FI130414B - Electrochemical indicator and method of manufacturing an electrochemical indicator - Google Patents

Abstract

The present invention presents an electrochemical indicator that includes a component sensitive to temperature, UV radiation, humidity or pressure, such as a thermistor (21), additionally a switch (31, 110, 113, 140) and the desired number of electrochemical cells (22, 22a–e ) i.e. pairs in parallel or in series with suitable resistors (21, 23, 25, 32a–e, 41a–d, 91), and transistor (24). One cell consists of an anode (62, 125b, 133), a cathode (51-54, 61, 125a, 132, 132a–e) and an electrolyte (17, 127) on a suitable substrate, and the arrangement is printable and the cells (22, 22a– e) downloadable during the manufacturing phase. A visual line of sight from the outside is arranged for either electrode. When the indicator experiences, for example, a high temperature or a dose of UV radiation for a long enough time, a chemical reaction changes the substance of the visible electrode into another, and this can be seen visually by the color change of the substance. Discharged in series or in parallel, the cells can form an optical, digitally readable code. The change in the dielectric constant of the electrode can be expressed with the help of a capacitor and UHF antenna made in connection with the electrode, in which case when reading the UHF tag, the change in impedance of the antenna caused by the change of the electrode is detected.

Description

Electrochemical indicator and method of making an electrochemical indicator

Field of invention

The invention is related to press-made batteries, i.e. batteries, and their new use in, for example, the food industry.

Background of the invention

In the food industry, it is necessary to indicate the freshness or spoilage of various foods. Currently, this is done with product-specific use-by dates or "best before" dates, which are directly calculated for each product — from the date of manufacture or packaging. It follows that the expiration date is typically chosen earlier than what would be required for the product to deteriorate at an average rate. This again results in unnecessary wastage, which is a big problem in the handling of out-of-date products in stores, and from an economic point of view, a huge expense item. It is therefore advantageous to have, for example, more precise tools for monitoring the cold chain of foodstuffs, which can also be easily attached to packages or produced directly as part of the packages. In addition, it would be advantageous if the "indicator product" in question would be inexpensive to manufacture.

Chemical indicators have been around for a long time. A chemical indicator can be based, for example, on a reaction between a liquid substance and a substance in the indicator strip, which changes the color of the indicator strip. On the other hand, a chemical indicator could be used so that when it is exposed to air instead of a vacuum, it changes color, and thus reveals, for example, the moment the package is opened or broken. © When talking about TTI (Time Temperature Indicator) technology, this is it

A growing business area at the moment and in the foreseeable future. The biggest factor

O 25 — there is a need to reduce wastage, which is a significant cost factor in fresh products and

S in some medicines. At the moment, the most well-known operating system is the "best before"-

I date, which was developed in the 1970s and its shortcomings are widely recognized. Current TTIs are usually based on a mechanical, chemical, electrochemical, enzymatic & matic or microbiological principle. The principle can be e.g. the movement of the substance in a microfluidic channel (eng. "UWI technology" / "UWI label") > after opening the product package, or corrosion of the material (Israeli

method based on the Freshpoint indicator developed by Freshpoint Quality Assurance. Freshpoint uses chemical etching of the aluminum layer as its principle.

It can be stated that the TTI indicator is a device or so-called a smart label that cumulatively shows the time-temperature history experienced by the product. TTI indicators are commonly used in food and medical applications, such as pharmaceuticals, to indicate exposure to too high a temperature and also the exposure time at too high temperatures.

Publication "Pavelkova: Time temperature indicators as devices Intelligent packaging,

Mendel University, Brno (CZ), 5 October 2012" gives a good summary of TTI technology and companies using technology and their products in 2012.

The publication "Taoukis: Modeling the use of time-temperature indicators in distribution and stock rotation, National Technical University of Athens (GR), December 2001" describes the use of TTI technology in distribution chains and stock rotation optimization.

The problem with the currently used methods is the inaccuracy of the manufacturing process.

In the electrochemical method, the simulation can be accurately dimensioned using electronics design methods, and with several cells in a row, a better resolution is obtained. Even in printed electronics, the manufacturing tolerances of resistors are moderately large, but they can be calibrated using the so-called in the on-line R2R process ("roll to roll"), for example with a laser.

There have been electrotechnical solutions that are related to an indicator-like function, and that can be implemented rationally and cost-effectively in terms of printing technology, but in little-known technology.

In the publication EP 2256670 ("Furuya") describes an integrated circuit board and its purpose is to provide a secondary power source for a thin IC circuit board so that it is not dependent on the input energy obtained through the antenna purely by electromagnetic induction; in addition, the publication wants to do away with the liquid electrolyte for safety reasons and also to keep the circuit board thin. The product of the publication is related to energy obtained either through electromagnetic induction <Q or through a solar panel, which is charged by a thin-film

For an S type battery that also contains solid electrolyte material. Kpl's [0079]

Based on E and Figure 10, Furuya has a scale "62", from which the user can compare the color to the range "61". According to Kpl [0081], the color changes as a function of charging and discharging, and lithium ions are mentioned as an example. Furuya uses a transparent 2 layer (as collector) whose material is ”oxide of indium and tin? mentioned here

In N situations, linked to the indicator application. A matter related to the indicator is mentioned

In claim 4 of Furuya by reference to all prior claims 1-3. In the EP patent granted on Furuya's application, the indicator part is included in the protection circuit, i.e. in its patent claim 1.

The grocery chain Lidl has introduced in its fish products the so-called The Tempix smart sticker (Swedish technology), which is partially placed on top of the barcode of the fish product package. Tempix's idea is to monitor the integrity of the product's cold chain from the time the packaging is completed to the time of purchase. If the product is exposed to too warm a temperature in the meantime, the indicator liquid in the Tempix smart sticker expands and when it expands, it destroys the rest of the barcode on the package. This is enough to make the product unreadable at the checkout, and the sale of the product is prevented.

In general, the radiator can be built as a printed structure in two different ways, which are coplanar structure and stack-like structure. The coplanar structure is shown in Fig. 1A as a vertical cross-sectional view. The structure has a layered protective film or release liner 11 on the bottom, on top of which — there is a layer of an adhesive substance 12 such as glue ("adhesive"). On top of the adhesive is the actual substrate 13, on which the positive electrode 14 and the negative electrode 15 are printed. On the left side of the positive electrode 14, the resistor or resistors 16 (R) can be seen on top of the substrate 13. In turn, to connect the electrodes 14, 15, an electrolyte 17 is placed on and around them, which can be — for example, a solid or paste/gel-like electrolyte (to keep it in place).

In connection with the invention, the electrolyte 17 can advantageously be a transparent substance. Finally, a graphic layer 18 is printed on top of the electrolyte 17, the resistance area 16 and, in other respects, the substrate 13, which can simply be a sheath protecting the structure. In connection with the later description of the invention, and specifically with the indicator application in mind, a small part of the protective sheath at the second electrode is left = free to enable visual examination of the color change of the electrode > through the transparent electrolyte.

O

S From the lowest layers (11—15) in Figure 1A, it can be stated that

The electrodes 14-15 are practically pressed onto the substrate 13 before the glue 12 is added. After placing the adhesive layer 12 on the other side of the substrate, the release paper 11 is added on top of the adhesive layer 12.

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= In Figure 1B, on the other hand, there is a stack-like so-called stack structure for a printed battery vas-

N as a standard cross-sectional image. Layers 11-14, i.e. protective film or release paper 11, adhesive 12, substrate 13 and resistor(s) 16 are the same as in figure 1A. The electrodes now have a new structure. In this example, the positive electrode 14 is first printed on the substrate 13 (also as a wider structure in this picture), after which a solid or paste/gel-like electrolyte 17 is printed, which completely surrounds the positive electrolyte 14. In the examples, the area of the electrolyte 17 and the resistor 16 in the cross-section border each other. The negative electrode 15 is pressed on top of the electrolyte 17, which in this example is located directly above the positive electrode 14 of the same size. A graphic layer 18 is placed on top of the entire structure, which is also typically a sheath protecting the structure.

For clarity, the anode and cathode current collectors are omitted from Figure 1B. The disadvantage of the stack structure is that the electrolysis reactions on the electrodes take place — on the lower surface of the negative electrode 15 and on the upper surface of the positive electrode 14, to which there is no easy line of sight from the outside, even if the electrolyte is solid and transparent, and even if an opening is made in the protective jacket at a suitable point. One way to solve this problem is to make a stack structure with a color-changing electrode at the bottom, a transparent electrolyte next, and another electrode with a hole on top. The color change of the second electrode can be seen through the hole.

However, the coplanar structure is a more efficient solution.

In the known technology, the main problem has therefore been that an inexpensive solution based on a printed radiator for indicator use, for example in monitoring the cold chain of the food industry, has not existed. —Summary of the invention

The present invention presents an electrochemical indicator, and a corresponding method for producing an electrochemical indicator.

According to the first aspect of the invention, an electrochemical indicator is presented, which comprises one or more interconnected electrochemical cells, > 25 — where each cell comprises an anode and a cathode as electrodes, and an electrolyte. The hallmark of the invention is that at least the physical changes of the second electrode

K is used to indicate the charging status of each cell.

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E In one application of the invention, the indicator is produced as a printed, thick-film type and coplanar structure.

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0 30 —In one application of the invention, the electrochemical cell is thermally disassembled

Through a variable resistance or resistance network as a function of S, pressure, radiation dose or chemical change.

In one application of the invention, the electrochemical cell is discharged through an active circuit connection containing at least one transistor that changes as a function of temperature or radiation dose.

In one application of the invention, the state of charge of the cell or cells is recognized optically based on the color of the electrode.

In one application of the invention, the state of charge of the cell or cells is identified capacitively based on the change in the dielectric constant of the electrode.

In one application of the invention, the change in the dielectric constant of the electrode is indicated by means of a capacitor made in connection with the electrode, and the capacitor is connected to the UHF antenna in such a way that the change in the electrode changes the impedance of the antenna, and that change can be indicated when reading the UHF tag.

In one application of the invention, the change in the dielectric constant of the electrode is indicated by means of a passive resonant circuit formed by a capacitor and a coil made in connection with the electrode.

In one application of the invention, the charge status of the cell or cells indicates the heat dose, radiation dose, moisture dose, pressure dose or change in the concentration of the chemical compound received by the cell or cells from the moment the indicator is turned on.

In one application of the invention, several cells are connected in the indicator either — in parallel so that each cell has a different-sized discharge resistor and a different discharge current, or several cells are connected in series so that only one cell discharges serially at a time, and after discharge, the part of the circuit containing that cell electrically opens. 00

N In one application of the invention, the indicator has several cells connected in such a way,

S 25 — that the discharging cells form an optical, digitally readable code. Code - can be, for example, a QR code or a traditional barcode.

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= In one application of the invention, the charging of the cells is carried out by separate

Q through resistors, with the help of which all the cells charge each other to essentially the same amount of charge during the manufacturing phase of the indicator.

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N 30 —In one application of the invention, one Zn and the other AgzO are selected as electrode materials, so that after the electrode reactions ZnO and Ag are formed as the surface materials of the electrodes, respectively.

In one application of the invention, the cells are discharged or charged using a separate power source.

In one application of the invention, each cell is connected to the source of the electronic circuit, in which case the cell can be used to indicate the state of the electronic circuit. —In one application of the invention, either the anodes or the cathodes of the electrochemical cells are connected to form a /-segment type digital display.

In one application of the invention, the indicator comprises a switch with which the discharge or charging of the cell or cells is started.

In one application of the invention, an anisotropically conductive material is printed or added between two adjacent or overlapping conductors, with the help of which the connection is made by pressing the material to become conductive.

In one application of the invention, the anisotropically conducting material is a paste, which paste comprises a binder, where the binder is cured with UV radiation.

In one application of the invention, solder is used to connect the poles of the switch, which is melted either by thermocompression, ultrasound, laser or an inductive loop included in the circuit.

In one application of the invention, crimping is used to connect the poles of the switch either with a separate metal piece or with a printed or added paste containing metal particles. —In one application of the invention, printed metal oxide is used to connect the poles of the switch, which is photo-sintered to become conductive with strong radiation, or a plasma discharge is used to reduce the oxide, or chemical catalysts are added to the printing ink, with the help of which the reduction of the oxide is accelerated by the effect of external energy.

S

I 25 —In one application of the invention, a printed transistor in the OFF state is used as a switch, which is switched to the ON state by cutting off the gate & conducting current circuit at the moment of commissioning. c/o

D In one application of the invention, a switch area is added to the indicator circuit, which

On N there is a foldable strip on which conductive glue is printed, where the still conductive glue short-circuits the switch area and keeps the switch area connected together when the strip is folded over the switch area.

In one application of the invention, the indicator circuit has a switch area next to which there is a conductive area and next to this a foldable strip of conductive glue, where on both sides of the conductive area, extending into the area of the surface of the conductive adhesive, there are two parallel incisions, which are located symmetrically and perpendicularly to the fold, where the middle strip separated by the incisions has a strip up, and on both sides of this, strips down, where the conductive area short-circuits the switch area and the conductive glue keeps the switch area connected together when the strip with the center strip is folded over the switch area.

In one application of the invention, the indicator comprises a switch part and a contact part, — where the switch part comprises two approximately triangular holes symmetrically placed and two switch contact ends, and the contact part comprises two tongues and a conductive area, where the contact part can be slid upside down relative to the switch part so that the conductive area connects the switch contact ends together after sliding, and at the same time the tabs fit into the narrower end of the triangular holes, locking — the contact in place.

According to another aspect of the invention, a method for producing an electrochemical indicator is presented. The distinguishing features of the method are that the method includes the following steps: — the conductor layer is printed or prepared by etching on the substrate; —the anode and cathode per cell are printed on the conductor layer as electrodes, and the electrolyte is printed on the electrodes, and the necessary number of interconnected electrochemical cells are printed in this way; — protect the structure at least with a visible light filtering layer so that at least one of the electrodes is visible from the outside of the indicator; and where, when using a ready- © 25 — indicator:

N — by means of the physical changes of the at least second electrode in question, it is expressed when

S kin cell charging status.

The so-called

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A brief description of the drawings

Figure 1a depicts a coplanar structural alternative for the radiator in generally known technology,

Figure 1b depicts a stack-type stack structure for a battery in generally known technology,

Figures 2a—2b describe the basic solution from the point of discontinuity implemented with one cell and a transistor to the temperature change curve,

Figure 3 depicts a circuit example related to the invention that applies parallel connection,

Figure 4 depicts a circuit example related to the invention with five cells, which applies — series connection,

Figure 5 shows an example of an X-shaped indicator structure,

Figure 6 shows one cathode area indicator and switch for manual switching,

Figure 7a shows an anisotropic connection between two opposite conductors, — Figure 7b shows an anisotropic connection where the particle size is > 0.5 * conductor spacing,

Figure 8a shows a /-segment display type display structure where electrochemical cells can be used,

Figure 8b shows a bar graph-type display structure with LEDs, which can be replaced by electrochemical cells,

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© Figure 9 shows the principle connection in the UV dosimeter application, which in this example contains five cells,

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= Figure 10 shows an implementation method for the switch used by the invention,

O io Figure 11 shows the prototype implementation of the switch structure formed by two overlapping membranes,

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Figure 12 shows one possible structural image of the invention made into a paper sticker,

Figure 13 shows the basic structure of the UV dosimeter circuit without resistance layers in one application of the invention,

Figure 14a shows one more example change for a reversible disposable switch, and

Figure 14b shows the so-called "cold prototype" in the application of the switch in Fig. 14a

For the UV dosimeter.

Detailed description of the invention

The basic idea of the invention is that printed radiators can be used for more than just an energy source. — When the structure of the printed battery is made coplanar as already shown in Figure 1A, and the electrolyte is a transparent substance, the chemical changes occurring at the electrode can be studied through the electrolyte. When the materials are chosen in such a way that the electrochemical changes fall into the light range, a good contrast is obtained between the charged and discharged electrode. — Electrochemical changes fall into the range of light, e.g. in the case of silver oxide.

Silver oxide is very black and silver is light gray or clear.

The phenomenon can be used to indicate the state of the measuring circuit outside the battery, or it can also be used to indicate the state of the electronic circuit, i.e. as a digital display when the rate of change of the electrochemical process is sufficient. status was indicated.

By choosing the materials of the external measuring circuit appropriately, the humidity, UV or COo > dose experienced or received by the examined element can be simulated as a function of time. Other changes in physical quantities can also be simulated. When the external measuring circuit is equipped with a response that changes according to the temperature

With K 25 —, the spoilage process of a fresh product or medicine can be simulated as a function of temperature (the so-called TTI or "Time temperature indicator").

Ao a n In its simplest form, the circuit that indicates the spoilage of fresh produce contains a battery and an io thermistor, i.e. an NTC resistor (NTC = Negative Temperature Coefficient). The thermal behavior of the circuit then follows the resistance-temperature curve of the thermistor. By adding

O

N 30 — active components can simulate temperature changes more precisely. By designing the circuit in such a way that the resistance changes sharply at, for example, +3 degrees Celsius, it is possible to implement a TTI circuit that complies with the FDA (supervisory authority

in the USA; Food and Drug Administration) requirements for monitoring fish products to prevent botulism.

Figures 2a-b show the basic solution from the point of discontinuity to the temperature change curve implemented with one cell and transistor. It should be noted that the resistance values in Figure 2B are only indicative. In Figure 2a, there is a thermistor 21, i.e. an NTC resistor, which is connected directly to the poles of the 1.5 V battery 22 (which is also only an example value).

When the temperature rises, the resistance of the thermistor 21 in this case decreases.

The magnitude of the resistance determines the discharge speed of the battery cell, and the larger the magnitude of the resistance, the smaller the current that discharges the battery 22 through the thermistor 21 — . In the examples of Figures 2a-b, the temperature tc = 25 °C.

In figure 2b, in addition to the NTC resistor 21 and the battery 22, there is a transistor 24, which with the help of resistors 23, 25 in the connection according to the figure produces a point of discontinuity in the temperature change curve.

By connecting separate radiators in parallel or in series, a better resolution is obtained for the simulation. Since the number of components in printing technology does not affect the price, pixels can be added within the framework of the resolution and cell capacity requirements of the printing technology. In Figure 3, the structure has five cells, where parallel connected identical batteries 22 each have their own discharge resistance 32a—e. In addition, there is a switch 31 (S1) in the circuit. This kind of parallel connection, where each cell has its own discharge resistor of a different size (in the example, the resistance doubles from left to right every time you go to the next resistor) is simple, but the problem is that the cells discharge simultaneously. A better resolution is obtained when every second cell is connected oppositely, whereby the cells are discharged one at a time according to the connection in Figure 4. Figure 4 represents an advantageous embodiment of the invention. The structure has an NTC thermistor 21 on the left similar to Fig. 2B and

A circuit equipped with N transistors 24, which also includes resistors 23, 25. E.g.

The adjustment margin of O kissd NTC resistor 21 is between 0.1 ... 2 MQ and resistors 23, 25 resis-

S dance is 1 MO. The principle in the structure works in such a way that switch 31 (S1) closes

Then the first battery 22a starts to discharge, so in terms of current flow, the situation = 30 — corresponds to the circuit in figure 2b. The second battery 22b does not discharge because its polarity is opposite to that of battery 22a. It follows that the circuit components 41a, 22b, 0 41b and the conductors and components on the right side of these do not contain current, i.e. > on the right side of the circuit corresponding to the structure of figure 2b, each wire | = O.

When the charge of battery 22a has been completely discharged, i.e. when the first cell has — discharged, its internal resistance rises and the current passing through it stops, effectively opening the current circuit of that cell. The discharge moves to the next cell and in this case the current flows on the part of the circuit on the right side of the switch 31 through the resistor 41a and the second battery 22b to the emitter of the transistor connection. In this situation too, no current flows through the circuit components 41b—d, 22c—e and also through the previously disassembled battery 22a.

The process continues in the same way until all the cells have been discharged. When the third battery 22c discharges, the resistors 41a and 41b are on the right side of the switch 31 as part of the circuit. When the fourth battery 22d discharges, 41a, 41c and 41b are then respectively in the circuit. Correspondingly, when the fifth battery 22e discharges — on the right side of the vertical line of the switch, 41a—d are included in the circuit, i.e. all the resistors shown in the picture. The operation of the circuit stops when the last cell, i.e. the battery 226, is discharged. This gives the cell a longer temporal operating time and also a series-type activation possibility, which directly gives the indicator application good additional possibilities (a more detailed description of these — later). The advantage of the connection is also better resolution and better contrast compared to cells connected in parallel. The advantage of the connection is also a smaller capacity requirement per cell, because only one cell is discharged at a time.

Since the number of cells practically does not affect the manufacturing costs, it is possible to manufacture several different graphic designs. Cells can be arranged linearly, polarly or randomly (on the random principle).

One significant possibility of the present invention is the presentation of analog information in successive areas, which can be understood as pixels of digital information. Thus, the optical information of e.g. five consecutive electrical pairs can be placed in a digital code, which can be optically read with digital identification methods such as, for example, an OR code or a traditional bar code. This ma-

N dollizes the quick interpretation of information with the desired resolution. Because printing technology

O niic accuracy is the only limiting practical factor, one can place in the code a hel-

S posti e.g. 10-step scale. One new application is automatic pricing

I for example, for milk cans, where the successively changing cells form an auto = 30 — mathematically readable digital code, with the help of which the cash register automatically determines the price of the product based on its freshness based on the 0 criteria given to the cash register system. Of course, this can be applied to any food > or other product that is susceptible to spoilage, such as fish products. When using an OR or barcode, it can also contain product identification information. —In the described digital code reading application, the cells, i.e. electric pairs, can be discharged serially one after the other, but on the other hand, parallel discharge of the cells and digital reading of the resulting code is also possible in this application.

Next, examples of the graphic layout of the indicator will be discussed. An example of a graphic appearance is shown in Figure 5. This structure shows an X-shaped indicator with four cells, i.e. cathode areas, parts 51—54. The other parts can be connected to each other by a wire, and thereby connected to the ground connection 55. The end result of the operation of the X structure in Figure 5 as a function of time is that, in the first step, the cathode area 51 is colored in another color (such as from black to light/silver, or vice versa). the battery starts to discharge, and this can be seen as a color change in the cathode area 52. Correspondingly, after this, the third cathode area 53 changes its color, and after that the fourth cathode area 54. The color change from light to dark as a function of time is illustrated by the dashed line at the bottom of Figure 5. In the invention, this type of indicator structure is one perceptual and user-friendly way to indicate, for example, the level or risk of product spoilage.

Figure 6 shows one cathode range indicator and switch for manual switching. The circular area in the center is the cathode 61, which is surrounded by an open rectangular anode 62. There is a gap between the cathode 61 and the anode 62. Anode 62 is under the color mask in this application, and in practice this graphic may be printed so that — the gap between the cathode and the anode is not visible from the outside. Above the anode area, the diagram shows, for example, a switch circuit 63 made of graphite. Above this, there is a foldable folding area 64 with conductive glue on its surface, which functions as a manual switch to determine the start moment of the indicator's operation. When the user bends the folding area containing the conductive glue over the switch circuit 63 so that — the conductive glue is in electrical contact with the switch circuit, the indicator circuit starts = to work, i.e. the anode and cathode reactions start with the discharge of the battery. Because

N glue is of course sticky, after folding the left and right parts of the switch circuit

The electronic contact between S is also maintained. In the initial situation, the lower edge of the indicator

S more observation image 65 is filled, i.e. it describes the color of the surface of the cathode 61 of the indicator,

E 30 — when cathodic reactions have not occurred to a significant extent, i.e. when the temperature conditions of product n (as an example) are okay. In the "OK" situation, according to observation image io 65, the surface material of the cathode 61 remains black, as is the case with, for example, 2 silver oxides. When, on the other hand, the cold chain breaks somewhere

N din, the battery begins to discharge, and the cathodic reaction through this changes — silver oxide to silver (in the example situation). The change happens very quickly, and the right observation picture 66 of the lower part of the indicator then shows the end result, i.e. the light color of the cathode area (like the color of silver). In this case, the conclusion is made that "the product is not in OK condition" (= "OK*). Since the product is typically disposable, there is no need to worry about the reactions between the cathode 61 and the anode 62 that take place afterwards. After use, the product can be recycled in the relevant — recycling container.

One significant advantage of the silver oxide-zinc cell used as an example of the invention is the uniformity of the voltage until the end of the life cycle, which means that the discharge is also uniform and predictable, as long as the leakage currents of the cells are small compared to the discharge resistance. However, this can very well become a problem — in long simulations. Assuming a simulation time of a week, a voltage of 1.5 volts, 10

UAh capacity/cell and 5 cells in a row for a total capacity of 50

UAh, we get the value of the discharge resistance R:

R = 168 h x 1.5 V / 50 uAh = 5.0 MQ (1) which is still reasonably small compared to leakage resistances. Moisture can speed up — the simulation if the resistance values are high.

Simulations lasting months require increasing the capacity of each cell and at the same time higher manufacturing costs.

Next, an application option of the invention is explained, in which the electrode change of a TTI-type indicator can be measured with the help of a UHF antenna (English "ultra high frequency"), so-called When reading a UHF tag (RFID tag). Generally, TTI is meant to be read by the end user, but in logistics chains there is a need to measure things automatically. Current camera technology enables fast optical reading, but it requires a short distance and precise placement. When the electrochemical pa- = rin's charge state change can be transmitted as wireless fast-moving information, there are new application possibilities for the invention in places where the reading performed by the user <Q is too slow. By connecting the circuit according to the invention via radio

It is possible to reach a readable tag, especially a UHF tag, up to several meters

E to access the indicators that can be read quickly. & RF Micron (now Axzon) has developed a UHF chip that measures the impedance of the antenna circuit and converts it into a digital, e.g. 5-bit word, and this information is linked > to the identification information. Smartrac (NL) uses this principle to measure humidity

in its DogBone sensor.

In connection with the present invention, Elcoflex has developed a physical quantity measurement method based on a UHF chip, in which the reader device scans UHF tags at different frequencies and deduces from the results changes in the impedance of the antenna. Both methods can be used in a TTI-type indicator, when the change of the electrode is expressed through the change of capacitance and the capacitor prepared for the electrode is connected as part of the resonance circuit of the antenna. In the former method, standard type reader devices can be used, while the latter requires a customized reader that infers the impedance by scanning several different frequencies.

Since the latter method uses mass-produced standard chips, it is better suited for automatic monitoring of fresh products, also due to its low cost.

The resonant frequency of the HF (high frequency) range of RFID applications is 13.56 MHz, which makes it difficult to use the same principle in NFC technology with small capacitance values. In NFC technology, the measurement can be transferred into readable data, e.g. by means of the analog input of the NFC circuit, e.g. by connecting the electrode to be measured as part of the RC circuit connected to the NFC circuit. Austrian Micro Systems (AMS AG) has developed an NFC chip AS39513, which has an analog input and also a digital output. With these, it is possible to measure the electrode change in the desired frequency range. — A more affordable solution is probably to build a separate UHF antenna and UHF chip

with NFC.

In one application of the invention, in addition to the RFID solutions described above, it is possible to connect the capacitance of the TTI indicator described above as part of a passive resonance circuit whose frequency is read by a reader device designed for the purpose. © 25 The coil of a resonant circuit can be made in the same process as other conductors

With N. The absence of an active component means that reading can be done

S only performs at close range.

Nn 7 Next, the so-called features of the present invention will be discussed. switch application. Since there can be a considerable time between the time the indicator is manufactured and the time it is used, it makes sense to equip the circuit with a power switch. If active 3-phase conductors are used in the circuit, the switch can be realized with e.g. a channel transistor, in which case the current can be

D turn on by breaking the circuit of the transistor gate. Good enough at 1.5 V voltage

However, the production of n functioning transistors requires a very precise gate insulator printing technique, which increases costs. The goal is to print the product with a silk screen — using thick film technology, thus achieving favorable manufacturing costs

fuck you. Other techniques such as sputtering,

CVD (Chemical Vapor Deposition), ALD (Atomic Layer Deposition), dispensing, lamination, chemical coating and all other printing techniques including gravure and flexo printing techniques. In this context, the word "printed? refers to all technologies. It is essential that the manufacturing takes place from reel to reel "reel-to-reel" (R2R), which achieves the required cost level.

All printed batteries require an easy-to-switch ON-OFF switch, not only in the electrochemical indicator according to this invention. For example, in an RFID tag that contains a printed battery integrated into the structure, there is the same need to switch the battery on only at the time of commissioning. TTI and

In RFID applications, the connection can be made with an automatic device and thus the connection method can be more complicated. In a product aimed at the end user, the situation is more challenging. The switch must be able to be switched manually without an external light or other energy source. — The switch of the invention can be implemented using several different methods. The required resistance of the ON state of the switch can be large, up to 1 kO, which would be only 0.2 ppm of the resistance of the previous example. If the resistor's nominal value is accurate, it can be part of the total resistance of the discharge circuit.

One option is to use the known anisotropic adhesive technique as shown in figures 7a-7b. Figure 7a shows an anisotropic connection between two opposite conductors. In this method, the conductive particles in the weakly conductive glue are compressed in the direction of the Z axis to become conductive. When the diameter of the particles is approx. one-fifth of the distance between the conductors, as in figure 7a, no conductivity occurs in the horizontal plane. By enlarging the particles in relation to the distance between the conductors © 25 — conductivity can also be created in the horizontal plane, in which case there is no need for two vertical

N parallel conductive surface, but the contact is created between adjacent conductors.

O This is shown in Figure 7b, in which the particle size (diameter

S position) is at least half the distance between the conductors. In Figure 7b, the substrate

There are two conductors 72 on top of I 71. On top of this structure is glue 73, among which = 30 are conductive particles 74. When the size of the conductive particles in relation to the distance between the conductors is large enough, by physically pressing or 0 squeezing the area contained in the glue 73, an electrical contact is formed through the conducting particles 74 lead- > melta 72 to another.

In general, the binder of anisotropically conductive paste is a thermosetting type substance (for example, a polymer), which is dried by heating. R2R-

in the process, a more advantageous way is to use a binder that can be cured with ultraviolet radiation (UV), which increases the speed of the process many times over. There is no obstacle to the use of UV radiation, because the conductors are parallel, so they do not prevent light from entering the adhesive. If the long-term stability of the joint is not a requirement, it is also possible to use just pressing. This method is close to crimping, where metal particles are pressed onto the conductor, i.e. connected to it by pressing.

Solder is the best in terms of conductivity, but leads to manufacturing technical problems. The solder must be made to remain in a non-conductive state before melting. Melting itself — can be done either with a laser, a soldering iron, an inductively heated loop or ultrasound.

The new manufacturing technology for conductive circuits is the so-called photonic sintering. In it, the metal oxide is reduced to a conductive metal with a high light output.

Since the forward resistance can be high, this method is very potential already — also for the reason that it is commercially available in R2R form. Novacentrix offers screen-printable copper oxide and exposure devices. Other methods can be found in the literature to reduce several different metal oxides.

Next, one application of the present invention is discussed, which is the use of the indicator arrangement as a display component. This is shown in figures 8a-b, — of which figure 8a shows the so-called A 7-segment display type display structure that can use electrochemical cells. Figure 8b shows the so-called Bar Graph-type display structure with LEDs, which can be replaced by electrochemical cells. © When the electrochemical pair is broken down with an external voltage source with a sufficiently large current > 25, the optical change of the electrode can be made to occur in a few seconds.

O By connecting the cell to e.g. the output of the processor, the cell can be used as a display pixel 7 lind. The method can be used to build e.g. 7-segment, Bar Graph or dot matrix 7 displays that cannot change their state back without bipolar voltage. However, this = (i.e. one-way / one-time element appearance change) is frequent

Q 30 — a sufficient function in cheap disposable products, for example, to indicate the status of the device, a disposable code or a measurement value.

N A typical application in RFID products could be, for example, battery charge indication with e.g. ten pixels indicated every 10% or so-called "tamper evident" type indicator.

The left element "Arduino Uno" in Figure 8a is a processor whose outputs D2-D9 go to each of the seven display elements through a resistor and additionally from D5 to the DP point indicating the activation status via the corresponding connector. The ground terminal is "cc". In the invention, each of the areas a—g can be a cathode experiencing a color change or an anode from an electrochemical pair, as described above.

In Figure 8b, on the other hand, the element "Arduino" on the left represents the processor of the Bar Graph display application. Outputs D2-D11 are connected to components marked as LEDs, and in the invention these LEDs can be replaced with electrochemical cells according to the invention. Included in the connection of the pattern are, in this example, the 220 Q series resistors, and the control resistor connected to AO, i.e. the potentiometer. The operating voltage in this example is 5 V.

As another application example, the invention can be used as a UV dosimeter.

In the method according to the invention, the NTC resistor can be replaced by any resistor that changes according to a physical phenomenon. Semiconductors are typically — materials whose conductivity changes under the influence of external energy, such as electromagnetic radiation. For example, zinc oxide (ZnO), whose so-called "band gap" is 3.37 eV, reacts to UVA and UVB wavelengths 280 ... 400 nm. This is why zinc oxide is used in UV protective creams. — radiation-responsive dosimeter ZnO is just an example and the photoresistor can be made with several other different materials.

Figure 9 shows an example of the principle connection with five cells in a UV dosimeter application. On the left is a UV-sensitive resistor 91 connected to the rest of the circuit via switch 31 (S1). The structure otherwise resembles the mu- © 25 — strip radiator and resistor network in Figure 4. Batteries 22a—e are also 1.5 V in this example

N batteries (ie electrochemical cells), and resistors 41a-d are in this example

S 1 kO resistors.

Nn 7 When the UV dosimeter is a product of the end user, switching on must be done = manually, e.g. using conductive glue. The connection takes place, for example, by folding

Conductive adhesive area placed on the edge of the sticker printed with Q 30 on top of two adjacent conductors located outside the measurement area. Adequate conductivity is

D can be made, for example, by mixing conductive carbon, graphene or metal particles

N for PSA glue (English pressure-sensitive adhesive). In this case, the glue is isotropic, which does not need special pressure to achieve conductivity. Another — possible option is to make a molded membrane switch, which remains on the bottom when pressed. However, it is a more expensive solution than printed glue and requires a suitable plastic film.

Figure 10 shows one embodiment of a switch used in an application of the invention. At the bottom of the indicator film is a UV measurement area, the other narrower end of which is built with wiring that forms the switch elements. These conductor wires can be shaped in a fork-like fashion as parallel conductor wires extending between each other, which in the basic state do not form a connection between each other.

Above the switch element (on the other side than the UV measurement area) is a fold, the surface of the separated fold part has an area of conductive adhesive such as PSA material. A separate perforation could also have been made for the fold. When the user folds

The folding part containing PSA glue onto the switch elements and presses it onto the counterpart, the conductive PSA glue acts as an electrical connection of the branches of the switch elements, and the circuit is thus closed in this respect. The glue keeps the connection closed, and since the connection only needs to close, and opening after this is typically not necessary, the glue is a usable material for forming the connection.

The switch can also be two conductive surfaces that slide relative to each other, which can cause switching when the sticker is removed from its delivery package. This requires a second membrane layer and is therefore a more expensive solution than the one above.

Figure 11 depicts another type of switch structure with switch part 110 and contact part 113 in two separate membranes. The left-hand switch part 110 contains two approximately triangular holes 111 symmetrically placed and two switch contact ends 112. The switch part 110 functions here as a lower membrane. The right-hand contact part 113 acts as an upper membrane, on which tabs 114 are punched (two pieces also symmetrically placed). The contact part 113 is additionally printed © 25 — conductive area 115. When the right membrane 113 is turned over the left membrane 110 and

N is then slid down, the conductive region 115 slides down and hits the clutch

O with the contact ends 112 for contact. In this case, the switch contact ends 112 are connected

S electrically together. At the same time, the tabs 114 are placed in the narrower end of the holes 111

I he who locks the contact in place. In contrast to Fig. 11 from the paper observation image = 30 — the switch part 110 and the contact part 113 can therefore be freely movable relative to each other as separate parts, or at least they are arranged so that they are movable relative to each other in a vertical direction.

O

N Figure 12 shows one possible structural image of the product of the invention, where the product is made into a paper sticker. The bottom layer is a protective film or release paper 121 (release liner). PSA glue is made on top of this as a second layer

122, which is therefore a pressure-sensitive adhesive. On top of this, in turn, a paper layer 123 is prepared. Above this, a conductor layer, or electrode layer 124, is prepared, which can be made of, for example, silver. These are in practice conductive wirings on top of the paper layer 123, and the conductor layer 124 is — designed — for example — with the IDE design principle (eng. — "Inter-digitated electrode"). The cathode and anode are then printed on the conductor layer 124, which are marked with plus 125a and minus 125b electrodes. In the example picture, the plus electrode or cathode 125a can be silver oxide (Ag20) and the minus electrode or anode 125b zinc (Zn). Outside of the cathode 125a and anode 125b, a zinc oxide layer 126 (ZnO) is printed on top of the conductor layer 124, which is an ink-like substance in composition ("ZnO ink"). After this, a layer of electrolyte 127 is pressed or dispensed on top of the cathode 125a and anode 125b. The electrolyte can be a solid or paste-like substance. The electrolyte in this application is a transparent substance. Finally, visible light is printed as the top layer — a filterable filter layer, on which graphic elements, i.e. markings and/or colors, can be made on or as part of it. This layer acts as the outer shell of the indicator. Since there is an opening in the filter layer at the cathode 125a (cathode here only as an example), the substance changes caused by the electrical reactions take place there, and thus the color changes can be observed through the opening — of the graphic envelope. Of course, the electrolyte layer 127 can advantageously be covered with a thin transparent plastic (not shown) that protects the structure.

Naturally, the opening point can be arranged alternatively at the anode 125b, or for example at the points 125a—b of both electrodes, if the need for illustration so requires.

PSA glue 122 can also be selected as a substance that meets the requirements of medical applications (English "Medical Grade"). © Figure 13, on the other hand, shows the basic structure of the UV dosimeter circuit without

S resistance layers. In this structural solution of the UV example application, the

The ros structure can consist of the same parts and in the same order as the layer structure of figure 12 = 30. In this context, the circuit layer 130 and the filter and graphics layer & 131 are considered separately in the UV dose application. The circuit layer 130 comprises 0 here anodes 133, cathodes 132, finger-shaped silvered conductor wires 134 and zinc oxide (ZnO) layer 135. In this example, there are five cells, i.e. there are five pairs of anodes 133 and cathodes 132 next to each other. — In a preferred application, a pattern like a finger pattern is used in the layout of the conductor wires 134. This is due to the very high specific resistance of the zinc oxide layer 135, and with the finger-like conductor structure, the effective resistance value of the circuit can be calculated.

The right side partial drawing of Figure 13 shows the filter and graphics layer 131 in the same structure, which is placed on top of the left side structure in the finished product. Here you can see the light filter 136, which has a rectangular window or opening 137. The filter layer therefore prevents the passage of visible light, e.g. at the conductor wires 134, but an opening 137 is located at the cathodes 132. Graphics can be directly printed on the filter layer. In this example, the graphic contains the info texts "UV Guard" i.e. "UV guard?", "DOSE" i.e. "UV dosage", and — in percentages from zero to one hundred in 20% intervals, the corresponding info texts starting at 20%.

When using a UV dosimeter, initially each indicator cathode 132 is black (ie silver oxide colored in the example using silver/silver oxide). When the indicator absorbs a sufficient amount of UV radiation, the cathode 132a of the first cell changes from black to silver (ie bright). The bright area thus extends — in this case up to the 20% limit in the dosing window, i.e. in the opening 137. As the UV dose increases, the cells (including cathodes 132a—132e) change their color starting from the bottom one by one from black to bright. The last to change color is the top cathode 132e. Here

The UV dose has reached the set maximum threshold value, which is indicated by the number 100% on this scale. This dose (100%) can represent, for example, the UV dose received by a user with average — pigment when the skin has just burned. In this way, the dosimeter informs the user of the safe time in the sun and specifically the UV dose received in real time. This is advantageous, because otherwise the burning of the skin appears with a slight delay, typically after moving indoors, when skin damage may have already occurred. — The substances used and their colors in the reactions of the substances can of course be more than clear (silver color) and black (silver oxide color) in the UV = dose meter,

N as long as there is visibility in the progress of the UV column in the direction of the user of the device

S does not suffer.

S

There are several uses for the I UV dosimeter, e.g. in industry there is a need to measure - 30 — the UV powers of production equipment and at the beach it is useful to know the amount of UVA and & UVB dose received to avoid a possible melanoma risk.

LO

= To return to the switch solutions of figures 7a—b and 10-11, in figures 14a—b the brochure

Here is one more possible option for implementing a disposable switch. This option can also be produced on an automatic roll-to-roll type line. The structure of the indicator 140 in Figure 14a comprises an adhesive surface 141 at the other end of the strip, which can be the aforementioned PSA-type adhesive. A conductive area 145 is printed on the other side of the fold 144, which can be graphite or other conductive material. Vertical incisions are made from the lower edge of the conductive area 145 on either side of it, which extend to the other side of the fold 144 in the area of the adhesive surface, so that the incisions — extend the same distance from the fold point to both sides symmetrically.

In the place of the incisions, notches can be made advantageously, which make it easier for the tongue to turn in the right direction, i.e. when folded upwards. Immediately below the conductive area 145 is the switch area 142, for which there are separate switch contacts 143.

Switching on the switch is done by folding the part of the indicator containing the adhesive surface 141 downwards around the fold 144, so that the middle tab separated by the cuts turns towards the inner corner with the help of the rivets, as illustrated in the drawing on the right of Fig. 14a. When the folding part containing the adhesive surface is completely bent against the other surface of the indicator area, and this is pressed together with the fingers, the adhesive surface 141 sticks to the opposite part so that the conductive area 145 and the switch area 142 are brought into contact with each other. In other words, through the graphite (or more generally the conductive area 145), the switch contacts 143 with the switch areas 142 connect together. Since an area with a thickness of four substrate layers is formed at the folded-off tab part, but around it an area with a thickness of only two substrate layers, a pressure is generated in the switch area 142 thanks to the glue, which keeps the contact — closed. Since the switch is disposable in the indicator application, it is not necessary to remove the adhesive surface from its counterpart later. Since conductive paste is printed in the product of the invention in any case, the additional cost of the materials of the application example in Fig. 14a consists only of the glue and the film to be installed to protect it. In terms of manufacturing technology, of course, the difference is the making of incisions, and the manufacturing of the rivets, but this solution is also very feasible in terms of printing technology with the R2R principle.

O

> Figure 14b shows the switch solution of the previous figure = applied to a UV-<Q dosimeter application. The drawing shows a cold prototype made of paper,

S where components and aperture views are drawn in pencil for illustration.

E 30 — Figure 14b shows the region of tab n folded in the direction of the inner corner, where the conductive region approaches the coupling region, similar to Figure 14a. The five-cell UV dose detector shows the amount of UV exposure from the opening in the graphic as a color change in five areas 2, so that area "1" changes its color first, and area "5" last. UV

The reception of N dose starts at the moment when the fold containing the switch is — glued to the opposite surface by pressing with the fingers. In this way, the "calculation" of UV radiation can be precisely started manually from the moment the switch is turned, and the storage time of the product is practically irrelevant to the functioning of the indicator product.

Here is one significant advantage that the switch offers. Likewise, the use of glue and the 4-layer structure described above in the area of the switch makes the electrical operation of the switch reliable. —The invention can therefore use a UV-sensitive resistor when measuring the UV dose, i.e. a so-called photoresistor, which element 91 in figure 9 represents. The chemical change, on the other hand, can be measured using, for example, a moisture-sensitive resistor instead of the NTC resistor 21 (see figure 2a-b and 4), i.e. the thermistor 21. One additional application of the invention is to use a pressure-sensitive resistor instead of the thermistor 21. — In one application of the invention, the state of charge of the cell or cells is identified capacitively based on the change in the dielectric constant of the electrode. This can be measured by pressing the capacitor plate over the changing electrode and also the electrolyte, and thus the state of charge can be indicated by means of a change in capacitance without galvanically disturbing the cell, i.e. the electrochemical couple. — In one example of the invention, the charge status of the cell or cells indicates the heat dose, radiation dose, moisture dose, pressure dose or change in the concentration of the chemical compound received by the cell or cells from the moment the indicator is turned on.

In one example, the chemical compound in question can be CO? i.e. carbon dioxide.

In one application of the invention, several cells are connected in the indicator either — in parallel so that each cell has a different-sized discharge resistor and a different discharge current, or several cells are connected in series so that only one cell discharges serially at a time, and after discharge, the part of the circuit containing that cell electrically opens. The circuit structure using parallel connection enables a display application and, for example, a bar graph type display like Figure 8b, because the cul- > 25 — cap cell (electrochemical pair) has a different discharge time.

S In one application of the invention, the charging of the cells is done by separate

S through the resistors, with the help of which all the cells charge each other essentially

E ses to a charge of the same size during the manufacturing phase of the indicator. & In one application of the invention, Zn 0 30 — (zinc, anode) and Ag2O (silver oxide, cathode) are selected as electrode materials, so that after the electrode reactions, ZnO (zinc oxide) and Ag (silver) are formed as the surface materials of the electrodes, respectively. If silver is used as the cathode, then the silver must be oxidized in a separate manufacturing process, where each pair is given the same charge. Because of this, the charging resistors should preferably be equal in order to obtain good accuracy for the measurement. In this way, the application of charging resistors of the same size (previous piece), and the choices of Zn and Ag2O as anode and cathode (this piece) are linked together.

However, when choosing any other anode and cathode material, each pair can be charged to the same amount of charge.

When the battery (i.e. cell or pair) is charged in advance, a situation is reached where the exact amount of charge is known. Then the discharge also happens accurately if the resistance values of the resistors are accurate. Another option is to use silver oxide as the cathode, i.e. a ready-made charged cell. The problem in this case is the inaccuracy arising from the amount of silver oxide in the printing process. — In one application of the invention, the cells are manufactured as pre-charged electrodes. An example of this is a cell made of zinc oxide (ZnO) and silver (Ag) electrodes, which is charged before use. In this case, zinc (Zn) and silver oxide (Ag20) are formed as electrode materials in the electrode reactions that cause charging. After this, the indicator is ready for use. In one — another application of the invention, the cells are discharged or charged using a separate power source.

In practice, this means a situation where there is a directly manufactured cell formed by zinc and silver oxide electrodes, which does not need separate charging, but is directly ready for use. In the third application option, a galvanic pair is used, where a second battery (power source) is used to charge the measuring pair, i.e. to change the color by a galvanic process. In practice, this means using a separate battery for the conversion, i.e. charging the cell(s), because the disassembly does not require an external power source. This third option is a more complicated and expensive solution than the first two options.

It should be noted that the use of silver and silver oxide in the indicator is only one © 25 favorable example, because with these two materials the mutual color change is vi-

Visually so clear, and easy to spot. Any other substance will do if electro-

S direaction only changes its color perceptibly with the eyes.

Nn 7 In the switch application of the invention, an anisotropically conductive material is printed or = added between two adjacent conductors, for example as a paste or film (such as 2 30 ACP, anisotropic conductive paste; or ACF, anisotropic conductive film), with the help of which 3 the connection is made by pressing the material to become conductive (see Figure 7b above). Pu-

S-crossing can be done manually, i.e. by squeezing with the user's hand as desired

N at the time of indicator launch.

In relation to the display application of the invention, it is possible to build different display combinations, other than the traditional /-segment type display. Pairs, or cells, can be connected in such a way that they form, for example, a bar graph-type analog display. Since the number of cells does not affect the price much, they can easily be built in e.g. 10 units, i.e. in 10% increments on a 0-100% scale.

On the other hand, electrochemical pairs according to the invention can be connected, for example, to the outputs of the processor, resulting in a slowly changing digital display. With additional circuits, it becomes reversible. One application for such structures is in temperature measuring tags, which can have, for example, a three-pixel display. It doesn't have to be two-way. Another application of a "slow" display is price display screens in, for example, shops, supermarkets and gas stations, and anywhere else where the display information does not have to change all the time.

The switch application of the invention involves the following. Since the manufacturing and commissioning times of the indicator are different, there must be some kind of switch with which the unloading — is started at the same time as the product is packed. The switch must be sufficiently conductive that its resistance does not substantially change the discharge time, but at the same time insulating enough that discharge does not occur between the completion of the indicator and the time of packaging. This will be a common problem in all products containing printed radiators. — In the switch application, solder is used to connect the poles of the switch, which is melted either by thermocompression, ultrasound, laser or the inductive loop included in the circuit.

In the case of anisotropically conducting substances, the so-called ACP (conductive paste) and ACF (conductive film) are known technologies in themselves. The rule of thumb in the application of the invention is that the particle size must be 5 x smaller than the size of the conductors, so that

N lateral conduction does not occur. If the particle size is larger than that,

O lateral conduction. In the clutch application, in the situation of Figure 7b, it is a matter of side-

On S-directional conductivity by means of anisotropically conducting materials. I invent-

In this case, this is an affordable option because ACP is easy to press into the structure. - 30 If the pasta is partially cured with UV radiation, it remains stable between the moment of preparation & and the moment of packaging, after which it can be cured again with UV until completely o hard.

OF

In one of the switch applications of the invention, solder is used to connect the poles of the switch, which is melted either by thermocompression, ultrasound, laser, or an inductive loop included in the circuit. In this application related to the use of solder, it is noteworthy that the best conductivity is obtained with solder, but it must be printed as a paste and the problem may be the stability of the paste before melting.

In one switch application of the invention, crimping is used to connect the poles of the switch, either with a separate metal piece or with a printed or added paste containing metal particles. For this application, crimping as a procedure is a straightforward and inexpensive method, but it usually requires two overlapping conductors or a metal plate connecting adjacent conductors. In the invention, the use of ACP is therefore a more affordable option than crimping. — In one switch application of the invention, printed metal oxide is used to connect the poles of the switch, which is photo-sintered to become conductive with strong radiation. Photonic sintering is an inexpensive alternative for connecting the poles of a switch, and a useful and easy method for printed products. For example, copper oxide paste (CuO) exists, as well as exposure devices, so photo-sintering works as a manufacturing method for the switch application of the invention. In addition to light radiation, a plasma discharge can be used to reduce the oxide, or chemical catalysts can be added to the printing ink, with the help of which the reduction of the oxide is accelerated by the effect of external energy.

In one switch application of the invention, a pressed transistor in the OFF state is used as a switch, which is switched to the ON state by cutting the current circuit leading to the gate at the time of commissioning. A transistor can be used if the conductivity of the channel is weak

in OFF mode. The ON state conductivity of the transistor does not have to be good if it is well known, because it can be included in the discharge resistance of the cell. In other words, the transistor could also be a production method, especially if it is also needed for modifying the T/R curve (temperature/resistance).

N In one switch application of the invention (corresponding to Figure 10), the indicator circuit has

O added switch area, on top of which there is a fold-out strip printed with conductive li-

S ground where the still conductive adhesive short-circuits the switch area and keeps the switch area together

I do connected when the strip is folded over the switch area. This is particularly suitable for = 30 —manual switching (by hand / fingers), but this can also be easily au-

S tomatize. = In a switch application of the invention (corresponding to Figures 14a-b), the silicon of the indicator

In N there is a switch area, next to which is a conductive area and next to this a foldable strip of conductive glue, where on both sides of the conductive area, extending to the area of the surface of the conductive adhesive, there are two parallel incisions, which are located symmetrically and perpendicularly with respect to the fold, where the middle strip separated by the incisions has a pull up, and on both sides of this the strips down, where the conductive area short-circuits the switch area and the conductive glue keeps the switch area connected together when the strip with the middle strips is folded over the switch area. —In a switch application of the invention (corresponding to Figure 11), the indicator comprises a switch part and a contact part, where the switch part comprises two approximately triangular holes symmetrically placed and two switch contact ends, and the contact part comprises two tongues and a conductive area where the contact part can be slid upside down relative to the switch part so that the conductive after sliding, the area connects the switch contact ends together, and at the same time the tabs fit into the narrower end of the triangular holes, locking the contact in place.

The inventive idea of the present invention also includes a manufacturing method of an electrochemical indicator. The manufacturing method includes all the manufacturing options for the various applications of the device itself, which are described above and in the accompanying patent claims. Likewise, the manufacturing method of the switch is included in the inventive idea of the present invention.

In the manufacturing method for the manufacture of an electrochemical indicator, the method in its general form (see Figure 12) comprises the following steps: — a conductor layer is printed or prepared by etching on the substrate; —the anode and cathode per cell are printed on the conductor layer as electrodes, and the electrolyte is printed on the electrodes, and the necessary number of interconnected electrochemical cells are printed in this way; — protect the structure at least with a visible light filtering layer so that at least one of the electrodes is visible from the outside of the indicator; and where, when using a ready- © 25 — indicator:

N — by means of the physical changes of the at least second electrode in question, it is expressed when

OK, the charging status of the cell. 5

I So the manufacturing process does not necessarily start with a printed conductor pattern, but the conductors = 30 — can also be manufactured by etching the metal layer in the film. Metal layer & ros can be, for example, copper or aluminum.

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00 > The applications of the present invention are the monitoring of cold chains in the food industry with indicators placed in product packages, monitoring of other temperature-sensitive products and facilities, display applications, measuring UV dose, e.g.

as a personal UV radiation meter, humidity or pressure meters in a wide range of applications, and for example measuring the carbon dioxide concentration in the air.

The present invention is not limited to only the application examples presented above, but the invention may vary within the scope of the protection defined by the accompanying patent claims. 00

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Claims (26)

Patent Claims 1. — An electrochemical indicator comprising one or more interconnected electrochemical cells (22, 22a—e), where each cell comprises as electrodes an anode (62, 125b, 133) and a cathode (51-54, 61, 125a . during discharge to change physically, whereby the state of charge of the respective cell (22, 22a-e) can be seen based on the color of the respective electrode or as a color change through the transparent electrolyte (17, 127), and that the indicator is a printed, thick-film type and coplanar structure. 2. An indicator according to claim 1, characterized in that the electrochemical cell (22, 22a-e) is discharged by a variable resistance or resistance network (21, 23, 25, 32a-e, 41a) as a function of temperature, pressure, radiation dose or chemical change —d, 91) through. 3. An indicator according to claim 2, characterized in that the electrochemical cell (22, 22a—e) is discharged through an active circuit connection containing at least one transistor (24) that changes as a function of temperature or radiation dose. 4. The indicator according to claim 1, characterized in that the charge state of the cell or cells (22, 22a—e) is optically recognized based on the color of the electrode. 5. The indicator according to claim 1, characterized in that the state of charge of the cell or cells (22, 22a—e) is identified capacitively based on the change in the dielectric constant of the electrode. S 6. An indicator according to claim 5, characterized in that the change in the dielectric constant of the electrode N is indicated by means of a capacitor made in connection with the electrode, and the capacitor is connected to the UHF antenna in such a way that a change in the electrode changes the impedance of the antenna, and that change can be free UHF tag I when reading. a Q 7. An indicator according to claim 5, characterized in that the change in the dielectric constant of the electrode 3 is indicated by means of a passive resonant circuit formed by a capacitor S 30 — tor and a coil made in connection with the electrode. 8. The indicator according to claim 2, characterized in that the charge status of the cell or cells (22, 22a—e) indicates the heat dose received by the cell or cells, radiation dose, moisture dose, pressure dose or change in the concentration of a chemical compound from the moment the indicator is started. 9. An indicator according to claim 1, characterized in that the indicator has several cells (22) connected either in parallel such that each cell (22) has a discharge resistor of different size and a different discharge current, or several cells (22a-e) are connected in series - divide so that only one cell (22a—e) discharges serially at a time, and after the discharge, the part of the circuit containing that cell (22a—e) electrically opens. 10. An indicator according to claim 1, characterized in that the indicator has several cells (22) connected in such a way that the discharging cells form an optical, digitally readable code. 11. The indicator according to claim 1, characterized in that the charging of the cells (22, 22a—e) is done through separate resistances of the same size, with the help of which all the cells (22, 22a—e) charge each other to essentially the same amount of charge during the indicator manufacturing phase. 12. An indicator according to claim 1 or 11, characterized in that one Zn and the other Ag20 are selected as electrode materials, whereby after the electrode reactions ZnO and Ag are formed as the surface materials of the electrodes, respectively. 13. An indicator according to claim 1, characterized in that the cells (22, 22a-e) are discharged or charged by means of a separate power source. 14. An indicator according to claim 13, characterized in that each cell (22, 22a-e) is connected to the output of an electronic circuit, whereby the cell (22, 22a-e) can be used to indicate the state of the electronic circuit. IS & 15. An indicator according to claim 13, characterized in that either the anodes (62, 125b, 133) or the cathodes (51-54, 61, 7 125a, 132, 132a) of the electrochemical cells (22, 22a—e) e) is connected as a 7-segment type digital display. a a n 16. An indicator according to claim 1, characterized in that the indicator io comprises a switch (31, 110, 113, 140) with which the discharge or charging of the cell or cells (22, = 22a—€) is started. OF 17. An indicator according to claim 16, characterized in that an anisotropically conductive material (73, 74) has been pressed or added between two adjacent or overlapping conductors (72), with the help of which the connection is made by pressing the material to become conductive. 18. An indicator according to claim 17, characterized in that the anisotropically conductive material (73, 74) is a paste, which paste comprises a binder, where — the binder is cured with UV radiation. 19. The indicator according to claim 16, characterized in that solder is used to connect the poles of the switch (31), which is melted either by thermocompression, ultrasound, laser or an inductive loop included in the circuit. 20. An indicator according to claim 16, characterized in that crimping is used to connect the poles of the switch (31) with either a separate piece of metal or a printed or added paste containing metal particles. 21. An indicator according to claim 16, characterized in that a printed metal oxide is used to connect the poles of the switch (31), which is photo-sintered to become conductive with strong radiation, or a plasma discharge is used to reduce the oxide, or chemical catalysts are added to the printing ink, with the help of which the reduction of the oxide is accelerated by the effect of external energy . 22. The indicator according to claim 16, characterized in that a pressed OFF transistor is used as the switch (31), which is switched to the ON state by cutting off the current circuit leading to the gate at the moment of commissioning. 23. Indicator according to claim 16, characterized in that a switch area is added to the indicator's circuit, on which a strip can be folded, on which conductive glue is printed, where the still conductive glue short-circuits the switch area and keeps the switch base connected together when the strip is folded onto the clutch area. N & 24. Indicator according to claim 16, characterized in that the circuit of the indicator + 25 — has a switch area (142) next to which there is a conductive area (145) and next to this - conductive glue (141) with a foldable strip, where on both sides of the conductive area = conductive glue extending to the area of the surface (141) there are two parallel incisions, Q which are located symmetrically and perpendicularly to the fold (144), where the middle strip separated by the incisions has a knot up, and on both sides of this, knots down, where the leading area ( 145) short-circuits the switch area (142) and the conductive glue N (141) keeps the switch area (142) connected together when the strip with the middle strips is folded over the switch area (142). 25. The indicator according to claim 16, characterized in that the indicator comprises a switch part (110) and a contact part (113), where the switch part (110) comprises two approximately triangular holes (111) symmetrically arranged and two switch contact ends (112), and a contact part ( 113) comprises two tongues (114) and a conductive area (115), where the contact part (113) can be slid upside down in relation to the switch part (110) so that the conductive area (115) connects the switch contact ends after sliding (112) together, and at the same time the tabs (114) are positioned at the narrower end of the triangular holes (111), locking the contact in place. 26. A method for the production of an electrochemical indicator, characterized in that — the method comprises the following steps: — the conductor layer (124) is printed or prepared by etching on the substrate — the anode (125b) and the cathode (125a) are printed as electrodes for one cell on the conductor layer (124) and electrolyte (127) on top of the electrodes, and in this way the required number of interconnected electrochemical cells (22, 22a—e) are pressed — the structure is protected with at least a visible light filtering layer (128) so that at least one of the electrodes is visible from the outside of the indicator; and where, when using the manufactured indicator, the indicator acts as a battery when electrochemical changes occur at the electrodes, and in addition — at least one electrode of each cell (22, 22a-e) is arranged to change physically when charging it, or — when discharging, in which case the state of charge of that cell (22, 22a-e) is visible by the color of that electrode or as a color change through the transparent electrolyte (127), and that the indicator is manufactured as a printed, thick-film type, coplanar structure. S O N O <Q < O I = O N LO LO 00 O N