DE102007012693A1 - Miniaturized and encapsulated battery, especially for mobile telecommunications, is filled with a liquid electrolyte from a dispenser by evacuation of the intermediate zone - Google Patents

Abstract

The miniaturized battery has a filling (61,61') in the intermediate zone between the battery and its encapsulation as a polymer matrix and/or a co-polymer matrix with locked-in particles and/or a polymer matrix with a softener. An opening (70,70') is wholly within the intermediate zone, closed in the encapsulation. The opening is connected by the material to the active battery zone for evacuation and filling with electrolyte.

Description

The The invention relates to a battery having an active battery area, which is filled with liquid electrolyte, as also an electrolyte dispenser for filling a battery. Furthermore, a method for filling a battery described with liquid electrolyte.

by virtue of the increasing miniaturization of microelectronic components and microelectronic systems, efforts are being made the associated energy storage in the form of batteries to downsize. The miniaturization of batteries in foil construction However, it reaches its limits. That's why developed for very small batteries vacuum process. to Production of particularly small batteries, for example the batteries are made on a substrate and coated with a thin film hen as encapsulation or as housing hen. This is among other things as technology, the thin-film technology with vapor deposition used. However, the batteries thus produced are due to the high investment costs of production and low deposition rates very expensive in the manufacturing process. Furthermore, the layer thickness the thin-film batteries limited and the capacity consequently low. The continuous increase in energy density in conventional battery manufacturing can therefore be due to elaborate new developments in production are not always used become.

The DE 103 46 310 A1 describes a battery with very small dimensions, which has an encapsulation that meets the tightness requirements of lithium batteries. The encapsulation contributes so little to the total weight or the total thickness of the battery, so that the achievable total energy density per volume is essentially not or only slightly affected. The encapsulation is applied so that the batteries can be arranged directly on an electrical component. This is usually done with techniques from lithium technology or from the production of foil batteries.

mostly become metallic conductors as outer walls used, being between an electrochemical cell and the current conductors There is a gap which is sealed with a polymer becomes. However, this method only works well in use of solid state electrolytes. But these have at room temperature only insufficient conductivity. Therefore must for most applications liquid electrolyte can be used, which is absorbed by the electrochemical cell must become.

The Introducing liquid electrolyte into the electrochemical Cell is fraught with difficulties. Is for example the Battery separator of the electrochemical cell already with electrolyte soaked, it is almost impossible than encapsulating one To produce polymer layer or to cure an adhesive, without a reaction between the polymer and the electrolyte takes place. Also divorce vacuum coating process for sealing because there is too much electrolyte during the pumping process the battery evaporates again.

In the EP 1 730 801 describes an encapsulation of alkaline flat batteries, in which a multi-component barrier between electrolyte and encapsulation is produced. But this is very expensive and requires a minimum size of the battery.

A Another alternative is to use the electrochemical cell encapsulate and with the help of a small hole direct access to expose the electrochemical cell and through this small Hole to fill the electrochemical cell. However, it will especially when closing the hole the electrochemical Cell exposed to high mechanical or thermal loads, which can damage the cell irreversibly and too Evaporation of electrolyte from the electrochemical cell being able to lead.

The The object of the present invention is to provide a liquid electrolyte to create a fillable battery that fills efficiently can be and is inexpensive to manufacture.

The Problem is solved with an inventive A battery according to claim 1 and an electrolyte disc according to claim 14, as well as a method for filling a battery according to claim 26.

A battery according to the invention has a carrier on which at least two electrodes, wherein a first electrode is an anode and a second electrode is a cathode, and at least one separator are arranged in layers, wherein the separator between the anode and the cathode is applied, and the stacked anode, cathode and separator form an active battery area, wherein a plurality of electrochemical cells may also be included. The active battery area is equivalent to the electrochemical cells mentioned in the introduction. The active battery area is arranged in an interior space which is given by the carrier and an encapsulation. Between the carrier and / or the encapsulation and the active battery area is a gap, which is filled with electrically non-conductive material and at least one hole for filling the interior with Flüs having sigelektrolyt. The space is filled with at least one material, wherein the material has cavities and the hole is arranged so that it is located exclusively within the gap and the material with the cavity inclusions connects the at least one hole to the active battery area. In particular, the at least one hole does not provide direct access to the active battery area of the battery: access is only via the void inclusion material. Furthermore, the hole is lockable.

Of the Advantage of the battery according to the invention is that the battery is then filled with liquid electrolyte when the battery is completely encapsulated. Around to fill the electrolyte is in the encapsulation Inserted hole or opening, so that a connection between the exterior and the cavity-containing material will be produced. In this way, the battery before dried with electrolyte or flushed with gases be used to clean the batteries. The arranged in the space Material with cavity inclusions should be the intermediate space at least partially, preferably in half. This allows the hole to connect to the material with void inclusions produces, but this hole exclusively the material with cavities and not with the active battery area In contact, mechanical and thermal loads when filling the active battery area with electrolyte and minimized when closing the hole. When filling with electrolyte, the material may contain cavities pick up the liquid electrolyte in the cavities and spread very well on the active battery area, so that the liquid electrolyte very well from the active masses and The separator structure is absorbed and almost no unbound Liquid electrolyte remains. Dependent From the electrolyte used, the battery can be used as a primary battery or be designed as a rechargeable secondary battery. Of Further, due to the cavities enclosed in the material an effective evacuation of the battery interior before filling be carried out with electrolyte. Also a conditioner of the active battery area with gases is via the connection of the material with cavity inclusions possible.

By the complete encapsulation of the battery ent are none Problems with the fact that after filling with electrolyte electrochemical cell subsequently sealed at the edge Need to become. There is no risk that the edge seal reacts with the electrolyte or due to the nature of the material, as with polymers, do not crosslink or cure can. This results in the advantage that base-containing electrolytes for alkaline batteries and the very reactive electrolytes and their conductive salts of lithium-ion batteries, such as. B. lithium chloride, used for the battery according to the invention Since the battery does not have the problem of subsequent reactance having the electrolyte with the material of the seal.

by virtue of the small size of the openings can evaporate only a small amount of the electrolyte. As a result of that the hole is located exclusively in the intermediate space, and so on the void inclusions access to active battery area can be closed of the hole different techniques or materials are used which can not react with electrolytes or electrolyte and does not heat up the active battery area due to the distance.

advantageous Further developments of the battery according to the invention are described in the subordinate claims.

A advantageous development of the invention Battery is given by the fact that the wearer a recess and the active battery area disposed in the recess is. Through the depression, a cavity is created, which can easily absorb the active battery area and the space between between the active battery area and the vehicle easily can fill. Furthermore, the encapsulation be applied flat and almost flat. The advantage is that depressions in the carrier, such as a circuit board, are inexpensive to apply and can be made with conventional methods. Advantageously, for the carrier and / or the encapsulation materials used that low uptake and permeation rate of gases and liquids, such as Metal, glass or silicon.

A Advantageous further development is that the carrier has at least two components, wherein a first component a flat, substantially planar, substrate is and second component is an insulating frame, which on the first component is arranged. The advantage is that with the help of the isolation frame, which can be subsequently coated metallically, different battery shapes are possible. This offers especially if conventional techniques are not available on the substrate. The isolation frame Can be welded or glued on, but also by curing deposited by polymers or electrodeposition and lithographically structured become.

It is expedient that for the material with the cavity inclusions a polymer matrix or with entrapped particles and / or a trapped particle co-polymer matrix and / or a polymer matrix with plasticizer. This development is particularly advantageous if the polymer matrix is a polyvinylidene-di-fluoride polymer matrix (PVDF) or a polyvinylidene fluoride-co-hexafluoropropylene polymer matrix (PVFD-HFP). As a result, the material with the cavity inclusions has a porous structure. Due to the trapped particles in the polymer matrix, a highly porous structure can be produced which is easy to produce and incurs low cost. The use of a polymer matrix with plasticizers is recommended in particular when the active materials or the separator structure of the battery according to the invention has been produced with the aid of plasticizers. Generally, the material of the porous structure is chosen to be compatible with the materials of the active battery region, in the sense that there will be no reactions between the porous material and the materials of the active battery region.

advantageously, the battery is filled with two holes in the Space provided. The advantage is that at the same time over a hole the battery of gases can be evacuated, and over the other hole the electrolyte can be filled. As a result, due to the negative pressure in the battery interior of the electrolyte be recorded faster, which saves time. On the other hand, the evacuation of gases from the battery interior which are due to the drying of the battery or when rinsing the battery with gases, have remained stuck. Here is in particular to call the gas argon, where there is evidence that it is the hampers trouble-free filling with electrolyte.

To a better filling of the gap with the material With cavity inclusions, it may be advantageous that the two electrodes have a different size have, wherein the larger electrode on the Carrier and the smaller electrode arranged on the separator is. This creates a gap, which has a small cross-section at the lower surface of the carrier, which increases steadily upwards. This generally prevents air pockets from forming can.

A Another advantageous development is that the at least one Hole in the battery with a plug and / or with welded Metal particles and / or with a solder with a low melting point is closed. The advantage is that for closing of the hole used other materials than for encapsulating the battery can be. This means in particular that before the Fill with electrolyte, for example, polymers are used can, which do not cure in the presence of electrolyte or wetting, for closing the hole however, metals which are resistant to electrolytes, such as, for example, base-containing electrolytes can be used.

The battery according to the invention is particularly advantageous if the active battery area on the carrier has an area of less than 100 mm ² , preferably less than 10 mm ² , and a thickness perpendicular to the area of less than 10 mm, preferably less than 500 μm , The advantage is that a low-cost battery is manufactured in very small dimensions, which can be effectively filled with electrolyte. The use of liquid electrolyte in such small batteries is also advantageous because liquid electrolyte, in contrast to solid state electrolytes at room temperature has a satisfactory conductivity. This means in particular that the flat liquid electrolyte-filled batteries can be used in everyday use. Another advantage is that the same materials can be used that are used for the mass production of lithium polymer batteries and are optimized with respect to all battery properties such as stability, Zyklisierbarkeit, energy density, power density and security.

To the Filling the battery according to the invention For example, an electrolyte dispenser according to the invention can be used become. The electrolyte dispenser comprises at least one electrolyte tank and at least one nozzle, wherein the at least one nozzle a sealing system for making a tight connection with a device to be refueled and the electrolyte tank directly or via at least one valve with the at least a nozzle for filling the device to be refueled is connectable, characterized in that a suction pump available which is directly or via at least one valve at least one nozzle for producing a negative pressure in the can be connected to refueling device.

Of the Advantage of the electrolyte dispenser according to the invention is that before filling with electrolyte Vacuum preferably a coarse or a fine vacuum in the battery interior is generated, which on the one hand volatile gases from the battery interior evacuates and on the other hand, the electrolyte faster in the battery compartment distributed because it is sucked in due to the negative pressure.

Here, a nozzle, which is attached to a hole of the battery, wherein both the suction pump and the electrolyte tank via a valve with the one nozzle in connection, or two nozzles, wherein both the electrolyte tank and the suction pump have their own nozzle, which are arranged on two different holes of the battery can be used. Premature evacuation eliminates weak points when filling the battery.

Further advantageous developments of Elektrolytdispensers are in the subordinate claims against.

A advantageous development is that the suction pump as a vacuum pump or membrane vacuum pump is formed. The use of a dry oil-free Pump is advantageous. Due to the high negative pressure will be both a larger amount of gases from the battery interior evacuated as well as the suction pressure for the electrolyte increased. Overall, this has better enforcement of the battery interior with electrolyte and a faster filling result.

A Another advantageous embodiment of Elektrolytdispensers is it is that at least one valve designed as a two-way valve is. This means, especially in the presence of only one piece, that over a single two-way valve the interior one after the other can be evacuated and filled with electrolyte. Furthermore Can be over the execution as a two-way valve a device for flushing the battery interior with Gases, such as argon, dry air or nitrogen become.

expedient it is that at least two nozzles are present, with a first Nozzle directly or via a valve with the electrolyte tank and a second nozzle directly or via a valve with the suction pump is connected. That way you can a simultaneous evacuation or application of negative pressure and Fill the interior of the battery with electrolyte. This allows a particularly efficient filling and production an electrolyte-filled battery. Another advantage when using at least two openings and nozzles is it that the diameter of the filler neck and the Extractor can be adapted to their task. For accurate dispensing of the electrolyte cannulas be used with only a few microns inside diameter. For an evacuation, for example a vacuum evacuation, is a large suction cross-section advantageous, so that the suction nozzle a larger inside diameter in the millimeter range should have. For large and very flat Batteries can also make sense, each with several holes for filling and evacuation.

One Another advantage is given by the fact that at least one nozzle has a closure to the outside. With the help of a lock it may be possible to dispense with a valve at the nozzle. The valve or the valve function would thus be in the nozzle self-installed. Furthermore, it may be advantageous if the connected to the device to be refueled side of the nozzle is heated, so that at the same time after filling or Evacuate the hole in the enclosure of the battery or to refueling device can be closed. This would allow a particularly efficient filling, because after filling the battery is closed and thus finished is placed.

A Another advantageous embodiment is that the suction pump with a pressure gauge is connected, with the pressure gauge of the negative pressure is measured in the device to be refueled. This allows one Control when the for the electrolyte filling suitable negative pressure in the battery interior is reached.

There the electrolyte dispenser expediently at is used very small batteries, it is advantageous if the valves or pumps designed as micro valves or micropumps are. This allows a miniaturization of the electrolyte dispenser to the dimensions of the very small battery.

expedient It is also when the filling of electrolyte and manufacturing a negative pressure are independently controllable, d. h., Especially in the presence of valves, the valves independently are controllable from each other.

Farther it is expedient if the electrolyte dispenser having a control, which the at least one valve and the Actuates suction pump. In this control, the information about the negative pressure and / or the valve status and / or the filling status of the electrolyte tank are merged and so different Evacuation or filling processes switched become. So can be evacuated first and then filled, or be filled during evacuation, or first evacuated, a short period filled simultaneously and then only be filled.

The Use of a controller is particularly advantageous when the control electronic and / or mechanical-electronic components and / or includes a timer.

The inventive method for filling a battery with a liquid electrolyte, wherein the battery comprises an active battery area, comprises at least the subsequent steps. First, at least one hole is applied in an encapsulation of the battery. Thereafter, gases are evacuated from an interior of the battery and then the interior of the battery filled with an electrolyte. Finally, the hole of the battery is closed. The advantage lies in the particularly efficient filling of the battery. By evacuating disturbing gases are removed from the interior and the electrolyte can thus maximally flood into the interior of the battery.

By the introduction of a very small hole, which expediently especially not touching the active battery area, but with the material with cavity inclusions in the intermediate layer connected, no additional charges or mechanical loads on the active battery area. The Method is both for filling primary batteries as well as for charging rechargeable secondary batteries suitable.

Further advantageous developments of the invention Methods are given in the subordinate claims.

advantageously, the method is used in conjunction with an inventive Battery and / or an electrolyte dispenser according to the invention performed.

The Advantages result from the advantages of the invention Inventions.

advantageously, When evacuating the gases at least a rough vacuum, preferably a fine vacuum, generated in the interior of the battery. This results a very complete evacuation and fast Filling the battery. During or before evacuation the gases may be the interior of the battery with a gas, preferably with argon or dry air or nitrogen. The advantage is the cleansing effect of the conditioner with gases.

A Particularly advantageous embodiment of the method is, if after filling the battery with electrolyte and before closing of the at least one hole of the battery charges the battery or is formed. The advantage is that during Charging gases can evaporate from the battery and so no pressure in the battery is introduced.

Further advantageous developments of the invention Objects and the procedure are in the further subordinate Claims described.

in the The following are the devices of the invention explained in more detail with reference to some embodiments become. Show it

1a to 1e various embodiments of the battery according to the invention,

2 Top view of a battery arrangement according to the invention,

3a and 3b various embodiments of a fuel dispenser according to the invention.

In the 1a to 1e is discussed on different aspects of a battery according to the invention. In 1a is a battery 1 to see which one has an active battery area 2 and on a support, which consists of a substrate 3 and an isolation frame 4 is constructed, is arranged.

The structure of the active battery area 2 is in 1b explained. The battery has an anode 201 and a cathode 202 on which by a separator 203 are separated from each other. Furthermore, on the anode and on the cathode in each case a current conductor 204 respectively. 205 applied. The separator 203 consists of an electrically non-conductive material, but is permeable to certain molecular compounds or ions.

In the 1 is through the insulation frame 4 a depression 5 limited, in which the active battery area 2 is arranged. The isolation frame 4 is inert to the materials of the active battery area and has good hermiticity. It is made of glass or Teflon, for example. On the substrate 3 can do a variety of isolation frames 4 be arranged and a variety of wells 5 be generated. The shell of the insulation frame 4 should be about the thickness of the active battery area 2 correspond. The recess shown here 5 however, it can also be generated by other technologies. For example, the depression 5 also be a deep-drawn metal foil, an injection-molded metallized polymer part, a recess in a printed circuit board or a recess made by etching in a silicon substrate.

The active battery area will be in the recess 5 used, with an electrical connection between the underlying current conductor 204 and a bottom metallization deposited on the substrate. This happens, for example, by electrically conductive bonding. The current collector 204 respectively. 205 consists here of a metal foil such. B. copper. It is also possible that on the current collector 204 respectively. 205 is omitted, with the anode below 201 , is laminated directly onto a deposited on the substrate bottom metallization. The bottom metallization then serves as a current conductor for the anode 201 , Of course can also be the cathode 202 be applied to the bottom of the carrier.

Between the active battery area 2 and the isolation frame 4 there is a gap 6 . 6 ' where the gap is with a porous material 61 . 61 ' and another mechanically more stable material 62 . 62 ' is filled. The porous material 61 . 61 ' and the other material 62 . 62 ' serves to seal the gap. For the porous material 61 respectively. 61 ' For example, glass or ceramic particles which are held together by a PVDF come into question. In this case, the particles are coated only with a thin layer of PVDF, wherein the PVDF layer ensures a cohesion of the particles, but leaves enough gaps, ie forms a porous structure with cavity inclusions. To improve adhesion, the particles may also be used with the aid of a co-polymer such as PVFD-HFP. The porosity can also by other means, for. B. by means of plasticizers. In this case, for example, a polymer matrix such as PVDF with a plasticizer, such as. As dibutyl phthalate (DBP) used. The plasticizer is after placing in the space 6 . 6 ' extracted and the resulting PVDF layer is retained and has a porous structure. The use of plasticizers is particularly useful if the active battery area 2 is also produced with the aid of plasticizers and after the introduction of the plastic matrix interspersed polymer matrix, a common extraction process for the battery and the filled space can be carried out. Generally speaking, the porous material must be 61 respectively. 61 ' electrically insulating and compatible with the materials of the active battery area 2 be selected. After application of the porous material 61 . 61 ' becomes the battery 1 under vacuum or a protective gas, such as argon, dried at elevated temperature. In the case of lithium batteries, the water content within the battery or the porous material must be reduced down to a few ppm.

The porous material 61 . 61 ' fills the gap 6 respectively. 6 ' only halfway, approximately to the height of the separator 203 , After the introduction of the porous material, it must be dried before another material 62 . 62 ' completely fills the gap. It is advisable to use a polymer which has a higher mechanical stability than the porous material 61 . 61 ' has. For lithium batteries, the more mechanically stable polymer must also have a very low water content and be inert to a liquid electrolyte and the electrode materials to be used.

In 1c is an alternative embodiment of the battery 1 shown in which the porous material 61 . 61 ' almost completely fills the gap. This can be in the space 6 . 6 ' a larger amount of liquid electrolyte to be applied later be absorbed. Unlike the execution in 1a However, the mechanical stability is lower.

After filling the gap, the battery with the material layer 7 encapsulated. This encapsulation layer must be anhydrous and have a very low permeation rate. For this purpose, metal layers are suitable, as these simultaneously an external electrical contact for the cathode 202 deliver. It is also possible to use a layer which consists of numerous polymer and / or metal layers. For metal coating should primarily dry processes such. As vapor deposition, sputtering or vapor deposition method can be used. Another way to produce a encapsulating layer is to apply an adhesive over the entire surface, wherein the adhesive also compensates for unevenness in the gaps or the active battery area and on the adhesive, a thin substrate or a film is applied. In particular, UV-curable adhesives and glass substrates are suitable here. To get to the electrical external contacts of the active battery area holes are then applied in the enclosure, which make the external contacts freely accessible. For this, the holes must be metallized. These additional holes are different from the holes in the space for evacuating or filling the battery.

In the material layer 7 are two openings 70 . 70 ' and the underlying other material 62 . 62 ' with the openings 70 . 70 ' in flight holes 63 . 63 ' brought in. The openings 70 . 70 ' , if necessary in connection with the holes 63 . 63 ' , connect to the porous material 61 . 61 ' ago. It should be noted that both the openings 70 . 70 ' , as well as the holes if necessary 63 . 63 ' in the space 6 . 6 ' be introduced. The openings are preferably largely from the active battery area 2 arranged remotely to minimize the mechanical and thermal loads on the active battery area at a later closing of the holes, so that, for example, almost no liquid electrolyte can evaporate from the active battery area. Both at the openings 70 . 70 ' and the holes 63 . 63 ' These are holes that can be made mechanically or with a laser. Because the openings 70 . 70 ' or the holes 63 . 63 ' are designed for filling the battery with electrolyte and for evacuating gases from the interior of the battery, two openings per battery can be connected to a filling system. However, it can also be a single opening 70 , possibly with hole underneath 63 , available be, which then serves both for evacuating gases and for filling with electrolyte.

Another form of training of the battery is in 1d outlined. Here is the anode 201 and the separator 203 bigger than the cathode 202 formed, resulting in easier filling of the space with porous material 61 . 61 ' can lead and a greater choice for the introduction of openings 70 . 70 ' allows, as the cathode 202 is smaller.

In 1e be the openings 70 respectively. 70 ' with small plugs 8th respectively. 8th' hermetically sealed, with the plugs 8th . 8th' stick by positive engagement and friction effect. Alternatively, small metal balls can be pressed or small balls or metal plates by means of ultrasound or thermocompression with the encapsulation 7 be welded. Flux-free soldering with low-melting solders is also used to seal the openings 70 respectively. 70 ' possible.

The in the 1a to 1e shown batteries are before closing the openings 70 . 70 ' filled with a liquid electrolyte. The refueling takes place when the battery 1 already finished and dried, with the filling through the openings 70 . 70 ' takes place. The liquid electrolyte is thereby in the openings 70 . 70 ' filled and from the porous material 61 . 61 ' and of the pores of the separator and the active materials, such. B. the cathode and the anode sucked up. This applies to lithium-ion batteries or lithium polymer batteries as well as for alkaline systems, such as. Alkali metal, Zn-Ni, Zn-air, AgO-Zn. Because the porous material 61 . 61 ' allows indirect access to the active masses and the separator, it is not necessary to fill the battery the active battery area 2 expose. This means in particular that the electrically insulating embedding of the active battery area 2 by using a polymer matrix before filling the electrolyte happens. This brings, for example, in alkaline batteries the advantage that polymers or adhesives can be used as a seal in the space, since there are so far only a few polymers that in the presence of alkaline bases such. As KOH or NaOH, can crosslink or cure and so form a stable interface to the active battery area. With the help of the batteries used here, a base that is stable with respect to bases can be produced with a metal plastic composite. The closing of the filling openings for the electrolyte then takes place with metal compounds stable in the alkaline range. In lithium batteries are used as the electrolyte conductive salts, which are dissolved in a solvent. Since the electrolyte is filled in a closed except for very small openings volume, and this volume is accessible only through very small openings, it does not lead to the otherwise occurring evaporation of the solvent, which increases the concentration of the conductive salt.

The battery shown here can be made very small. These are areas of less than one square centimeter and thicknesses of the active battery area 2 be produced between 50 microns and about 1 mm. Of course, the active battery area may also comprise a plurality of electrochemical cells. The electrochemical cells are stacked on top of each other. The connection between the individual electrochemical cells takes place via electrically conductive adhesives or additional metallization layers or further processes known from the prior art. The encapsulation then includes all electrochemical cells, ie the entire active battery area.

In 2 is a space-saving arrangement of batteries 1 . 1' with filling openings 70 respectively. 70 ' on a substrate 3 shown. The edge provided with the microporous filling 6 is only thin, in the range of 50-500 μm, around the area-related energy density of the batteries 1 . 1' keep as high as possible. The openings 70 respectively. 70 ' are therefore on with the border area 6 connected webs 9 Applied, because so the holes are not the active battery area 2 respectively. 2 ' touch. Also, by attaching additional webs 9 the hole 70 . 70 ' larger, which allows a cheaper production of the battery. The narrow edge area 6 . 6 ' is necessary as it further miniaturizes the batteries 1 . 1' allowed up to the millimeter range. Thus, for example, lithium flat pack polymer batteries, which are packed in a sealing film, are provided with an edge region of approximately 5 mm. Chip card batteries, where the current collector foils are sealed with a polymer, require a sealing edge of approx. 2 mm. With a battery according to the invention can be achieved much smaller edge areas. The edge region, which is filled with the microporous structure, can be reduced according to the invention between 10 .mu.m and 100 .mu.m. Additional space is required for the holes to be filled with electrolyte or evacuated gases, but this can be made smaller than 1 mm.

In 3a becomes an electrolyte dispenser 10 for filling a battery 1 shown. The electrolyte dispenser 10 has an electrolyte tank 11 on, which has a valve 12 with a neck 13 connected, with the connecting piece 13 is designed as a filling nozzle and a sealing system 14 has, which is designed as an O-ring. Furthermore, the electrolyte dispenser 10 a suction pump 15 on which via a valve 16 with a neck 17 is connected, wherein the nozzle a seal 18 has, which is designed as an O-ring. Furthermore, the suction pump 15 with a pressure gauge 19 connected. In addition, an electronic control system 20 present, which the suction pump 15 , the outflow of the electrolyte tank 11 and the valves 12 and 16 controls and the individual components during operation of the electrolyte dispenser 10 matches each other. The one with the electrolyte tank 11 connected sockets 13 gets on an opening of the battery 1 put on, with the opening 70 smaller than the diameter of the O-ring 14 , The O-ring 14 must be placed so that it completely surrounds the opening. The with the suction pump 15 connected sockets 17 will be on another opening 70 the battery is attached and with a gasket 18 sealed.

The stub 17 , which serves as a suction port for the vacuum pump, has a larger diameter than the port, which through the nozzle 13 is formed, since the pumping power of the suction pump 15 decreases sharply with decreasing cross-section. For filling through the nozzle 13 is a very small diameter sufficient, since only very small volumes of electrolyte must be dosed. In 3a are two neck 13 . 17 shown. Of course, the outer diameter of the nozzle must be chosen so that both nozzles can be placed simultaneously and each nozzle covers only one of the two marked openings. So z. For example, with a battery area of 10 mm × 10 mm and a distance to an adjacent battery (as in 2 shown) the neck 17 have an outer diameter of 2 mm to 10 mm. For a smaller battery area of 1 mm × 1 mm, the outer diameter of the nozzle 17 up to 1 mm. The stub 13 for filling the battery with an electrolyte is advantageously smaller and even be designed such that the nozzle like a cannula through the opening 70 in the hole 63 fit. In this way, the electrolyte can be dosed very finely, since there is no risk of leakage. The diameter of the cannula can advantageously be between 50 μm and 1 mm. The valves 16 respectively. 12 , which of the suction pump 15 or the electrolyte tank 11 can be designed similarly. The vacuum valve 16 may have a larger cross-section to the pumping power of the suction pump 15 not to reduce. For the valve 12 , which is connected to the electrolyte tank, a smaller valve is sufficient, since these, as already mentioned, only have to deliver small volumes of electrolyte. For this reason, the valves can also be designed as microvalves. The amount of electrolyte dispensed per battery depends, on the one hand, on the porosity of the entire active battery area and, on the other, on the total area of the battery. With a battery area of 1 cm 2 and a thickness of 200 μm, the electrolyte quantity at a porosity of the active battery area is from 30% to 40%, ie the void volume of the active battery area related to the total volume of the active battery area, approximately 6 to 8 μl , With a battery area of 1 mm ^ 2, correspondingly 100 times less.

The suction pump 15 is a dry oil-free pump, such as. B. a diaphragm pump. In this version, it is designed as a vacuum pump, which can generate a fine vacuum in the battery interior. The control electronics 20 monitors the opening and closing of the valves 12 and 16 or the operation of the suction pump 15 ,

The operation of the electrolyte dispenser will be explained below. The pillars 13 and 17 be on the battery 1 docked and sealed. The valve 12 is initially closed. The battery interior is by opening the valve 16 by means of the pump 15 evacuated. Once a predetermined negative pressure is reached, the valve becomes 16 closed and the valve 12 opened for a short time to dose an exact amount of electrolyte. For larger batteries, it may be useful to have both valves within a short period of time 16 and 12 are open. As a result, a vacuum is still generated on one side of the battery when electrolyte is already being filled in on the other side. As a result, the filling process can be accelerated by the generated negative pressure and possible leaks in the seal 18 be compensated.

Since the battery starting from the filling a microporous structure 61 . 61 ' has a uniform evacuation and distribution of an electrolyte in all battery areas can be ensured. Between the vacuum evacuation and the filling with electrolyte, a gas scavenging can be carried out via a further device, in which the interior of the battery is evacuated intermittently and flushed with gases such as argon, nitrogen or dry air. For such additional gas purging, the valves must 12 and 16 be designed as two-way valves, so that the gas through a filler neck, in this case neck 13 , filled and through another neck, in this case neck 17 , is sucked off again. By evacuating gases from the battery interior results not only easier filling of the battery due to the negative pressure, but also because no annoying noble gases, such as argon, the uniform filling of the battery 1 can hamper.

The control 20 takes over in Dispensiersystem 10 the task of timing the valves and sucking and filling with electrolyte vote. For this purpose, microelectronic mechanical components or microelectronic components can be used.

In 3b is an alternative embodiment of the electrolyte dispenser 10 shown. In the case of the electrolyte dispenser shown here 10 is only a nozzle 13 with seal 14 attached, which both as a filling nozzle for the electrolyte from the electrolyte tank 11 as well as a suction nozzle for the operation of the suction pump 15 serves. In doing so, the valve must 21 be designed as a two-way valve, so that can be switched between the evacuation of gases by means of a vacuum and the filling with electrolyte. The changeover happens in the control electronics 20 ,

The electrolyte dispenser shown here 10 is suitable for filling very small batteries with liquid electrolyte. Since liquid electrolyte is needed for operation at room temperature in almost all currently relevant batteries with sufficient current capacity and capacity, with the help of Elektrolytdispensers and the inventive method is given a cost-effective and fast way, a battery which is encapsulated in advance and is accessible only through small openings to fill. The battery according to the invention can be used in numerous applications. Here, all miniaturized electronic devices or microsystems are relevant, which require a very small battery as a primary energy storage or as a buffer memory. These are z. As sensors from medical technology, which are used in implants, such as electronic dental implants or medical probes. Furthermore, sensors can be supplied with energy to the batteries, which are extremely miniaturized (egrain) and serve there as temporary storage for energy recovered from the environment. Furthermore, data storage with volatile media, which require a battery conceivable. The battery according to the invention can also be used in cards with an integrated circuit for processing payment transactions or for recognition or for use in portable telecommunications devices such as mobile phones or laptops and are characterized by long durability and their flat design. The use in active transponders or smart labels is also possible. In the course of being able to insert electronics into various garments, this field also offers opportunities to use the batteries.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - DE 10346310 A1 [0003]
• - EP 1730801 [0006]

Claims (38)

A battery having a support on which at least two electrodes, wherein a first electrode is an anode and a second electrode is a cathode, and at least one separator are layered on each other, wherein the separator between the anode and the cathode is applied and the one another arranged anode, cathode and separator form an electrochemical cell and the at least one electrochemical cell forms an active battery area and the active battery area is disposed in an interior, which is surrounded by the carrier and an encapsulation, and between the carrier and / or the encapsulation and the active battery area is a gap which is filled with electrically non-conductive material and has at least one hole for filling the interior with liquid electrolyte, characterized in that at least one in the space ( 6 . 6 ' ) filled material ( 61 . 61 ' ) Has void inclusions and the at least one hole ( 63 . 70 ; 63 ' . 70 ' ) exclusively within the interval ( 6 . 6 ' ) and in the encapsulation ( 7 ) is closable and for evacuation and filling with electrolyte, the material with void inclusions ( 61 . 61 ' ) the hole with the active battery area ( 2 ) connects. Battery according to claim 1, characterized in that the material with cavity inclusions ( 61 . 61 ' ) the at least one hole ( 63 . 70 ; 63 ' . 70 ' ) with the separator ( 203 ) and / or the cathode ( 202 ) and / or the anode ( 201 ) connects. Battery according to claim 1 or 2, characterized in that the carrier ( 3 . 4 ) a recess ( 5 ) and the active battery area ( 2 ) in the depression ( 5 ) is arranged. Battery according to one of the preceding claims, characterized in that the carrier ( 3 . 4 ) and / or the encapsulation ( 7 ) consists of a material with low absorption and permeation rate for gases or liquids. Battery according to one of the preceding claims, characterized in that the carrier ( 3 . 4 ) has at least two components, wherein a first component is a planar, substantially planar, substrate ( 3 ) and a second component is an insulation frame ( 4 ), which is arranged on the first component. Battery according to one of the preceding claims, characterized in that the interior with liquid electrolyte is filled up. Battery according to claim 6, characterized in that the liquid electrolyte is completely separated from the active battery area ( 2 ) and the material with cavity inclusions ( 61 . 61 ' ) is receivable. Battery according to one of the preceding claims, characterized in that the material with the cavity inclusions ( 61 . 61 ' ) is an entrapped particle polymer matrix and / or entrapped particle co-polymer matrix and / or a plasticizer polymer matrix. Battery according to claim 5, characterized in that that the polymer matrix is a poly-vinylidene-di-fluoride polymer matrix (PVDF) or a poly-vinylidene fluoride-co-hexafluoropropylene polymer matrix (PVFD-HFP). Battery according to one of the preceding claims, characterized in that at least a first hole ( 63 . 70 ) in the space for evacuation and at least one second hole ( 63 ' . 70 ' ) are introduced in the space for filling the inner space, wherein the first and second holes do not touch each other. Battery according to one of the preceding claims, characterized in that the two electrodes ( 201 . 202 ) have a different size, the larger electrode ( 201 ) on the support ( 3 ) and the smaller electrode ( 202 ) on the separator ( 203 ) is arranged. Battery according to one of the preceding claims, characterized in that the at least one hole ( 63 . 70 ; 63 ' . 70 ' ) in the encapsulation ( 7 ) with a stopper ( 8th . 8th' ) and / or sealed with welded metal particles and / or with a solder having a low melting point. Battery according to one of the preceding claims, characterized in that the active battery area ( 2 ) on the support ( 3 ) has an area of less than 500 mm 2, preferably less than 10 mm 2, and a thickness perpendicular to the area of less than 10 mm, preferably less than 500 μm. Electrolyte dispenser, which comprises at least one electrolyte tank and at least one nozzle, wherein the at least one nozzle has a sealing system for establishing a tight connection with a device to be refueled and the electrolyte tank directly or via at least one valve with the at least one nozzle for filling the device to be refueled is connectable, characterized in that a suction pump ( 15 ) which is directly or via at least one valve ( 16 ) with at least one nozzle ( 17 ) for producing a negative pressure in the device to be refueled ( 1 ) is connectable. Electrolyte dispenser according to claim 14, characterized in that the suction pump ( 15 ) is designed as a vacuum pump or membrane vacuum pump. Electrolyte dispenser according to one of claims 14 or 15, characterized in that at least one valve ( 21 ) is designed as a two-way valve. Electrolyte dispenser according to one of claims 14 to 16, characterized in that the electrolyte tank ( 11 ) and the suction pump ( 15 ) via at least one valve ( 21 ) with an identical neck ( 13 ) are connectable. Electrolyte dispenser according to one of claims 14 to 17, characterized in that at least two connecting pieces ( 13 . 17 ) are present, with a first neck ( 13 ) directly or via a valve ( 12 ) with the electrolyte tank ( 11 ) and a second nozzle ( 17 ) directly or via a valve ( 16 ) with the suction pump ( 15 ) connected is. Electrolyte dispenser according to one of claims 14 to 18, characterized in that at least one nozzle ( 13 . 17 ) has a closure to the outside. Electrolyte dispenser according to one of claims 14 to 19, characterized in that the suction pump ( 15 ) with a pressure gauge ( 19 ), whereby with the pressure gauge ( 19 ) the negative pressure in the device to be refueled ( 1 ) is measured. Electrolyte dispenser according to one of the claims 14 to 20, characterized in that at least one microvalve and a micropump are present. Electrolyte dispenser according to one of the claims 14 to 21, characterized in that the filling of Electrolyte and creating a negative pressure independently are controllable. Electrolyte dispenser according to one of claims 14 to 22, characterized in that a controller ( 20 ) is present, which the at least one valve ( 12 . 16 ) and the suction pump ( 15 ). Electrolyte dispenser according to claim 23, characterized in that the controller ( 20 ) comprises electronic or mechanical-electronic components and / or a timer. Electrolyte dispenser according to one of claims 14 to 24, characterized in that the at least one nozzle ( 13 ) for filling a device with electrolyte, an internal diameter of 50 microns to 2 mm, preferably from 100 microns to 1 mm, and for evacuating gases ( 17 ) has an inner diameter of up to 10 mm. Method for filling a battery with a liquid electrolyte, wherein the battery has an active Battery area comprising the following steps: a) Applying at least one hole in an encapsulation of the battery; b) Drying the battery at elevated temperatures; c) Evacuating gases from an interior of the battery; d) filling the interior of the battery with electrolyte; e) sealing the hole of the battery. A method according to claim 26, characterized in that for evacuating gases and filling with electrolyte a nozzle ( 13 . 17 ) of an electrolyte dispenser according to one of claims 14 to 25 with the at least one hole ( 63 . 70 ; 63 ' . 70 ' ) of the battery ( 1 ) is connected. Method according to one of claims 26 or 27, characterized in that when evacuating the gases at least one rough vacuum, preferably a fine vacuum, in the interior ( 2 ) of the battery ( 1 ) is produced. Method according to one of claims 26 to 28, characterized in that during the evacuation of gases of the interior ( 2 ) of the battery ( 1 ) is purged with a gas, preferably with argon or dry air or nitrogen. Method according to one of claims 26 to 29, characterized in that the filling with electrolyte is started before the evacuation of gases is completed. Method according to one of claims 26 or 30, characterized in that a battery ( 1 ) according to one of claims 1 to 13 is used. Method according to one of claims 26 to 31, characterized in that the hole ( 63 . 70 ; 63 ' . 70 ' ) of the battery ( 1 ) outside the active battery area ( 2 ) into the battery ( 1 ) is introduced. Method according to one of claims 26 to 32, characterized in that after filling with electrolyte and before closing the at least one hole ( 63 . 70 ; 63 ' . 70 ' ) of the battery ( 1 ), the battery ( 1 ) is charged or formed. Method according to one of claims 26 to 33, characterized in that a closure of the at least one hole ( 63 . 70 ; 63 ' . 70 ' ) in the Encapsulation ( 7 ) of the battery ( 1 ) is performed with interference fit and / or micro rivets and / or ultrasonic welding. Card with an integrated circuit for processing payment transactions and / or for recognition and / or for use in portable telecommunications equipment, characterized in that the integrated circuit for powering a battery ( 1 ) according to claims 1 to 13. Medical-technical sensor with a battery ( 1 ), characterized in that the battery is designed according to one of claims 1 to 13. Data memory with a battery, characterized in that the battery ( 1 ) is designed according to one of claims 1 to 13. Clothing with a battery, characterized in that the battery ( 1 ) is designed according to one of claims 1 to 13.