CN101326539A - RFID tag - Google Patents
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- CN101326539A CN101326539A CNA2006800458687A CN200680045868A CN101326539A CN 101326539 A CN101326539 A CN 101326539A CN A2006800458687 A CNA2006800458687 A CN A2006800458687A CN 200680045868 A CN200680045868 A CN 200680045868A CN 101326539 A CN101326539 A CN 101326539A
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- rfid label
- power supply
- substrate
- sealant
- battery
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
Disclosed is a RFID tag comprising a light-weighted thin foldable built-in power supply which is reusable by charging. Specifically disclosed is an RFID tag comprising an IC module (2), an antenna (3) and a power supply. This RFID tag has a thickness of not more than 0.9 mm, and the power supply is a built-in organic radical battery having a thickness of not more than 0.7 mm.
Description
Technical field
The present invention relates to a kind of RFID label, comprise integrated circuit (IC) module, antenna and power supply, particularly a kind ofly comprise chargeable and the RFID label of secondary cell that can discharge as power supply.
Background technology
For RFID label (adopted name that is used for the wireless device of radio-frequency (RF) identification (RFID)), and IC-card that use electromagnetic wave and read write line (read/write) device and similar device communicate hand-held by the people is called as non-contact IC card.Non-contact IC card consists essentially of plastic clip and is arranged on antenna and IC module in the plastic clip.By using electromagnetic wave at non-contact IC card be used for carrying out power supply between the read-and-write device of this IC-card, the supply of clock signal and so on and such as the input and output of the information of data and instruction.
In addition, some non-contact ICs are stuck in and also comprise power supply (for example with reference to patent document 1) outside IC module and the antenna.This IC-card is constructed with two plastic sheets, and power supply is sealed between these two plastic sheets with IC module and antenna.Comprise the non-contact IC card of power supply compare with the non-contact IC card that does not comprise power supply have can long-distance transmissions information (tens meters) advantage.As the power supply that is arranged in this IC-card, can consider the thin film lithium button cell as one-shot battery, and rechargeable lithium ion batteries, rechargeable nickel-hydrogen battery and excide battery are as rechargeable battery (secondary cell).
Yet there is such problem in the IC-card that wherein has one-shot battery, and promptly IC-card is no longer carried out its function when battery life exhausts.By comparison, when above-mentioned rechargeable battery is installed in the IC-card, by also reusable this IC-card that rechargeable battery is charged.As this trial, there is the project of describing in the patent document 2 for example.Yet when adopting above-mentioned rechargeable battery, its charging needs for a long time, for example at least one hour.Also have, when through 2 years or longer, the capacity of rechargeable battery obviously descends; Unless the replacement battery, otherwise need frequent charge.
In addition, the size of non-contact IC card roughly meets the international standard size that is called the ID-1 card, and with the size identical with thickness (long 54.0mm * wide 85.7mm * thick 0.76mm) of cash card and credit card.Yet card thickness roughly is the 0.76mm that meets international standard, in fact can change, and some jigs have the thickness of about 0.9mm.Therefore, as the power supply that will be arranged in this IC-card with international standard size, consider the thickness of card, this power supply thickness must reduce and be equal to or less than about 0.7mm.Yet above-mentioned thin film lithium button cell, rechargeable lithium ion batteries and rechargeable nickel-hydrogen battery need be equal to, or greater than the thickness of 1mm, therefore can not make the IC-card with international standard size.In the prior art, although there is the thin film capacitor as supply unit that can be installed in the card that thickness is 0.76mm, it has the problem of little memory capacity.
In addition, suppose that also this non-contact IC card can be placed in the back pkt. of trousers, and when the holder bends over, can be bent.In addition, suppose the state of being held by its holder except this non-contact IC card, this card also is used to be fixed to the object with curved surface.Yet, thin film capacitor, lithium button cell and traditional rechargeable lithium ion batteries are too hard and can not be crooked.Therefore, have such problem, promptly above-mentioned power supply can not be applicable to RFID label and non-contact IC card in the situation of label and card bending.
Patent document 1: the open sequence number No.Hei-7-262333 of Jap.P..
Patent document 2: international open sequence number No.WO01/97300.
Patent document 3: the open sequence number No.2002-151084 of Jap.P..
Patent document 4: the open sequence number No.2002-304996 of Jap.P..
Patent document 5: the open sequence number No.2003-308839 of Jap.P..
Summary of the invention
The problem to be solved in the present invention
In above-mentioned situation, the power supply that expectation will be arranged in the RFID label of non-contact IC card that also supposition can be bent or analog can be installed in the label with 0.9mm or littler thickness, and can be crooked.In addition, expect that also this battery is to pass through the reusable secondary cell of charging, and charging was finished with the short time.In addition, need a kind of like this RFID label, wherein can replace this rechargeable battery with new battery according to service time.
Therefore an object of the present invention is to provide a kind of thickness is 0.9mm or littler RFID label, and comprising passing through the reusable flexible power supply of charging.
The scheme of dealing with problems
RFID label of the present invention is the RFID label that comprises IC module, antenna and power supply or comprise IC module, antenna, display element and power supply, is characterised in that to comprise that organic free radical battery (Organic Radical Battery) is as power supply.Even the 0.9mm of RFID label or littler thickness, this organic free radical battery also can be installed in wherein.
The organic free radical battery that adopts among the present invention is the battery of a kind of use as the redox reaction of the organic free radical compound of active substance.Patent document 3 has disclosed a kind of organic free radical battery, wherein uses nitroxid compound (nitroxide radical compound), aryloxy group free radical compounds (aryloxy radical compound) or has the material of the polymer compound of specific amino triazine (aminotriazine) structure as positive electrode.In addition, patent document 5 has disclosed a kind of base battery, and wherein the electrode reaction at least one is that a kind of free radical compounds that has thia nitrogen (thiazyl) free radical therein is used as reaction product or product and the reaction that obtains in positive electrode and the negative electrode.
By adopting this organic free radical battery, can provide film, light, folding and chargeable IC-card power supply.This organic free radical battery can charge and be suitable as most the power supply of the device of IC-card size the short time.
In the present invention, can consider the power supply in the RFID label and the layout of IC module in every way.Can consider wherein to be provided with the substrate that comprises cavity part and at least power supply leave situation in this cavity part in, and the substrate comprise recessed portion is set wherein, at least power supply leaves in this recessed portion, and further is provided with sealant and covers the situation that is arranged in the power supply in the recessed portion.In addition, it is also conceivable that IC module wherein is arranged on the substrate and power supply is arranged in the situation in the sealant that covers this substrate.Setting is used for depositing the cavity part of this power supply and the recessed portion of placing this power supply in substrate as described above, can guarantee the flatness of this RFID label.
In addition, by being provided with on the substrate surface of power supply and on surface, monox (SiO being set in the face of the sealant of this power supply
xX=1 to 2) layer and silicon oxynitride (SiO
xN; X=0.5 to 1.5) layer can strengthen water proofing property.This is because consider that its environment for use is for the higher water proofing property of organic free radical battery expectation.Can also strengthen water proofing property in the sealant by power supply is sealed in.In addition, antenna arrangement can be existed thereon on the substrate of power supply and IC module, also can adopt the antenna of closed type and this antenna also as sealant.Perhaps, this antenna can be used as substrate.
Also have, but can easily replace battery when being positioned at sealant strip off with the position that power supply is relative at least when making.
In addition, display element can be arranged in the RFID label of the present invention.This display element can comprise film liquid crystal display cells, electroluminescence (EL) element, Electronic Paper and light emitting diode (LED) display element.This makes it possible to show Useful Information on this RFID label, such as remaining sum.
In addition, temperature sensor can be arranged in the RFID label of the present invention.Thereby this RFID label can be fixed on food, beverage, fresh flower, blood product, medicine, exact instrument and the similar articles, and its temperature is sent to the external unit that is used to monitor these article.
Also have, can be with the transducer arrangements that is used for the detection of biological characteristic information at RFID label of the present invention, biological information such as pulse frequency, blood pressure, ECG information, electromyogram information etc.Therefore, by this sensor is fixed on the human body, can obtains biological information and this information is sent to other staff.
Also have, position information sensors can be arranged in the RFID label of the present invention.Therefore, this label can be used to obtain object and people's positional information.
In addition, notification element can be installed in the RFID label of the present invention.The device that this notification element can comprise and be used for using up by making, sound, vibration, taste and similar approach are notified.The result is, can use up by making, sound or vibration indication traffic operation, and notifying communication state and result of communication.
Subsidiary, in display element, temperature sensor, biometric information sensor, position information sensors and the notification element not only, and also two or more combination in any wherein can be arranged in the RFID label of the present invention.
Advantage of the present invention
According to the present invention, a kind of RFID label is provided, this RFID label is thin, light and be suitable for carrying, and it is collapsible and comprise power supply.
Preferred forms
Below, by providing the description of the preferred embodiments of the present invention with reference to the accompanying drawings.
[1] RFID label (non-contact IC card)
At first, will describe according to RFID label of the present invention.In addition, in the following description,, element identical or of equal value is repeated in this description for being endowed identical reference number and will omitting.Also has the dimension scale during the unnecessary coupling of the dimension scale in the diagram is described.
Fig. 1 shows the example of the structure of RFID label.The RFID label that illustrates has the structure with the sequential cascade of overlayer 9a, core sheet 8a, core sheet 8b and overlayer 9b.Core sheet 8a and 8b are as substrate.
Fig. 2 (a) is that Fig. 2 (b) is the X-Y xsect of Fig. 2 (a) from the diagram of the overlayer 9b that watches.Overlayer 9b is the thick overlay of about 0.1mm, is made by the resin of PVC, ABS, PET-G or similar material.In overlayer 9b, be provided with porose 11 in charging terminal 7 (Fig. 3 (a)) position overlapped with core sheet 8a.
Fig. 3 (a) is that Fig. 3 (b) is the X-Y xsect of Fig. 3 (a) from the diagram of the core sheet 8b that watches.Core sheet 8b is the plastic sheet of thickness from 0.25mm to 0.35mm, is made by the resin of PVC, ABS, PET-G or similar material.In core sheet 8b, be charging wiring and charging terminal 7 layout through holes 6, and core sheet 8b comprises that cavity part 10 (recessed portion) is to hold organic free radical battery 1.
Fig. 4 (a) is that Fig. 4 (b) is the X-Y xsect of Fig. 4 (a) from the diagram of the core sheet 8a that watches.Core sheet 8a is the plastic sheet of thickness from 0.25mm to 0.35mm, is made by the resin of PVC, ABS, PET-G or similar material; On core sheet 8a, be provided with organic free radical battery 1, IC module 2, antenna 3, lead-in wire 4 and charging wiring 5.Organic free radical battery 1 is arranged on here the power supply as drive IC module 2.Antenna 3 is for being connected to the planar coil antenna of IC module 2.
Fig. 5 (a) is that Fig. 5 (b) is the X-Y xsect of Fig. 5 (a) from the diagram of the overlayer 9a that watches.Overlayer 9a is the thick overlay of about 0.1mm, is made by the resin of PVC, ABS, PET-G or similar material.
According to the order of overlayer 9a, core sheet 8a and 8b and overlayer 9b with they hot rolling contract (100 ℃ to 150 ℃ of temperature, pressure 1kg/cm of carrying out stacked together
2To 10kg/cm
2, crispatura 30 seconds to 10 minutes time), this lamination merges mutually afterwards, thereby obtains the RFID label of exemplary embodiment shown in Figure 1.
In above-mentioned RFID label, although being arranged in core sheet 8a, goes up power supply (organic free radical battery 1) to be contained in the cavity part 10 that forms among the core sheet 8b, the structure of power supply of the present invention is not subjected to the restriction of this structure.For example, power supply can be arranged in the sealant of covered substrate.Fig. 6 (a) has been for having installed the cross-sectional view of the sealant 100 of organic free radical battery 1 therein, and Fig. 6 (b) is the diagram of the sealant 100 watched from below.Outer peripheral portion 102 on the back side of sealant 100 is a viscosity.In addition, organic free radical battery 1 is contained in the battery cover 101, and the little teat of being made by metal or carbon 11 extends from battery 1.Little teat 11 is used to be electrically connected to each electrode of battery 1.
Fig. 7 (a) is that wherein organic free radical battery 1 is arranged in the planimetric map of the RFID label of sealant 100.The cross-sectional view that obtains for line X-Y along Fig. 7 (a).This RFID label has wherein overlayer 9a, core sheet 8a, core sheet 8b, overlayer 9b and the stacked in this order structure of sealant 100 that comprises organic free radical battery 1.Viscosity part 102 in the outer peripheral portion at the back side by using sealant 100 can be fixed to sealant 100 on the core sheet 8b.When sealant 100 was fixed, the little teat 11 of battery 1 was overlapping with the terminal 12 of IC module 2.As a result, battery 1 is electrically connected to IC module 2.In addition, overlayer 9b and core sheet 8b have opening portion, and little teat 11 and battery 1 are arranged in this opening portion when fixing seal layer 100.
In addition, in order to strengthen water proofing property, sealant 100 and battery cover 101 with opening portion that battery 1 wherein has been installed and battery 1 facing surfaces on, can for example form the monox (SiO of the about 30nm of thickness to 200nm by evaporation
xX=1 to 2) layer.
Fig. 8 (a) is the planimetric map that comprises the RFID label of sealant, the part of sealing layer covered substrate (core sheet) and organic free radical battery 1, the cross-sectional view that Fig. 8 (b) obtains for the line X-Y along Fig. 8 (a).In core sheet 8b, form space segment between surface and the lower surface thereon, the organic free radical battery 1 that is arranged on the core sheet 8a is accommodated in this space segment of core sheet 8b.In addition, sealant 100 is arranged in overlayer 9b upward to cover organic free radical battery 1 and to seal this space segment.Here, sealant 100 is peelable; By peeling sealant 100 off, can easily replace organic free radical battery 1 wherein.In addition, although flexible plastic material is used to core sheet 8a and 8b and overlayer 9a and 9b so that the bending of battery is preferably adopted flexible resin material or tinsel for sealant 100 similarly.
Fig. 9 (a) is the planimetric map with RFID label of display element, and this label comprises the part of covered substrate (core sheet) and the sealant of organic free radical battery 1.The cross-sectional view that Fig. 9 (b) obtains for the line X-Y along Fig. 9 (a).The cross-sectional view that Fig. 9 (c) obtains for the line W-Z along Fig. 9 (a).Form space segment to hold organic free radical battery 1 in core sheet 8b, the organic free radical battery 1 that is arranged on the core sheet 8a is contained in this space segment of core sheet 8b.In addition, form spatial portion and assign to hold display element 102 in core sheet 8a and 8b, the display element 102 that is arranged on the overlayer 9b is contained in this space segment of core sheet 8a and 8b.In addition, sealant 100 is arranged in overlayer 9b upward to cover organic free radical battery 1 and to seal this space segment.Here, sealant 100 is strippable; By peel seal layer 100, can easily replace organic free radical battery 1 wherein.
In addition, the display element 102 of this example can be used for the RFID label that organic free radical battery 1 wherein is arranged on the cavity part 10 between core sheet 8a and the 8b, as in example shown in Figure 1.
Display element can be liquid crystal display cells, EL display element and Electronic Paper.An example of liquid crystal display cells comprises counter electrode 301, liquid crystal layer 302, drive electrode 303 and backlight 304, shown in Figure 10 a.In addition, an example of EL display element comprises glass substrate 305, anode (transparency electrode) 306, EL film 307, and negative electrode 308, shown in Figure 10 b.In addition, an example of Electronic Paper comprises transparent resin substrate 309, transparency electrode 310, microcapsule layer 311 and drive electrode (TFT electrode) 312, shown in Figure 10 c.
Aspect this, in order to strengthen water proofing property, sealant 100 with recessed portion that battery wherein has been installed (space segment) and battery 1 facing surfaces on, can for example form the monox (SiO of the about 30nm of thickness to 200nm by evaporation
xX=1 to 2) layer or the about 30nm of thickness are to the silicon oxynitride (SiO of 200nm
xN; X=0.5 to 1.5) layer.
Figure 11 (a) is the planimetric map that has the RFID label of any sensor and notification element.The cross-sectional view that Figure 11 (b) obtains for the line X-Y along Figure 11 (a).The cross-sectional view that Figure 11 (c) obtains for the line W-Z along Figure 11 (a).Form cavity part 10 (recessed portions) and hold organic free radical battery 1 in core sheet 8b, the organic free radical battery 1 that is arranged on the core sheet 8a is contained in this cavity part 10 of core sheet 8b.In addition, core sheet 8a is provided with sensor 14 and notification element 15.Sensor 14 and notification element 15 are connected to organic free radical battery 1 and IC module 2 via wiring 13.And although sensor 14 is covered by core sheet 8b, and notification element 15 is exposed via the hole that is arranged among the overlayer 9b.
In addition,, yet can replace battery 1 by peel seal layer 100 although be fixed in the label at Figure 11 (a) organic free radical battery 1 in the example shown in Figure 11 (c), as Fig. 7 (a) to shown in the structure of 9 (b).In this case, in order to strengthen water proofing property, be preferably in sealant 100 with recessed portion that wherein is provided with battery (space segment) and battery facing surfaces on, the monox (SiO of the about 30nm of thickness to 200nm is set
xX=1 to 2) layer or silicon oxynitride (SiO
xN; X=0.5 to 1.5) layer.In addition, display element 102 can also be increased to the RFID label of this example, shown in Fig. 9 (a).
An example of sensor 14 can be temperature sensor, be used to detect biological information sensor such as the biological information of pulse frequency, blood pressure, ECG information, electromyogram information or similar information etc.
An example of notification element 15 can be the element that produces light, sound, vibration or taste.As light-emitting component, available LED or EL element.Sounding component can be the ultrathin membrane loudspeaker of paper shape.As vibrating elements, available piezoelectric element or magnetostriction element (Magnetostrictor Element).
The element that produces taste as electricity consumption can be considered wherein element that a kind of perfume is combined with electrothermal transducer such as well heater, and this perfume is at room temperature tasteless and vaporize and the generation taste when environment temperature raises.Perhaps can adopting exerts pressure to the microcapsule that wherein comprises perfume breaks the element of this microcapsule to emit a smell.
Under the situation of temperature sensor,, can monitor its temperature if this label is fixed on food, beverage, fresh flower, blood product, medicine, exact instrument and the similar articles as the sensor of RFID label of the present invention with above-mentioned example.For example, can adopt real-time mode to monitor its temperature history in conveying and storing process; If take place unusually, this temperature history can be used to help follow-up investigation.In addition, this sensor can also be as being fixed to the body temperature trans to use on the human body thereon.For example, in hospital, can obtain the variation of patient temperature in real time at the nurse center.
In addition, if display element 102 is installed on the RFID label with temperature sensor, then except sending the Current Temperatures or temperature history that is detected, can on display element 102, show it.
In addition, if with the biological information sensor as the sensor in the RFID label 14, can obtain to wear the elderly or unsound people's the active state or the information of health status of the independent life of this RFID label, and information can be sent to doctor and Ta or her household.
In addition, when display element 102 is installed on the RFID label with the biological information sensor, blood pressure, pulse frequency and the similar information that detects like this can be sent to external device (ED) and wearer can know these projects by using display element 102.If temperature sensor also has been installed, can send and show body temperature in label.
And, if position information sensors is fixed on object or the people as the sensor in the RFID label 14 and this label, can obtain this object or people's positional information from the outside.For example, can find the children that lose, perhaps detect the article of sending, perhaps obtain the information of independent the elderly who lives or unsound people's active state at recreation ground.
In addition, if one or more in this position information sensors and display element 102, temperature sensor and the biological information sensor is installed on the RFID label, for example, external transmission be can pass through, biological information and temperature information in the elderly who obtains life separately or unsound people's positional information, obtained; And the wearer also can use display element 102 to know biological information and temperature information.
In addition, if notification element is installed in the RFID label, can or when detecting, produce light, sound or vibration when using antenna 3 to carry out RF communication by sensor 14.Also have, comprise that therein when the carrier passed through the ticketing spot, this card self can pass through light, sound or vibration informing RF successful communication under the situation of RFID label as the non-contact IC card with electronic coin function of notification element 15.In the case, can be by the remaining sum of sound notification blind person electronic coin.In addition, the RFID label that comprises notification element 15 therein leaves in wallet or the certificate folder or when being fixed on wallet or the bunch of keys, if this relative article is lost, label is sounded or light is convenient to find it.
In addition, if one or more in notification element 15 and display element 102, temperature sensor, biological information sensor and the position information sensors is installed on the RFID label, can be outside above-mentioned function, use the unusual of the old man of sound or the only work of similar approach advice note or biological characteristic information of unsound people and temperature information, go to bed to impel it.
As mentioned above, the preferred embodiments of the present invention are described, yet, in RFID label according to the present invention, antenna 3 also can be arranged in the same substrate (core sheet 8a) that is used for organic free radical battery 1, perhaps also can be arranged on the sealant 100 to be used as sealant 100.
Figure 12 illustrates the concept map of the example of the IC module that adopts in the RFID label of the present invention.This IC module 2 comprises storer 2a (ROM, RAM), control microprocessor 2b, instruction 2d, clock 2e and front end 2f.Here, be used to electric energy from organic free radical battery 1 to send radiowave and rewriting and record data by IC module 2.
[2] film organic free radical battery
Below, the film organic free radical battery that adopts in the RFID label of present embodiment is described.Figure 13 is the skeleton view of film organic free radical battery, and Figure 14 is the decomposition diagram of the inner structure of demonstration battery.
Film organic free radical battery is that thickness is the organic free radical battery of 0.7mm or littler film-type.Have in the basic structure of machine battery at film, comprise stable free radical compounds as the free radical positive electrode 202 of its material, comprise porous polypropylene and cellulosic separator 203, comprise that the negative electrode 204 of lithium metal or similar material is stacked in this order.In this stepped construction, the separator 203 that has permeated electrolytic solution is clipped in the middle and is sealed in therebetween by being positioned at adventitia 201 on its two sides.In addition, thus positive electrode 202 and negative electrode 204 are connected respectively to positive electrode lead-in wire 205 and negative electrode lead-in wire 206 obtains electric energy by these lead-in wires in this structure.As adventitia 201, adopt the thin laminated film of the aluminium that for example has low vapor permeability.
Below, each component parts of the organic free radical battery that adopts among description the present invention.
(1) free radical positive electrode
As the positive electrode active substance that is used for free radical positive electrode 202, can adopt the nitroxid polymkeric substance, the nitroxid that this nitroxid polymkeric substance comprises following molecular formula (1) expression at reducing condition in its molecule as part-structure, the state of oxidation comprise oxygen ammonium (oxoammonium) (nitroxide kation) by following molecular formula (2) expression in its molecule as part-structure.
If adopt the organic free radical battery, consider that when it discharges electric charge shifts between the oxygen ammonium group that the nitroxid group and the following molecular formula (2) of following molecular formula (1) expression are represented as one-shot battery.In addition, if adopt this battery, consider that when its charging and discharge, electric charge reversibly shifts between the oxygen ammonium group that the nitroxid group and the following molecular formula (2) of following molecular formula (1) expression are represented as secondary cell.Here, the nitroxid group refers to a kind of substituting group, and the oxygen atom that wherein constitutes the nitroxid of the combination that comprises oxygen atom and nitrogen-atoms comprises not paired electronics.In this nitroxid group, not paired electronics is owing to the electronics of nitrogen-atoms attracts characteristic to be stabilized on the oxygen atom.
By using this nitroxid polymkeric substance, the battery with high-energy-density can be operated with being stabilized.
[molecular formula 1]
Following molecular formula (3) to (7) has shown the schematic structure example of nitroxid polymkeric substance.
[molecular formula 2]
In the free radical polyalcohol that these molecular formula (3) are represented to (7), the positive electrode material is a nitroxid by molecular formula (3) to (7) expression at reducing condition, and be the oxygen ammonium of being represented by following molecular formula (8) to (12) respectively (nitroxide kation) in the state of oxidation.Consider that when battery operated electric charge arrives transfer between the oxygen ammonium (nitroxide kation) of (12) in nitroxid and the following molecular formula (8) that molecular formula (3) arrives (7).
[molecular formula 3]
[molecular formula 4]
[molecular formula 5]
In addition, these nitroxid polymkeric substance preferably have 500 or bigger weight-average molecular weight, are 5000 or bigger better.This be because weight-average molecular weight be 500 or bigger situation under polymkeric substance be not easy in the battery electrolytic solution, to dissolve, and weight-average molecular weight be 5000 or bigger situation under solubilized hardly.This polymkeric substance of polymer form can be the shape of chain, branch or network.Also have, can adopt the structure that comprises by the bridge of crosslinking chemical (crosslinkingagent) structure.
In addition, although every kind in these nitroxid polymkeric substance can be used as single composition use of planting, also can be with two kinds or more heterogeneous mutual combination wherein.In addition, also can be with these compositions and the combination of other active materials.
In addition, when using the nitroxid polymkeric substance to form electrode, can also hybrid conductive agent (conductivity giving agent) reduce impedance.The material of this conductive agent can comprise the fine granular of carbon, such as graphite, carbon black and acetylene black and conducting polymer, such as polyaniline, polypyrrole, polythiophene, polyacetylene and polyacene.
Also have,, can use bonding agent in order to increase bonding between nitroxid polymkeric substance and the conductive agent.This bonding agent can comprise resinoid bond, such as teflon, polyvinylidene fluoride, vinylidene difluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoeopropene multipolymer, butylbenzene copolymer rubber, polypropylene, tygon, polyimide and multiple polyurethane.
Free radical positive electrode 202 constitutes as the free radical positive electrode material by go up formation nitroxid polymkeric substance at positive electrode collector body (collector), as the positive electrode collector body, can adopt paper tinsel or the flat board made by nickel, aluminium, copper, gold, silver, aluminium alloy, stainless steel, carbon or similar material.Especially, battery is folding for convenience, is to constitute the nitroxid polymkeric substance that wherein forms gel state on the paper tinsel of current collector material preferably.
(2) negative electrode
As the active material that is used for negative electrode 204, lithium metal and lithium alloy can be used.Lithium alloy can comprise LiAl alloy, LiAg alloy, LiPb alloy, LiSi alloy, Li-Bi-Pb-Sn-Cd alloy and Li-Ga-In alloy.Its shape is not particularly limited, and can be the shape of for example film, the shape that constitutes by the powder that solidifies and the shape of fiber or thin slice.Also have, these negative electrode active materials can be used as homogenous material and use or be used in combination.
Construct negative electrode 204 by on collector body, forming above-mentioned active material,, can use and the collector body identical materials that comprises positive electrode as collector body.Naturally, for active material and collector body, material and thickness are selected to make things convenient for the bending of battery.
In addition, bonding between the component material that increases negative electrode 204 can be used bonding agent.This bonding agent can be teflon, polyvinylidene fluoride, vinylidene difluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoeopropene multipolymer, butylbenzene copolymer rubber, polypropylene, tygon, polyimide, carboxylated cellulose and the multiple polyurethane of part.
(3) separator
In order to prevent the contact between free radical positive electrode 202 and the negative electrode 204, can adopt the separator 203 of the perforated membrane that comprises tygon, polypropylene or similar material; Cellulose membrane and nonwoven fabrics.
(4) electrolyte
The electrolyte solution of separator 203 is used at electrode, promptly transmits charge carrier between negative electrode 204 and the positive electrode 202, and generally preferably this electrolyte solution have 20 ℃ down 10
-5To 10
-1The ionic conductivity of S/cm.As electrolyte solution, for example can adopt the electrolyte solution that obtains by dissolving electrolytic salt in solvent.
As electrolytic salt, for example can use LiPF
6, LiClO
3, LiBF
4, LiCF
3SO
3, LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2, LiC (CF
3SO
2)
3, and LiC (C
2F
5SO
2)
3
As the solvent that is used to dissolve this electrolytic salt, can adopt organic solvent, for example ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolacton, tetrahydrofuran, dioxolanes (dioxorane), sulfolane (sulforane), dimethyl formamide, dimethyl acetamide, N-N-methyl-2-2-pyrrolidone N-.In these solvents every kind can be used as that single solvent uses or wherein two kinds or manyly can mix use.
In addition, battery can comprise that solid electrolyte replaces separator 203.As solid electrolyte, can use (fluoride-vinylidene-based) multipolymer, such as polyvinylidene fluoride, vinylidene difluoride-hexafluoropropylene copolymer, vinylidene fluoride-ethylene copolymer, vinylidene fluoride-single fluoride copolymers, vinylidene fluoride-trifluoro-ethylene copolymer, vinylidene fluoride-TFE copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer based on vinylidene fluoride; Based on the polymkeric substance of vinyl cyanide (acrylnitrile), such as acrylonitrile methyl meth acrylat copolymer, vinyl cyanide-methyl acrylate copolymer, vinyl cyanide-ethyl methacrylate copolymers, vinyl cyanide-ethyl acrylate copolymer, vinyl cyanide-methacrylic acid copolymer, vinyl cyanide-acrylic copolymer and vinyl cyanide-vinyl acetate co-polymer; The polymkeric substance of polyethylene oxide, PEP-101 and acrylate and methacrylate.As solid electrolyte, can use the gel that produces in the above-mentioned this polymer material by electrolyte solution is penetrated into, perhaps can its virgin state use these polymer materials.For the ease of folding of battery, preferably the state with gel adopts electrolyte.
(5) cell shapes
The shape of the film organic free radical battery that adopts among the present invention is not restricted to sheet shape shown in Figure 13.Except the cell shapes of sheet shape, can use cylinder form, rectangular shape, coin shape shape and so on.This battery seals the stepped construction or the volume electrode that comprise above-mentioned positive electrode, negative electrode, electrolyte and separator by use can, resin box, metal forming, laminated film and so on and makes.Yet from being convenient to reduce the viewpoint of thickness, this cell shapes is preferably formed as and is the sheet shape by the laminated film sealing.As laminated film, can adopt single synthetic resin film, by will being fixed to one that obtains on the synthetic resin film such as the metal forming of aluminium foil, and by will be such as SiO
2Oxide be evaporated to one that obtains on the synthetic resin film.
(free radical polyalcohol synthesizes example)
The synthetic example of the free radical polyalcohol of describing by molecular formula (5) is as follows.
At first, synthon (2,2,6,6-tetramethyl piperidine-4-vinyl Oxy-1-oxygen base).This monomer is in the presence of as the iridium of catalyzer, by synthesizing for the reflux technology that comprises relevant free radical and vinyl acetate.Particularly, this monomer is according to zyanaru obu jiamerikan kemikaru sosaeti (Journal of The American Society, No.124, pp.1590-1591 (2002), Kokei Ishii et al) and the open sequence number No.2003-73321 of Jap.P. synthetic.
Then, this 2,2,6,6-tetramethyl piperidine-4-vinyl Oxy-1-oxygen base (monomer) is by the reactive polymeric by following molecular formula (13) expression.Its concrete method will be described below.
[molecular formula 6]
In ar gas environment, with 10g (50.4mmol) synthetic as mentioned above 2,2,6, the methylene chloride of 6-tetramethyl piperidine-4-vinyl Oxy-1-oxygen base (monomer) and 100mL adds in the three neck round-bottomed flasks to be cooled to-78 ℃.Further, 280mg (2mmol) boron trifluoride-ether complex is added to wherein and evenly distribution, then carries out it and handled 20 hours at-78 ℃.After this was finished dealing with, temperature was got back to room temperature, and the solid matter that obtains is filtered and by methanol rinse several times, thereby with the dry in a vacuum free radical polyalcohol (output capacity 70%) that obtains molecular formula (5) expression as red solid of the material that obtains.
Measure the IR spectrum of the free radical polyalcohol that obtains, this spectrum indication is because the loss of the peak value of 966674 (cm-1) of the vinyl of measuring under the situation of above-mentioned monomer.In addition, the free radical polyalcohol of acquisition can not dissolve in organic solvent and so on.The spin density of this free radical polyalcohol that obtains by ESR spectrum is 3.05 * 1021spin/g.This roughly meets the spin density that obtains based on such hypothesis, and promptly all bases of this polymkeric substance do not exist by deactivation and as base through polymerization.
(example of making of film organic free radical battery)
Below, the example of making of description film organic free radical battery.
1.68g the fine powder by the free radical polyalcohol of molecular formula (5) expression, 0.6g carbon dust (Raion make Ketjen black (Ketchen black) EC300j), the carboxymethyl cellulose of 96mg (CMC:HB-9 that Nihon Zeon makes), the teflon of 24mg (PTFE:F-104 that Daikin makes), and the water of 7.2mL stirs in homogenizer to be adjusted to uniform slurry.Make applicator by electrode this slurry is coated to (thickness 20 μ m: the positive electrode collector body), be the free radical positive electrode layer of 50 μ m with final formation thickness in 3 minutes 80 ℃ of dryings then on the aluminium foil.
Then, the free radical positive electrode that obtains like this is stamped into the square of 20mm * 20mm.3cm is long, and the wide nickel down-lead of 0.5mm is welded to the aluminium foil surface of this positive electrode.In addition, lithium paper tinsel (thickness 30 μ m) being fixed to Copper Foil (negative electrode collector body) goes up and is stamped into the square of 20mm * 20mm and finally form negative electrode.3cm is long, and the wide nickel down-lead of 0.5mm is welded to the copper foil surface of this negative electrode.
Then that the separator (25mm * 25mm square) and the negative electrode of free radical positive electrode, porous polypropylene is stacked together in this order, thus the relative electrode pair that forms of free radical positive electrode slurry with nickel down-lead with the lithium layer.
After this, aluminum composite membrane (length 40mm * width 40mm * thickness 0.76mm) melting on their three limits of two fusible welding is fetched the shape that forms sack, the electrode pair that then will have nickel down-lead is placed into wherein.In addition, with the electrolyte solution of 0.5cc (ethylene carbonate (EC)/diethyl carbonate (DEC of electrolytic salt that comprises the LiPF6 of 1.0mol/L; Mixing ratio EC: DEC=3: mixed solution 7)) be injected in this aluminium laminated cartridge.In this process, the end of nickel down-lead that each of 1cm has an electrode of nickel down-lead is arranged on the outside of this aluminium laminated cartridge, then this box is not had one side molten solder of fusion.As a result, electrode and electrolyte solution are sealed in this aluminium laminated cartridge fully.
By this way, made film organic free radical battery (length 40mm * width 40mm * thickness 0.4mm).This battery was with 100mA charging 30 seconds, and then the fixed current with 0.1mA discharges.As a result, this battery under the average voltage of 3.5V, discharge 5 hours (energy of 1.8mWh).
Example
(RFID forming label example 1)
Below, the example of making according to the RFID label of present embodiment is described.
As the IC-card of the RFID label of the cross-sectional structure shown in Fig. 1 by following acquisition.
At first, prepare the thick overlayer 9b that makes by PVC of 0.1mm; 0.28mm thick PVC core sheet 8b has wherein arranged to be used to the through hole 6 of wiring and charging terminal 7 that charges, and has comprised the cavity part 10 that is used to deposit organic free radical battery 1; 0.28mm thick PVC core sheet 8a wherein is provided with organic free radical battery 1, IC module 2, antenna 3, lead-in wire 4 and charging wiring 5; And the thick PVC overlayer 9a of 1.0mm.After this, overlayer 9a, core sheet 8a, core sheet 8b and overlayer 9a are stacked together in this order from the bottom, and contracted by hot rolling (120 ℃, pressure 2kg/cm
2, 2 minutes).As a result, made IC-card shown in Figure 1 fully.
(RFID forming label example 2)
As the IC-card of the RFID label shown in Fig. 7 (a) and 7 (b) by following acquisition.
Prepare the thick PVC overlayer 9b of 0.1mm, it comprises an opening portion, and organic free radical battery 1 and little teat 11 can pass through this opening portion; 0.28mm thick PVC core sheet 8b has wherein arranged to be used to the through hole 6 of wiring and charging terminal 7 that charges, and has comprised the space segment that is used to hold organic free radical battery 1; 0.28mm thick PVC core sheet 8a wherein is provided with IC module 2, antenna 3, lead-in wire 4 and charging wiring 5; And the thick PVC overlayer 9a of 1.0mm.After this, overlayer 9a, core sheet 8a, core sheet 8b and overlayer 9a are stacked together in this order from the bottom, and contracted by hot rolling (120 ℃, pressure 2kg/cm
2, 2 minutes) and to be shaped to card.The sealant 100 (length 40mm * width 40mm * thickness 0.4mm) that will comprise film organic free radical battery 1 is fixed on this card, makes battery 1 be contained in the space segment of core sheet 8b by the opening portion of the overlayer 9b of this card.As a result, made the IC-card shown in Fig. 7 (a) and 7 (b) fully.
(RFID forming label example 3)
As the IC-card of the RFID label shown in Fig. 9 (a), 9 (b) and 9 (c) by following acquisition.
Prepare the thick PVC overlayer 9b of 0.1mm, it comprises an opening portion, and organic free radical battery 1 and little teat 11 can pass through this opening portion; 0.28mm thick PVC core sheet 8b has wherein arranged to be used to the through hole 6 of wiring and charging terminal 7 that charges, and has comprised the space segment that is used to hold organic free radical battery 1 and display element 102; 0.28mm thick PVC core sheet 8a wherein is provided with IC module 2, antenna 3, lead-in wire 4, charging wiring 5 and display element 102; And the thick PVC overlayer 9a of 1.0mm.After this, overlayer 9a, core sheet 8a, core sheet 8b and overlayer 9a are stacked together in this order from the bottom, and contracted by hot rolling (120 ℃, pressure 2kg/cm
2, 2 minutes) and to be shaped to card.The sealant 100 (length 40mm * width 40mm * thickness 0.4mm) that will comprise film organic free radical battery 1 is fixed on this card, makes battery 1 be contained in the space segment of core sheet 8b by the opening portion of the overlayer 9b of this card.
As a result, made the IC-card shown in Fig. 9 (a), 9 (b) and 9 (c) fully.
Description of drawings
Fig. 1 is the cross-sectional view that the RFID label in the exemplary embodiment of the present invention is shown.
Fig. 2 (a) is the planimetric map of overlayer 9b.The cross-sectional view that Fig. 2 (b) obtains for the line X-Y along Fig. 2 (a).
Fig. 3 (a) is the planimetric map of core sheet 8b.The cross-sectional view that Fig. 3 (b) obtains for the line X-Y along Fig. 3 (a).
Fig. 4 (a) is the planimetric map of core sheet 8a.The cross-sectional view that Fig. 4 (b) obtains for the line X-Y along Fig. 4 (a).
Fig. 5 (a) is the planimetric map of overlayer 9a.The cross-sectional view that Fig. 5 (b) obtains for the line X-Y along Fig. 5 (a).
Fig. 6 (a) is for wherein having installed the cross-sectional view of the sealant of film organic free radical battery.Fig. 6 (b) is the diagram of the sealant among the Fig. 6 (a) that observes from below.
Fig. 7 (a) is the planimetric map of employing comprising the RFID label of the sealant of film organic free radical battery.The cross-sectional view that Fig. 7 (b) obtains for X-Y along the line.
Fig. 8 (a) is the planimetric map of RFID label that comprises the sealant of covered substrate and film organic free radical battery.The cross-sectional view that Fig. 8 (b) obtains for the line X-Y along Fig. 8 (a).
Fig. 9 (a) is the viewgraph of cross-section that has the RFID label of display element in the exemplary embodiment of the present invention.The cross-sectional view that Fig. 9 (b) obtains for the line X-Y along Fig. 9 (a).The cross-sectional view that Fig. 9 (c) obtains for the line W-Z along Fig. 9 (a).
Figure 10 (a) is the diagram that the structure of liquid crystal display cells is shown.Figure 10 (b) is the diagram that the structure of EL display element is shown.Figure 10 (c) is the diagram that the structure of Electronic Paper is shown.
Figure 11 (a) is the planimetric map with RFID label of any sensor and notification element.The cross-sectional view that Figure 11 (b) obtains for the line X-Y along Figure 11 (a).The cross-sectional view that Figure 11 (c) obtains for the line W-Z along Figure 11 (a).
Figure 12 is the concept map of the example of the IC module that adopts in the RFID label of the present invention.
Figure 13 is the skeleton view of film organic free radical battery.
Figure 14 is the decomposition diagram of the structure of demonstration film organic free radical battery.
The reference number explanation
1 film organic free radical battery
The 2IC module
3 antennas
4 lead-in wires
5 charging wirings
6 through holes
7 charging terminals
8a, the 8b core sheet
9a, the 9b overlayer
10 cavity parts
11 little teats
12 terminals
13 wirings
14 sensors
15 notification element
100 sealants
101 battery covers
102 display elements
103 display element switches
The wiring of 104 display elements
301 comparative electrodes
302 liquid crystal layers
303 drive electrodes
304 is backlight
305 glass substrates
306 anodes (transparency electrode)
The 307EL film
308 transparent resin substrates
309 transparent resin substrates
310 transparency electrodes
311 microcapsule layers
312 drive electrodes (TFT electrode)
201 adventitias
202 free radical positive electrodes
203 separators
204 negative electrodes
205 positive electrodes lead-in wire
206 negative electrodes lead-in wire
Claims (23)
1. a RFID label comprises the IC module, and antenna and power supply is characterized in that the organic free radical battery is installed in wherein as power supply.
2. RFID label as claimed in claim 1, wherein said RFID label thickness is 0.9mm or littler.
3. RFID label as claimed in claim 1 or 2 also comprises display element.
4. RFID label as claimed in claim 3, wherein said display element are any one in LCD, OLED display and the Electronic Paper.
5. as the described RFID label of one of claim 1 to 4, comprise substrate, wherein said power supply and IC module are disposed in the described substrate.
6. RFID label as claimed in claim 5, wherein said substrate comprises the cavity part, and power supply leaves in the described cavity part at least.
7. RFID label as claimed in claim 5, wherein said substrate comprises recessed portion, and power supply is arranged in the female part at least, described label comprises that also sealant is arranged on power supply in the female part with covering.
8. as the described RFID label of one of claim 1 to 4, comprise substrate and be used to cover the sealant of described substrate that wherein said IC module is set on the described substrate and power supply is arranged in the described sealant.
9. RFID label as claimed in claim 8, wherein said substrate comprises the recessed portion that is positioned at the position that power supply is set.
10. as the described RFID label of one of claim 7 to 9, wherein said antenna is arranged in the described sealant.
11. as the described RFID label of one of claim 5 to 9, wherein said antenna is arranged on the described substrate.
12. RFID label as claimed in claim 11, wherein said antenna is arranged on the same substrate with described power supply and IC module.
13. as the described RFID label of one of claim 7 to 12, wherein said substrate and described sealant comprise having flexible material respectively.
14. as the described RFID label of one of claim 7 to 13, wherein said sealant is set to can be from described strippable substrate.
15., wherein be provided with on the substrate surface of power supply and be provided with silicon oxide layer (SiO in the face of the surface of the sealant of described power supply as the described RFID label of one of claim 7 to 14
xX=1 to 2).
16., wherein be provided with on the substrate surface of power supply and be provided with silicon oxynitride layer (SiO in the face of the surface of the sealant of described power supply as the described RFID label of one of claim 7 to 14
xN; X=0.5 to 1.5).
17. as the described RFID label of one of claim 1 to 16, wherein said RFID label is a non-contact IC card.
18., comprise temperature sensor as the described RFID label of one of claim 1 to 17.
19., comprise the biological information sensor as the described RFID label of one of claim 1 to 18.
20. RFID label as claimed in claim 19, wherein said biological information sensor are any in pulse rate sensor, pre ure tra ducer, electrocardiography transducer and the electromyogram sensor.
21., comprise position information sensors as the described RFID label of one of claim 1 to 20.
22., comprise notifying device as the described RFID label of one of claim 1 to 21.
23. RFID label as claimed in claim 22, wherein said notifying device produces any in light, sound, vibration and the taste.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP350877/2005 | 2005-12-05 | ||
| JP2005350877 | 2005-12-05 | ||
| JP294271/2006 | 2006-10-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101326539A true CN101326539A (en) | 2008-12-17 |
Family
ID=40189199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800458687A Pending CN101326539A (en) | 2005-12-05 | 2006-12-04 | RFID tag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101326539A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102376206A (en) * | 2011-09-26 | 2012-03-14 | 无锡宇科万通科技有限公司 | Passenger ticket using reflective display screen |
| CN102509146A (en) * | 2011-09-26 | 2012-06-20 | 无锡宇科万通科技有限公司 | Card adopting reflective display screen |
| CN105008949A (en) * | 2012-10-09 | 2015-10-28 | Mc10股份有限公司 | Conformal electronics integrated with apparel |
| CN105526964A (en) * | 2015-12-02 | 2016-04-27 | 中国电子科技集团公司第四十九研究所 | Intelligent temperature and pressure sensing tag |
| CN105960667A (en) * | 2014-01-16 | 2016-09-21 | 马里利亚标签公司 | Fastening arrangement for replaceable voltage source for electronic price label |
| CN107210009A (en) * | 2015-01-19 | 2017-09-26 | 马里利亚标签公司 | Electronic price label and the battery unit for electronic price label |
| CN109255418A (en) * | 2017-07-13 | 2019-01-22 | 日本压着端子制造株式会社 | IC card and IC card charging connector |
| CN110729203A (en) * | 2019-09-27 | 2020-01-24 | 深圳赛意法微电子有限公司 | Packaging process of open electrocardiogram sensor |
| CN111816618A (en) * | 2020-09-03 | 2020-10-23 | 捷德(中国)科技有限公司 | Identification card and preparation method thereof |
| CN111956237A (en) * | 2020-07-31 | 2020-11-20 | 江苏麦酷博信息科技有限公司 | RFID blood collection card |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102509146A (en) * | 2011-09-26 | 2012-06-20 | 无锡宇科万通科技有限公司 | Card adopting reflective display screen |
| CN102376206A (en) * | 2011-09-26 | 2012-03-14 | 无锡宇科万通科技有限公司 | Passenger ticket using reflective display screen |
| CN105008949A (en) * | 2012-10-09 | 2015-10-28 | Mc10股份有限公司 | Conformal electronics integrated with apparel |
| US9846829B2 (en) | 2012-10-09 | 2017-12-19 | Mc10, Inc. | Conformal electronics integrated with apparel |
| CN105960667A (en) * | 2014-01-16 | 2016-09-21 | 马里利亚标签公司 | Fastening arrangement for replaceable voltage source for electronic price label |
| US10459682B2 (en) | 2015-01-19 | 2019-10-29 | Mariella Labels Oy | Electronic price label and a battery unit for an electronic price label |
| CN107210009A (en) * | 2015-01-19 | 2017-09-26 | 马里利亚标签公司 | Electronic price label and the battery unit for electronic price label |
| CN105526964A (en) * | 2015-12-02 | 2016-04-27 | 中国电子科技集团公司第四十九研究所 | Intelligent temperature and pressure sensing tag |
| CN109255418A (en) * | 2017-07-13 | 2019-01-22 | 日本压着端子制造株式会社 | IC card and IC card charging connector |
| CN110729203A (en) * | 2019-09-27 | 2020-01-24 | 深圳赛意法微电子有限公司 | Packaging process of open electrocardiogram sensor |
| CN110729203B (en) * | 2019-09-27 | 2021-03-09 | 深圳赛意法微电子有限公司 | Packaging process of open electrocardiogram sensor |
| CN111956237A (en) * | 2020-07-31 | 2020-11-20 | 江苏麦酷博信息科技有限公司 | RFID blood collection card |
| CN111816618A (en) * | 2020-09-03 | 2020-10-23 | 捷德(中国)科技有限公司 | Identification card and preparation method thereof |
| CN111816618B (en) * | 2020-09-03 | 2020-12-15 | 捷德(中国)科技有限公司 | Identification card and preparation method thereof |
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