer prices of raw materials, wide material sources, yield
The advantage such as abundant, renewable.And need to add various catalyst product is generated by polymerisation and be processed, this can increase
Production cost and process triviality.
Finally, used implanted nanometer generating machine equipment is taken to improve generator output in the prior art
Method is with photoetch method or other method produces nanoscale in polymer layer surface or micron-sized surface roughness, process are multiple
It is miscellaneous.
The content of the invention
It is an object of the invention to provide a kind of full degradable nano generator prepared by natural macromolecular material, this entirely may be used
Degraded nano generator can working time and degradation time play a part of regulation and control in vivo to implantation equipment, while can carry
The output performance of high generator.
To achieve these goals, the present invention provides a kind of full degradable nano generator of natural material, the nanometer generating
Machine, which includes friction electric generator and the encapsulating structure for encapsulating the friction electric generator, the friction electric generator, to be included
Polymeric layer；The polymeric layer and the encapsulating structure are formed by natural degradable material；The natural degradable material
For selected from fibroin albumen, soybean protein, egg white, cellulose, lignin, chitin, starch, rice paper, PHA and Portugal
One or more in sweet glycan.
Preferably, the natural degradable material is one kind in rice paper, egg white, fibroin albumen, chitin and cellulose
It is or a variety of.
Pass through above-mentioned technical proposal, a kind of full degradable nano generator can be obtained, can particularly obtained a kind of suitable
For the full degradable nano generator of medical embedded formula, it not only can with the working time of control device in vivo,
Can be with the degradation time of control device.Secondly, the full degradable nano generator that prepared by the natural material can be microsize
Bioelectronics equipment provides the scheme for solving driving problems, and also there are some researches show apply micro voltage, energy in damaged tissues both sides
The cell around damage is stimulated, is advantageous to its active and propagation, and then promote new tissue growth.In addition, prepare nanometer generating
Material used in machine is entirely to be made up of natural polymer, and it has abundance, wide material sources and the advantage such as cheap,
Finally, due to natural macromolecular material film surface carries the surface roughness of nanometer or micron level, it is not necessary to is additionally carried out table
Face handles the output performance that can improve generator.Therefore, full degradable natural high polymer material nano generator of the invention
With boundless application prospect.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the full degradable nano generator prepared according to the natural degradable material of the preferred embodiment of the present invention
Topology example figure.
Fig. 2 is the full degradable nano generator prepared according to the natural degradable material of the preferred embodiment of the present invention
In friction electric generator topology example figure.
Description of reference numerals
1st, encapsulating structure 2, friction electric generator
21st, first electrode layer 22, polymeric layer
23rd, the second electrode lay 24, micro-structural
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
In the present invention, in the case where not making opposite explanation, the noun of locality such as " upper and lower " used refers to the side in diagram
To；" interior " refers to towards full degradable nano generator, and " outer " refers to towards full degradable nano generator external；" the first face "
" the second face " refers to two faces relative in stereochemical structure, refers specifically to upper and lower two faces in diagram.It is mentioned in the present invention " can
Degraded " refer to by the body fluid natural degradation of institute's implant site or can be dissolved in institute's implant site body fluid formed ion it is molten
Liquid or particle solution, are then excreted by metabolism, without depositing in vivo.
The invention provides a kind of full degradable nano generator of natural material, the nano generator includes friction electricity and generated electricity
Machine and the encapsulating structure for encapsulating the friction electric generator, the friction electric generator include polymeric layer；It is described poly-
Compound layer and the encapsulating structure are formed by natural degradable material；The natural degradable material be selected from fibroin albumen,
One kind in soybean protein, egg white, cellulose, lignin, chitin, starch, rice paper, PHA and Glucomannan or
It is a variety of.
In above-mentioned material, the fibroin albumen refers to the extraction from silk fiber (comprising fibroin albumen and sericin)
A kind of natural polymer fibrin, its content account for the 70-80% of silk, contain 18 kinds of amino acid.Specifically, the fibroin
The preparation method of albumen can be：Silk is immersed in sodium carbonate liquor (such as can be for 0.02mol/L's) first and handled
(treatment temperature is 70-120 DEG C, and preferably 100 DEG C or so, processing time is 15-60 minutes, preferably 30 minutes or so), instead
After should terminating (such as being carried out by freeze drier) is dried with after distilled water flushing；Secondly dried sample is added to chlorine
Change after being dissolved in calcium dissolution system, then solution is placed in bag filter (such as can be 2-5K MWCO, preferably 3.5K MWCO)
Middle dialysis more than 1 day (being preferably 2-4 days, more preferably 2 days or so)；Finally the above-mentioned silk fibroin protein solution dialysed is dried
Fibroin albumen is obtained after (such as being carried out by freeze drier).
According to the preferred embodiment of the present invention, the natural degradable material is rice paper, egg white, fibroin egg
In vain, the one or more in chitin and cellulose.
Worked in the full degradable nano generator human implantable of the present invention, implant site can be heart, lung, liver
Etc. main organs surface；It may also be the particular organization positions such as subcutaneous, muscle surface and bone surface；It can also be internal various chambers
Gap, implanted is certainly not limited to, can also applied in vitro or in other environment.The size of full degradable nano generator
It can be changed according to implant site difference, areal extent is typically in 2-100cm2(it is preferably 2-50cm2).In addition, the present invention
The shape and structure of full degradable nano generator can be also designed according to demand.
In the preferred embodiment of the present invention, as shown in figure 1, the full degradable nano generator may include to seal
Assembling structure 1 and friction electric generator 2.
As the friction electric generator 2, it is preferable that as shown in Fig. 2 the friction electric generator 2 includes：First electrode
Layer 21, the upper surface of the first electrode layer 21 is in contact with the inner surface in the first face of the encapsulating structure 1；Polymeric layer 22,
The polymeric layer is fixed on the lower surface of the first electrode layer 21；The second electrode lay 23, the second electrode lay 23 is positioned at polymerization
The lower section of nitride layer, the lower surface of the second electrode lay 23 are in contact with the inner surface in the second face of the encapsulating structure 1.
According to the present invention, the available two kinds of different materials of position in friction potential sequence of friction electric generator 2 are mutual
Rub to provide electricity output.Because the friction electric generator 2 in Fig. 1 is used for implanted equipment, therefore, structure in the present embodiment
Material into each part of friction electric generator 2 selects natural degradable material of its security Jing Guo reliable authentication.
According to the present invention, encapsulating structure 1 is used to encapsulate friction electric generator 2, and its natural degradation time is more than treatment time.
Encapsulation is to realize the committed step of full degradable nano generator, if friction 2 unsealed encapsulation of electric generator, is implanted
Body fluid can be filled in the storeroom for triboelectricity afterwards, make that electrostatic charge can not be formed on its contact surface.According to the one of the present invention
Individual preferred embodiment, the encapsulating structure 1 are the one or more in fibroin albumen, chitin, cellulose and rice paper, more
One kind preferably in fibroin albumen, chitin and cellulose.
In the present invention, first electrode can be prepared in the upper surface of polymeric layer 22 by vacuum sputtering or vapour deposition method
Layer 21.The upper surface (surface not combined with polymeric layer 22) of first electrode layer 21 can be with encapsulating structure 1 (Fig. 2 is not shown)
The inner surface contact in the first face (i.e. in Fig. 1 above encapsulating structure 1).The lower surface of the second electrode lay 23 can be with encapsulating structure 1
The second face (i.e. in Fig. 1 below encapsulating structure 1) inner surface contact.The composition material of polymeric layer 22 and the second electrode lay 23
Diverse location of the material position in friction potential sequence, when it is in contact with each other, electrostatic charge can be produced on the contact surface.Ambient pressure
Or vibrations etc. can deform upon friction electric generator 2, such as make friction electric generator during the deformation of flexible encapsulating structure 1
2 deform upon, and Relative friction, contact and/or separation occur between polymeric layer 22 and the second electrode lay 23, with polymeric layer
22 and the second electrode lay 23 distance and/or relative position change, can be produced in first electrode layer 21 and the second electrode lay 23
The raw induced electricity potential difference changed therewith, to provide electricity output.
According to the preferred embodiment of the present invention, the polymeric layer is thin made of natural degradable material
Film.Preferably, the thickness range of the polymeric layer is between 10 μm -500 μm.
According to the preferred embodiment of the present invention, encapsulating structure film made of natural degradable material
Formed.Preferably, for formed the encapsulating structure film thickness range between 10 μm -500 μm.
According to the present invention, the polymeric layer 22 and encapsulating structure 1 are fexible film structures.
According to the present invention, the natural degradable material can form the encapsulating structure by the conventional method in this area
With the polymeric layer.It is specifically as follows cladding process or pressed film method.
As the forming method of the encapsulating structure, specifically, cladding process embodiment is as follows：Encapsulating material is applied first
Overlay at the gap opening of the friction surrounding of electric generator 2, to close gap and form enclosed construction, then dry coated material
Material, encapsulating material is finally coated on to whole surface and the drying of the enclosed construction again, to complete to encapsulate.Pressed film method embodiment
It is as follows：Two pieces can be done first and is both greater than 2 overall films of friction electric generator, then send out this two pieces of films with friction electricity respectively
The center that the upper and lower surface of motor 2 is bonded and makes generator be in film, it is finally thin by this two pieces with film laminator
The edge of film, which forces together, makes its sealing, to complete to encapsulate.As can be seen that the upper and lower surfaces and therewith of friction electric generator 2
Can be bonding or separation between the surface of the encapsulating structure of contact.
Especially, unless otherwise specified, the degradable natural macromolecule membrane structure institute of encapsulating structure 1 and polymeric layer 22
Material can be replaced mutually.
According to the preferred embodiment of the present invention, the lower surface of the polymeric layer has micro-structural, described micro-
Structure can increase effective contact area of the polymeric layer and the second electrode lay.In the present invention, the micro-structural is
The surface roughness of nanometer or micron level, in particular to relative to smooth film surface, the prominent of many is partially formed in film
Shape structure is played, can be confirmed by observing the cross-sectional configuration of polymer film, such as can be observed with SEM,
The thickness of micro-structural refers to the average relative altitude of the overshooting shape micro-structural formed on film surface.
Polymeric layer is directed in the prior art, it is conventional using such as photoetch method (Photolithography) and/or deeply anti-
Ion etching method (Deep Reactive Ion Etching) is answered to increase its surface roughness, to improve friction electric generator
Output.And in the present invention, due to the characteristic of natural macromolecular material itself, pass through the natural height prepared by following methods out
Molecularly Imprinted Polymer film surface has micro-structural (such as micro-structural 24 in Fig. 2), makes polymeric layer 22 and the second electrode lay
23 effective contact area increase, so as to improve the output of friction electric generator 2.There is the poly- of micro-structural 24 in order to prepare surface
Compound layer, the polymeric layer are preferably prepared using cladding process.
Specifically, can be for fibroin albumen film, its preparation method：First, that fibroin albumen is added into hexafluoro is different
In propanol solution, stir to be formed clear solution (for example, the wherein content of fibroin albumen is 3-10 mass %, preferably 6 matter
Measure %)；Secondly, above-mentioned clear solution is spread evenly across glass and pulled, then glass plate is statically placed in fume hood and spontaneously dried
(such as can be to dry more than 4 hours, preferably 6-18 hours, more preferably 12 hours) afterwards, it is thin to be prepared fibroin albumen
Film.
For cellophane, its preparation method can be：Cellulose is dissolved in the solution (example of sodium hydroxide and urea
Such as, the mass ratio of sodium hydroxide, urea and water is 5-9：10-14：79-83, preferably 7：12：81) in, it is uniformly mixing to obtain mixed
Solution (for example, wherein the content of cellulose can be 3-6 mass %, preferably 4.5 mass % or so) is closed, and the mixing is molten
Liquid is coated with a glass, and by the glass plate sulfuric acid and metabisulfite solution (for example, the content of sulfuric acid is 5 mass %, sulfuric acid
The content of sodium is 10 mass %) in immersion (such as can be more than 5 minutes, preferably 10-30 minutes, more preferably 15 minutes
Left and right), remove cellophane and clean, then be fixed in natural drying at room temperature on glass plate.
For chitin film, its preparation method can be：First, a certain amount of chitin powder is taken to be added to by hydrogen-oxygen
(mass ratio of sodium hydroxide, urea and water is 9-13 to the mixed solution of change sodium, urea and water three composition：2-6：83-87, it is excellent
Elect 11 as：4：85) in, stir to form clear solution (content of chitin is 4-10 mass %, preferably 7 mass %).
Secondly, a certain amount of above-mentioned solution coating is taken on a glass, then glass plate is completely soaked in absolute ethyl alcohol (more than 1 hour,
Or so preferably 2 hours).Finally, the chitin film on glass plate is removed and rinsed well with substantial amounts of water, then by it
Fix to be placed in spontaneously drying in room temperature on a glass and obtain chitin film.
The rice paper film, can be the medicine general's board rice paper film (specification produced purchased from Zhejiang Province Haining glutinous rice paper plant：
6 × 8cm, thickness：100 microns).
In the present invention, the membrane structure that the polymeric layer is prepared preferably by the above method.
In accordance with the present invention it is preferred that the thickness range of the micro-structural 24 on the surface of polymeric layer 22 10nm-1 μm it
Between.
In the present invention, the first electrode layer and the second electrode lay are conductive degradable metal membrane structure.
According to the preferred embodiment of the present invention, the degradable metal membrane structure is by containing magnesium, gold, silver, copper and stainless
One or more arbitrary proportion alloys in steel are made.
According to the present invention, the thickness of the first electrode layer and the second electrode lay can be commonly used in the art various
Thickness, it is preferable that the thickness of the first electrode layer and the second electrode lay is 10nm-100 μm.According to the present invention, described first
Electrode layer and the second electrode lay can be formed using various methods commonly used in the art, specifically, the first electrode layer
It can be formed with the second electrode lay using magnetron sputtering method, silk screen print method or vapour deposition method.
In the friction electric generator of the present invention, the distance between the polymeric layer and the second electrode lay can roots
It is specifically chosen according to needing, such as can be 200 μm of -1.5mm, preferably 500-1200 μm.
In order to regulate and control the working time of the full degradable nano generator of the present invention and degradation time, variety classes can be used
Degradable natural high polymer material make encapsulating structure, can also be carried out by any means that those skilled in the art are understood
The modification of material so as to reach regulation and control degradation time purpose.The degradation time distribution that full degradable nano generator implants
Scope was at -2 years 1 day.Degraded test is carried out to portion of material, specific method of testing is：It is 1.0 × 1.5cm's to take a piece of size
Membrane material is added in an appropriate size air-tight bottle with cover, and a certain amount of phosphate buffered saline solution is added into bottle
(PBS), it is ensured that salting liquid is totally submerged membrane material, air-tight bottle is placed in the insulating box that temperature is 37 DEG C.Measure each material
Degradation time is as shown in table 1.
The concrete principle and scheme of degradation time control are as follows：First, the degradation time of homogenous material in itself is certain
In the range of, and certain distribution is presented, as the degradation time of rice paper within -1 day 1 minute, when fibroin albumen is degraded
Between at 1 month or so, the cellulose degradation time was at 2 years or so.Therefore can be controlled to a certain extent from different types of material
The work of device processed and degradation time.Secondly, material is handled by chemical reagent to change the characteristic of material so as to enter
One step control degradation time.At 1 month or so as the degradation time of fibroin albumen.If by fibroin albumen in absolute ethyl alcohol
After (soak time is more than 30 minutes) is fully soaked in solution, its degradation time can extend to 6 months or so；If by silk
After fibroin fully soaks (soak time is more than 30 minutes) in absolute methanol, its degradation time can extend to 1 year left side
It is right.Finally, if doing further accurate control to soak time of the fibroin albumen in ethanol solution, such as 1 second, 5 seconds, 30
Second and 10 minutes, the degradation time of fibroin albumen will be between 31 days to 6 months.Like this can be with more rich material degradation
The selection of time.Summary process, it is possible to finer each component part of regulation and control in considerable time span
Degradation time, so as to control the work of whole device and degradation property.
Table 1
| Encapsulating material species | Processing method | Degradation time |
| Rice paper | Nothing | 1 day |
| Egg white | Nothing | 15 days |
| Fibroin albumen | Nothing | 31 days |
| Fibroin albumen | Absolute ethyl alcohol | 6 months |
| Chitin | Nothing | 9 months |
| Fibroin albumen | Absolute methanol | 1 year |
| Cellulose | Nothing | 2 years |
It will be appreciated by those skilled in the art that the full degradable nano generator can also have extraction circuit, (Fig. 1 does not show
Go out), the extraction circuit can lead to the electricity output that the electric generator 2 that rubs provides the object being powered.This area skill can be used
Any means that art personnel are understood realize the extraction circuit.It should be noted that if desired by the defeated of electric generator 2 that rub
Go out to lead to full degradable nano generator external, it is to be ensured that the sealing of full degradable nano generator, for example, will first can draw
Go out circuit and be electrically connected to the output block of friction electric generator 2, then prepare the encapsulating structure 1 for encapsulating friction electric generator 2,
To realize better seal.
Embodiment 1
1) a certain amount of chitin powder is taken to be added to the mixed solution (hydrogen being made up of sodium hydroxide, urea and water three
The mass ratio of sodium oxide molybdena, urea and water is 11：4：85) in, it is the transparent molten of 7 mass % to stir and to form chitin content
Liquid.Then, take a certain amount of above-mentioned solution coating on a glass, then glass plate is totally submerged 2 hours in absolute ethyl alcohol.
Finally, the chitin film on glass plate is removed and rinsed well with substantial amounts of water, be then fixed juxtaposition on a glass
Spontaneously dried in room temperature and obtain chitin film.The chitin film thickness prepared by this method is 300 μm, passes through scanning
Electron microscope (SU8020, Japanese HITACHI (Hitachi) company, similarly hereinafter) observation confirms that the chitin film surface has thickness
For 180nm micro-structural.
2) friction electric generator 2 as shown in Figure 2, friction electricity hair are prepared by the use of above-mentioned chitin film as polymeric layer
Motor 2 includes：First electrode layer 21；It is fixed on the polymeric layer of the lower surface of the first electrode layer 21；And positioned at polymerization
The second electrode lay 23 of the lower section of nitride layer.Wherein, first electrode layer 21 and the second electrode lay 23 are the magnesium electricity that vapour deposition method is formed
Pole, the thickness of first electrode layer 21 are 200nm, and the thickness of the second electrode lay 23 is 10 μm, polymeric layer and the second electrode lay it
Between distance be 900 μm.
3) fibroin albumen is added in hexafluoroisopropanol solution, stirs to form clear solution (wherein fibroin albumen
Content be 6 mass %)；Secondly, above-mentioned clear solution is spread evenly across glass and pulled, then glass plate is statically placed in fume hood
After middle natural drying 12 hours, the fibroin albumen film that thickness is 250 μm is prepared.
4) above-mentioned fibroin albumen thin-film packing structure 1 is formed by pressed film method in the outside of above-mentioned friction electric generator 2, had
Body, prepare the film in two pieces of first faces for being respectively greater than friction electric generator 2 and the second face first, and this two pieces of films are divided
Upper and lower surface not with the electric generator 2 that rubs is bonded, and then the edge of this two pieces of films is forced together with film laminator
Make its sealing, to complete to encapsulate.
5) the full degradable nano generator prepared is carried out with mechanical motor exporting test experiments in vitro.Experiment knot
Fruit shows that the output performance of generator is good, and voltage output value is -30/30V.
Embodiment 2
Method according to embodiment 1 prepares full degradable nano generator, unlike, use the fibre that thickness is 400 μm
Plain film is tieed up as polymeric layer.The preparation method of the cellophane is as follows：
Cellulose is dissolved in into the solution of sodium hydroxide and urea, and (mass ratio of sodium hydroxide, urea and water is 7：12：81)
In, the content for being uniformly mixing to obtain cellulose is 4.5 mass % mixed solution, and the mixed solution is coated on into glass plate
On, then by the glass plate, in the solution of sulfuric acid and sodium sulphate, (content of sulfuric acid is 5 mass %, and the content of sodium sulphate is 10 matter
Measure %) in immersion 15 minutes or so, remove cellophane and cleaned with substantial amounts of water, then be fixed in room temperature on glass plate
Spontaneously dry.The micro-structural for confirming that there is thickness to be 200nm on the cellophane surface is observed by SEM.
The full degradable nano generator prepared is carried out with mechanical motor to export test experiments in vitro.Experimental result table
Bright generator output performance is good, and voltage output value is -27/27V.
Comparative example 1
Method according to embodiment 1 prepares full degradable nano generator, unlike, encapsulating structure and polymeric layer are equal
For PLGA films.
The full degradable nano generator prepared is carried out with mechanical motor to export test experiments in vitro, it prepares hair
The voltage output value of motor is -16/16V.
Comparative example 2
Method according to embodiment 1 prepares full degradable nano generator, unlike, encapsulating structure is PLGA thin
Film, and the PLGA films as polymeric layer are handled by reactive ion etching method, it is 180nm its surface is had thickness
Micro-structural.
The full degradable nano generator prepared is carried out with mechanical motor to export test experiments in vitro, what it was prepared
The maximum voltage output voltage of generator reaches -30/30V.
By the contrast of above-described embodiment and comparative example, because natural material surface has the micro- knot of natural nanometer
Structure, the generator of output voltage and PLGA the films preparation after processing of its full degradable nano generator prepared is most
Big output voltage is suitable.Natural material cost is cheap, and it is easy to obtain, and does not need special surface treatment process, is to prepare
The excellent material of full degradable nano generator.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (11)
1. a kind of full degradable nano generator of natural material, it is characterised in that the nano generator includes friction electric generator
And for encapsulating the encapsulating structure of the friction electric generator, the friction electric generator includes polymeric layer；The polymerization
Nitride layer and the encapsulating structure are formed by natural degradable material；
The natural degradable material be selected from fibroin albumen, soybean protein, egg white, cellulose, lignin, chitin, starch,
One or more in rice paper, PHA and Glucomannan.
2. full degradable nano generator according to claim 1, wherein, the natural degradable material is rice paper, egg
Clearly, the one or more in fibroin albumen, chitin and cellulose.
3. full degradable nano generator according to claim 1, wherein, the friction electric generator includes：
First electrode layer, the upper surface of the first electrode layer are in contact with the inner surface in the first face of the encapsulating structure；
Polymeric layer, the polymeric layer are fixed on the lower surface of the first electrode layer；
The second electrode lay, the second electrode lay are located at the lower section of polymeric layer, the lower surface of the second electrode lay and the encapsulation
The inner surface in the second face of structure is in contact.
4. full degradable nano generator according to claim 3, wherein, the polymeric layer is natural degradable material
Manufactured film；
Preferably, the thickness range of the polymeric layer is between 10 μm -500 μm.
5. the full degradable nano generator according to any one in claim 1-4, wherein, the encapsulating structure is by day
Film made of right degradation material is formed；
Preferably, for formed the encapsulating structure film thickness range between 10 μm -500 μm.
6. full degradable nano generator according to claim 4, wherein, the membrane structure uses pressed film method or painting
The method of covering is formed.
7. full degradable nano generator according to claim 3, wherein, the lower surface of the polymeric layer has micro- knot
Structure, the thickness range of the micro-structural of the polymer layer surface is between 10nm-1 μm.
8. full degradable nano generator according to claim 3, wherein, the first electrode layer and the second electrode lay are equal
For conductive degradable metal membrane structure；
Preferably, the thickness of the first electrode layer and the second electrode lay is 10nm-100 μm.
9. full degradable nano generator according to claim 8, wherein, the degradable metal membrane structure by containing
One or more arbitrary proportion alloys in magnesium, gold, silver, copper and stainless steel are made.
10. full degradable nano generator according to claim 8, wherein, the polymeric layer and the second electrode
The distance between layer is 200 μm of -1.5mm, preferably 500-1200 μm.
11. full degradable nano generator according to claim 1, wherein, the full degradable nano generator also wraps
Include extraction circuit, the electricity output drawn circuit and be used to draw the friction electric generator.
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| CN108565048A (en) * | 2018-04-18 | 2018-09-21 | 天津大学 | Conformal biodegradable implanted flexibility energy supply device and preparation method thereof |
| CN109450288A (en) * | 2018-11-12 | 2019-03-08 | 浙江大学 | A kind of friction nanometer power generator and its method based on milk protein |
| CN109687756A (en) * | 2019-02-21 | 2019-04-26 | 中国科学院兰州化学物理研究所 | It is a kind of to be suitble to the friction nanometer power generator and the preparation method and application thereof based on biomembrane material used in high humidity environment |
| CN110138259A (en) * | 2019-05-21 | 2019-08-16 | 中国科学院兰州化学物理研究所 | A kind of resistance to high humidity flexible wearable friction nanometer power generator and its preparation method and application |
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