WO2015197597A2

WO2015197597A2 - Thin-film battery having low fluid content and an increased service life

Info

Publication number: WO2015197597A2
Application number: PCT/EP2015/064069
Authority: WO
Inventors: Miriam Kunze; Ulrich Peuchert
Original assignee: Schott Ag
Priority date: 2014-06-23
Filing date: 2015-06-23
Publication date: 2015-12-30
Also published as: WO2015197597A3

Abstract

The invention relates to a thin-film battery having an increased service life and low fluid content, wherein its fluid content is at most 2000 ppm, preferably at most 500 ppm, particularly preferably at most 200 ppm and most preferably at most 50 ppm. The invention further relates to an inorganic, silicon-containing, in particular silicate, substantially fluid-free material and to a method for producing such a thin-film battery.

Description

Thin film battery with low fluid content and increased service life

description

Field of the invention

The invention relates to thin-film batteries, in particular lithium-based thin-film batteries, which have a low fluid content and a resulting increased

Have life.

Background of the invention

Microelectronic components, in particular

miniaturized storage elements for electrical energy are becoming increasingly important, for example for so-called smart cards.

In particular, lithium-based thin-film batteries have a number of particularly preferred properties, for example, a low weight and a high

Power density. However, there are still significant difficulties in terms of their life, the

Cycle stability, i. the number of loading and unloading

Discharge cycles that you can perform with them, and generally with regard to their life. The reason for this is to be found in that lithium in elemental form, such as in the anodes charged

Lithium-based batteries or accumulators, has an extremely low reduction potential. Also, other of the active battery materials of a lithium-based battery or a lithium-based Accumulators are extremely vulnerable to

Degradation reactions. So is usually called

Anode material in a lithium-based electrical energy storage unit does not use elemental or metallic lithium, but rather a material that is improved in its durability, such as graphite, is incorporated into the lithium as an elemental material, i. with the

Oxidation level 0, can be intercalated. But even this material has a high reactivity. Other lithium-based battery materials also have high hygroscopicity, i. have an attractive effect on water.

Due to the diverse compounds, the lithium

Consequently, the contact of lithium-containing material with fluids can easily lead to the formation of undesirable compounds which are no longer available for the cyclical storage and delivery of electrical energy and accordingly the storage capacity of the lithium-based ones Battery or the lithium-based accumulator

to reduce. This can be for example

Lithium carbonate, Li ₂ CC> 3, lithium hydroxide, LiOH or

other poorly soluble compounds act in which the lithium ions or atoms are firmly bound and thus are no longer available for the charge transport.

Furthermore, most of these lithium compounds also have the property of binding fluids,

For example, H ₂ O, CO ₂ , N ₂ , so that not only the storage capacity of the accumulator or the battery is rescued by the disturbing reactions with fluids, but also further fluids are bound, the in turn also lead to Abreaktion with more lithium and thus a total of a kind of self-reinforcing process is set in motion. The question of the reduction, possibly even the complete avoidance of such unwanted reactions is thereby one of the core problems for the production

improved lithium-based storage elements for

electrical energy, so that in the literature for this a number of approaches are discussed.

For example, US 2004/0018424 A1 describes a rechargeable lithium-based thin film cell comprising a polyimide substrate. The polyimide substrate is specially dried by first placing the polyimide in acetone, replacing it

at least part of the water bound in the polyimide or adsorbed to the polyimide is replaced.

Subsequently, a thermal drying process takes place. Furthermore, the thin-film cell still has a

Parylene topcoat, which acts as a permeation barrier to protect cell materials from degradation.

However, the substrate material thus obtained is still not completely freed of water, but it has only come to a reduction of the water content. Furthermore have polymeric

Encapsulating materials usually have insufficient barrier to fluids, especially for particularly sensitive applications.

US 2004/0029311 AI describes an encapsulated

electrochemical storage unit, in which a Multilayer laminate is pressed onto the functional layers of the electrochemical storage unit. The multilayer laminate may contain a metallic layer. Furthermore, in contact with the

Underlying layers of the memory cell located layer of a stickable material, so as to the permanent contact between the laminate and the substructure

guarantee. However, as a rule, such laminates are susceptible to delamination, ie a replacement of

Layers. In addition, there is a risk that the

Organic adhesive material itself corrosively acts on the functional materials of the cell.

The US 2006/0216589 AI continues to describe a

Thin-film battery, in which different

Functional layers are applied to a substrate.

Furthermore, the thin-film battery comprises a cover, which at a distance from the surface of the

Functional layers is applied such that

between the surface of the cover and the

Functional layer creates a gap. Furthermore, the battery is protected by a seal or encapsulation based on an organic polymer between the substrate and the cover from environmental influences. The gap serves to compensate for thickness variations or thermal expansion of the functional layers of the battery, which can result in the respective charging and discharging cycles of the battery. The disadvantage here is that such a gap is naturally fluid-filled and thus

Reactions between the fluids and the battery materials can occur. Furthermore, have polymeric

Encapsulation materials usually have a permeation rate for fluids, such as water, which is d m ² at about 1 g / cc. Although this is sufficient for most applications of such sealing polymers, but you come in applications in the high performance area, ie

for example, miniaturized electronic

Devices such as a thin-film-based lithium-ion battery or a lithium-ion battery to the limits of performance.

Furthermore, US 2008/0003492 AI describes a

hermetic encapsulation for a lithium-ion battery. This can consist both of an encapsulation, that between the substrate and that on the substrate

applied overlapping Superstrat has been applied, so comparable, for example, a seal, or in the form of a multi-layer laminate with barrier properties. Here too, the difficulties discussed above are too high

Permeation rate of organic sealants on the one hand and on the other hand the risk of delamination of multilayer material in contact with functional materials on the other side.

US 2008/0213664 AI describes a method for

Production of a battery, in which a substrate material is baked. This way not only

superficial impurities are removed, but also in the substrate chemically bound water, such as water of crystallization. In this case, the heating of the substrate material can be carried out both before the coating thereof with a first layer and during the

thermal bake of functional layers of the battery, For example, of lithium cobalt oxide in the case of

Lithium Ion Battery. For the heating of water bound in the substrate, so for example of water of crystallization, are usually temperatures of several

One hundred ° C required. For example, the delivery of water of crystallization in the case of mica is usually carried out at temperatures above 500 ° C. Although it is possible in this way to significantly reduce the fluid content in a battery based on, for example, a mica, nevertheless, especially in phyllosilicates, which in their crystalline

Have structures cavities or between the individual layers forming the crystal ions or also

Absorb adsorbents, a perfect

Fluid freedom can not be achieved. This is all the more true as the water of crystallization is a constituent element of the mica and a complete expulsion

This would lead to a disintegration of the crystal structure and thus to a loss of mechanical stability of the substrate.

The US 2008/0263855 AI and the US 2009/0057136 AI

also respectively describe methods for the production of batteries on a substrate, which is baked for the reduction of fluids, in particular of water, wherein the heating substantially corresponds to the method described in US 2008/0213664 AI.

US 2009/0214899 AI describes for the protection of

Functional layers of a thin-film battery one

metallic seal, wherein this seal is formed as a layer and at least a part of

Functional layers covered, especially their edges. In addition to a first seal, there are usually several other other seals, the other, not yet covered by the first sealant layer

Protect functional layers. These too are made of metal and can also be contacted electrically.

US 2010/0190051 A1 describes a barrier layer for a thin-film battery. This can both off

Tin compounds, such as tin oxide, phosphate or - fluorophosphate exist, as well as be formed of glass, for example, a chalcogenide glass, a tellurite glass or a borate glass. The layer encapsulates the layers of the thin-film battery and even completely prevents or prevents the layers from being exposed to air or moisture. Although it is quite possible that these layers have a good barrier effect, in particular the glass materials themselves are extremely susceptible to environmental influences. For example, the chalcogenide glasses are not stable in air and decompose. Thus, the layer materials are not suitable for use in batteries which are to be stored under normal environmental conditions.

US 5,338,625 describes as a substrate for a

Thin-film battery based on lithium a glass as

Substrate. However, no statement is made here about its water content or its permeation effect.

US 6,214,061 Bl describes a protection for a

Lithium electrode. This consists of a protective layer, which may be formed amorphous or glassy, but at the same time ion conducting for the active battery material, that is lithium in this case, the layer always being produced by a coating process and being thinner than 5 ym. The system of lithium metal and deposited protective layer is referred to as an encapsulated electrode and has the consequence that the lithium electrode in contact with fluids, for example

Nitrogen, not degraded immediately. However, as a rule, there will not be sufficient barrier effect of the protective layer under normal atmospheric conditions, since lithium-ion conductive glasses, one for technical

Applications have sufficient conductivity, usually themselves are very vulnerable to

Degradation reactions with, for example, water or

Oxygen.

No. 6,387,563 B1 describes a protective layer for a thin-film battery, the protective layer consisting of an epoxy-based system and a glass layer. The epoxide layer acts as an adhesive layer for the

subsequently applied glass layer, which usually consists of a thin glass sheet. The epoxy layer can be cured through the glass layer. By using the initially plastic

Epoxy resin can thereby the formation of "gas pockets" in the battery and thus their reactions with the

Battery materials are largely avoided.

The disadvantage, however, is that in turn there is a direct contact with initially liquid material, which, although to a lesser extent than the more reactive fluids such as O ₂ or H ₂ O, may also lead to degradation of the battery materials. A very similar embodiment of an encapsulated

Battery describes the US 2013/0098532 AI. In addition, a heating of the substrate can take place here. The

Encapsulation consists of an organic compound onto which a "cap" or a superstrate is applied, leaving a gap in the battery, or that

Organic encapsulant material may also be applied so as to completely encase the layered structure of the thin film battery.

The US 2013/0260230 AI describes a method for

Making a Matterie on a Substrate. Here, too, it is described that the substrate can be baked out. Furthermore, an encapsulation around the structures of

Battery applied around; a superstrate is attached to the overall assembly using the organic encapsulant and completes it.

Furthermore, WO 2014/062676 Al describes the use of a glass substrate which has a thermal

Expansion coefficient of 7 to 10 ppm / K has.

Statements about the fluid content of this glass substrate or about its permeation properties are not made.

The document describes for sealing the battery rather different layers, in particular

Protective layers of metal, which rest on the layer structures.

US 2012/040211 A describes a glass film which can serve as a substrate for a lithium-ion battery.

This glass film has a water permeation rate of less than 1 g / m ² -d and an oxygen permeation rate of less than 1 cc / m ² -d. However, such a value is still extremely high and is more in the

Size of conventional polymers for encapsulation. Furthermore, no statement is made about the fluid content of the glass film.

The prior art thus shows a variety

various ways to avoid the degradation of a thin-film battery or a -akkumulator, especially for a lithium-based thin-film battery or accumulator. All mentioned approaches show certain advantages, but on the other hand, they take on considerable disadvantages, such as complex additional costs

Process steps in the form of tempering or

insufficient barrier effects due to the use of polymers for encapsulation or the risk of

Delamination connected by barrier layer. There is therefore a need for a material which is readily available for the manufacture of thin-film batteries, in particular lithium-based thin-film batteries, with increased

Lifespan can be used.

OBJECT OF THE INVENTION The object of the invention is to provide a thin-film battery with an increased service life and a low content of fluids, in particular of corrosive and / or degradative fluids. Another aspect of the invention relates to the provision of a

Low-fluid-content substrate material and a process for producing a low-fluid-content thin-film battery with increased life. Summary of the invention

The invention is achieved by a thin-film battery according to claim 1, an inorganic, silicon-containing,

in particular silicate, substantially fluid-free material according to claim 22 and a method for

Production of a low-fluid-content, extended-life thin-film battery according to claim 35. Preferred

Embodiments are found in the respective

Subclaims.

In the context of the present invention, the

As used herein, the thin film battery of the present invention is a rechargeable battery.

The thin film battery of the present invention is

in particular a lithium-based thin-film battery. Such thin film batteries typically include a substrate on which different ones in a particular sequence

Functional layers, such as Abieiter for cathode and anode, a cathode layer, an electrolyte and optionally an anode are applied as well as other layers, for example, for encapsulation of the battery to protect against degradation due to environmental influences. Such a construction of a battery is described by way of example in US 2004/0018424 Al, wherein the exact design of the battery may differ depending on the type and manufacturer. The thin-film battery, particularly the lithium-based thin film battery, of the present invention has a long life, and the life of such a battery can be specified in a variety of ways.

For example, for a rechargeable

Thin-film battery the so-called cycle stability of particular importance. With the cycle life is meant the number of feasible charging and discharging processes that are appropriate for a battery

Use, thus avoiding so-called

Deep discharges o. Ä. Are possible without causing a failure of the battery. A failure of the battery consists in the fact that the battery can no longer be supplied or removed energy or that the

Storage capacity of the battery to less than 80% of

original storage capacity has dropped. One cycle includes one charge and one charge each

Discharging.

Furthermore, the possibility of storage of the

Battery under environmental or "normal

Atmosphere ", i.e. uncontrolled temperature and

Humidity, of importance. Due to their small spatial extent, thin-film batteries can also be used in subcutaneous applications.

In addition to the storage and the cycle life of a

Thin-film battery is also the so-called

Continuous operational strength of importance. This means the time in which a battery can actually be actively taken or supplied energy.

The thin film battery of the present invention has an increased life such that at least one of the following features is satisfied:

Its cycle stability is at least 5000 cycles, preferably at least 10,000 cycles and more preferably at least 15,000 cycles,

Under normal, i. uncontrolled,

In particular, it can not be stored for at least 1 year, preferably for at least 2 years and more preferably for at least 5 years, in particular not in a controlled environment with respect to temperature and / or humidity, or it has a continuous operating stability of at least

5000 h preferably at least 10,000 h.

Furthermore, the thin-film battery of the present

Invention on a low content of fluids. In the context of the present invention, fluids are liquids and / or gaseous substances and also their chemical or physical adsorbates and / or their derivatives. A derivative in the present invention is understood to be a compound of a fluid which is present in solid form but can easily be converted back into a fluid form, for example by the addition of heat and the resulting decomposition of the fluid

Derivative. By way of example, fluid here means water in liquid form or as water vapor, or else its presence as chemically or physically bound surface water in Form of an adsorbate or its occurrence as, for example, water of crystallization in solid form in one

Structure as derivative in the sense of this invention. In an analogous manner CO ₂ can be present in gaseous or adsorbed form,

in particular adsorbed on LiOH, or else in the form of a carbonate.

The total content of the thin film battery of the present invention is 2000 ppm or less, preferably 500 ppm or less, and more preferably 200 ppm or less, and more preferably 50 ppm or less, based on the weight of the thin film battery. A thing,

For example, a thin-film battery, or a material having such a low fluid content is referred to in the present invention as substantially fluid-free.

Moreover, the thin-film battery of the present invention has at least one element made of an inorganic, silicon-containing, in particular

silicate, substantially fluid-free material

consists .

According to one embodiment of the invention, the fluids H ₂ O, O ₂ , N ₂ , CO ₂ and / or hydrogen halides and / or their chemical and / or physical adsorbates and / or derivatives.

According to a further embodiment of the invention, the inorganic, silicon-containing, in particular

silicate, substantially fluid-free material a fluid content, in particular an H ₂ <0 content, of less than 2 wt .-%, preferably less than 0.5 wt .-% and

more preferably less than 0.2 wt .-% and most preferably less than 0.05 wt .-%, wherein the fluid content and within the chemical structure of the material bound fluid substances, for example in the form of water of crystallization or hydrates or Count OH groups.

The fluid content of the inorganic, silicon-containing, in particular silicate, substantially fluid-free material is determined by thermal analysis, for example by a differential thermal analysis or a thermogravimetry or a dynamic

Differential calorimetry. In a further embodiment of the invention, the thin-film battery furthermore has at least one encapsulation, wherein the encapsulation at least partially seals at least one interface of at least one functional layer of the thin-film battery. It is under a

Functional layer of the battery understood a layer which is active in the loading and unloading for

electrical energy is involved in the battery,

For example, as a cathode, anode or in the form of an electron or ion-conducting function.

The at least one encapsulation is preferably at least partially in the form of the inorganic,

siliceous, in particular silicate, im

Substantially fluid-free material is formed.

However, the encapsulation may also be at least partially in the form of an organic and / or semi-organic Material, for example, be formed as a hybrid material of a SiC> 2 gel with functional organic groups. In this case, the inorganic, silicon-containing, in particular silicate, essentially fluid-free material of the present invention has a permeation rate for fluids, especially for water, of <10 ^-3 g / (m ² -d), preferably of <10 ^-5 g / (m ² -d) and more preferably of <10 ^{~ 6} g / (m ² -d).

In a further embodiment of the invention, the inorganic, silicon-containing, in particular silicate, substantially fluid-free material of the present invention

Invention further has a specific electrical resistance at a temperature of 350 ° C and a

Alternating current with a frequency of 50 Hz of greater than 1.0 -10 ⁶ ohm-cm. The inorganic, silicon-containing, in particular

Siliceous, substantially fluid-free material of the present invention is preferably characterized by a maximum load temperature 9 _Max of at least

300 ° C, preferably of at least 400 ° C, more preferably of at least 500 ° C and most preferably of at least 600 ° C. The maximum load temperature is the temperature at which the

Functionality of the material, for example in the form of its mechanical stability, is still fully guaranteed, or in which no significant conversion reactions have taken place. The maximum load temperature can be used for a connection Temperature at which it becomes significant

Decomposition of the material, for example by decomposition into several, including gaseous, components, or its melting or softening temperature. Unless it is a

glassy material is considered maximum

Load temperature thereby usually T _{g are} assumed. The so-called transformation or

Glass transition temperature T _g is determined by the intersection of the tangents to the two branches of

Expansion curve during the measurement with a heating rate of

5K / min. This corresponds to a measurement according to ISO 7884-8 or DIN 52324.

Invention a linear thermal

Expansion coefficient in the range of 2.0 x 10 ^-6 / Κ to 10 x 10 ^"6 / Κ, preferably of 2.5 ^{10" 6} / K to 9.5 10 ^"6 / K and particularly preferably from 3.0 x 10 ^-6 / Κ to 9.5 x 10 ^-6 / Κ on. Here, the linear thermal expansion coefficient, unless otherwise specified, is meant in the range of 20-300 ° C. the terms and 0 (20-300 are within the scope of this The value given is the nominal mean thermal

Coefficient of linear expansion according to ISO 7991, which is determined in static measurement.

The inorganic, silicon-containing, in particular

Silicate-like, substantially fluid-free material of the present invention preferably contains network formers and separation site formers, the molar ratio of separation site formers to network formers is less than or equal to 0.25, preferably less than or equal to 0.2 and particularly preferably between 0.015 and 0.16. In this case, network elements are elements which form coordination polyhedra with oxygen, these being

Coordination polyhedra interconnect and large, possibly even infinite macromolecules

can join together. In contrast, elements which interrupt the connections between the individual coordination polyhedra and thus lead to a reduction in the degree of polymerization are referred to as separation site formers. As Trennstellenbildner act thereby

For example, alkali and / or alkaline earth metals, as network formers are exemplified aluminum and / or boron and / or silicon into consideration.

The inorganic, silicon-containing, in particular

Silicate, substantially fluid-free material of the present invention preferably has in its structure a network of corner-sharing structural

Building units, made up of the

Oxygen coordination polyhedrons nerwerkwerkbildender

Elements, in particular a network corner-connected

Tetrahedra of the general formula [XO ₄ ], wherein X comprises at least silicon and / or aluminum.

Precisely because of the large number of possible connections of the coordination polyhedra, the structure of the solid formed in this way is relatively large

Cavities responsible for the storage of, for example

Fluids are suitable. For example, mica or phyllosilicates generally in their crystalline Structure on the one layers, in which the coordination polyhedron, in this case of oxygen tetrahedral coordinated silicon, in the form of

Hexagonal rings are arranged in the middle fluids can be stored. Furthermore, between the layers of the layered silicates further compounds

be stored. This great receptivity of

Phyllosilicates are also referred to as swellability and often exploited technically, for example, by targeted organic groups are added, but then represents a disadvantage when freedom from fluid is required.

However, other, denser silicon-containing, in particular silicate materials, for example silicates with a garnet structure, have in their structure preferred directions, which may show, for example, macroscopically as cleavage or in the form of a preferred permeability for certain materials. Thus, in the case of garnet structures, it is known that these channels have, by - in the case of a suitable chemical

Composition - for example, ions can migrate. This is in the case of so-called "LLZO" materials

exploited, these being materials which include lithium, lanthanum, zirconium and oxygen

are constructed (wherein a part of the zirconium may also be replaced by niobium or tantalum or similar elements) and have a particularly high lithium-ion conductivity.

To such preferential directions with the associated

To avoid the risk of permeability and / or storage capacity for fluids is according to a preferred

Embodiment of the invention isotropic. When isotropic, a material is then called, if its

Properties are formed in all directions towards the same. In a preferred embodiment this is

inorganic, silicon-containing,

in particular silicate, substantially fluid-free

Material formed amorphous. It is preferably a glass.

According to a further embodiment of the invention, inorganic, silicon-containing, in particular silicate, essentially fluid-free material can be present as substrate and / or as superstrate in the thin-film battery according to the invention.

Here, as a "substrate" the pad for the

subsequent constructions that the actual

Thin-film battery form, and as a Superstrat a cover, which, for example, on the finished coatings of the thin-film battery

is applied. As Superstrat is doing in the context of the present

Invention understood the inorganic, silicon-containing, in particular silicate, substantially fluid-free material then, if it is not used as a substrate, so as a base for the application of other finishes or structures, but as Auflagerndes element,

For example, cover or as a cover glass, is used. The Superstrat can also do that before his own Use as a superstrate, for example, as a cover glass, have been subjected to separate processes, during which it has the function of a substrate for these separate

Processes has taken, and wear, for example, structures or structures, such as optical coatings for selectively adjusting the optical transmission.

In the context of the present invention, the superstrate can be formed from the same material, that is to say with the same chemical composition, as the latter

Substrate. This is advantageous, for example, if the substrate and superstrate are as far as possible the same thermal in order to avoid thermal stresses

Expansion coefficients should have.

However, it is also possible that substrate and

Superstrat deliberately made of different materials. If, for example, the superstrate is merely used as a diffusion barrier with respect to the passage of fluids, ie, for example, optical or

chemical properties are of secondary importance, it is possible to have a rather inexpensive material,

For example, a glass with higher thicknesses, with the

Composition of a soda-lime glass as well as without

separate, for example, optical, compensation, too

use.

To ensure a sufficient diffusion barrier against the passage of fluids, an encapsulation between the substrate and the superstrate is still required. Such a lateral barrier can

for example, by suitable polymers. Farther it is also possible to create such a barrier by the use of glass solders, especially if a particularly high diffusion barrier is necessary or

is desirable. Furthermore, it is also possible to selectively adjust such glass solders with regard to their thermal expansion. If, for example, the

Expansion coefficients of substrate and superstrate are different, can be a thermal

Expansion coefficient of the glass solder are chosen so that it assumes an average value. Furthermore, the

coefficient of thermal expansion of the glass solder usually on the active components of the relevant

Store memory element. Preference is given to both the substrate and the

Superstrate of the same inorganic, silicon-containing, in particular silicate, substantially fluid-free material formed. If the inorganic, silicon-containing, in particular silicate material of the present invention is used in the thin-film battery according to the invention as a substrate and / or as a superstrate, it is according to a

Embodiment of the invention obtained by a

Melting process followed by shaping, wherein the material is preferably formed as a band or disc, for example as a glass band or glass pane, and wherein the shaping is inline as a hot forming process,

for example, in a float process, an overflow fusion process, or a downdraw process, or offline by separately heating a previously cooled vitreous body in a re-draw process. However, it is also possible for the inorganic, silicon-containing, in particular silicate, substantially fluid-free material of the thin-film battery according to the invention to be present as an alternative or additionally as a layer.

According to a preferred embodiment of the invention, the material, if it is present as a layer, by a vapor deposition, preferably by a

Electron beam evaporation process, obtained.

According to a further embodiment of the invention, the thin-film battery according to the invention further comprises at least one fluid getter. A getter is a material that can bind fluid.

Preferably, this getter is designed as

Reaction and / or sacrificial material which forms insoluble or only sparingly soluble compounds with fluids.

In a further embodiment of the invention, this getter comprises a metal, for example a non-noble metal, preferably an alkali metal or alkaline earth metal or a mixture or alloy of metals, for example

Alkali and / or alkaline earth metals, and / or an adsorbent. As an adsorbent while a material is referred to, which is capable of binding adsorptive fluids. Although fluid getters for electrochemical energy storage are not fundamentally new. For example, international patent application WO 2014/016039 A1 describes a Compound VI which is capable of having one

fluorine-containing compound V2 to form a nonvolatile, non-gaseous and fluorine-binding compound V3. Also, the US patent application US 2012/0050942 Al describes a material which is capable of binding HF or hydrogen.

Both fonts have in common that they turn off on lithium-based systems that have a liquid electrolyte, i. one which consists of a solvent and a conductive salt. If water or hydrogen in the

Energy storage, now forms hydrogen fluoride HF, which, for example, to inflate the battery, in the worst case to mechanical failure of the

Battery cover, associated with the escape of hazardous substances, may result. Furthermore, non-soluble lithium compounds, such as LiF, may continue to form, depriving the system of the element essential to electrical energy storage.

In contrast to these HF and / or hydrogen getters, on the other hand, the getter materials of the present invention are rather formed such that other fluids, for example, in addition to water, also oxygen and / or nitrogen,

adsorbed. The ones described above

Getter materials effective mechanisms can still be effective in a pure solid-state battery, which is an object of the present invention. Rather, here are missing important components, which for the course of the necessary in the prior art reactions are necessary. In particular, fluorine is in such

Solid state battery is not available, so that an RF gettering is not displayed.

According to a preferred embodiment of the invention, the inorganic, silicon-containing, in particular

siliceous, substantially fluid-free material of the present invention has a thickness less than 2 mm,

preferably less than 1 mm, particularly preferably less than 500 μm, very particularly preferably less than or equal to 200 μm and most preferably not more than 100 μm.

In a particularly preferred embodiment of the

Invention comprises the inorganic, silicon-containing,

in particular silicate, essentially fluid-free

Material has a certain content of lithium. This is particularly advantageous when it comes to the

thin-film battery according to the invention is a lithium-based thin-film battery. If one of the measures for generating the fluid freedom of the material is carried out, i. For example, an annealing, and this only after the application of functional layers takes place, for example, during the annealing of a

Functional layer, so that these increased performance, for example, in terms of storage capacity

having electrical energy, such a lithium content is particularly advantageous. The Li ₂ O content is 7.0% by weight or less, preferably 5.2% by weight or less, and especially

preferably at 2.5% by weight or less, especially preferably at 0.5% by weight or less, and most preferably at 0.2% by weight or less, wherein

Content of L1 ₂ O at least 0.1 wt .-%, the thin film battery of the invention can be prepared by a process comprising at least the

following steps include:

The provision of a substrate with a

Fluid content, in particular a H ₂ 0 content, of less than 2 wt .-%, preferably less than 0.5

Wt .-% and particularly preferably less than 0.2 wt .-% and most preferably less than 0.05 wt .-%, wherein the fluid content and within the chemical structure of the material bound fluid substances, for example in the form from

Crystal water or hydrates or OH groups, count,

Applying the functional layers of

Thin film battery, as well

Applying at least one encapsulation of the

Functional layers of the thin-film battery, wherein the

Encapsulation at least partially at least partially

Boundary surface of at least one functional layer of the thin-film battery seals. In a further embodiment of the invention, the substrate and / or at least one encapsulation of the thin-film battery is at least partially in the form of an inorganic, silicon-containing, in particular silicate, im

Substantially fluid-free material is formed.

In a preferred embodiment of the invention is the inorganic, silicon-containing, in particular silicate, substantially fluid-free material as a substrate in the form of a disc-shaped molding, wherein the substrate for generating the fluid freedom during or after the molding of a heat treatment, in particular a heat treatment at below 500 ° C, and / or flame treatment is subjected, wherein the Annealing preferably during the thermal treatment of at least one of

Functional layers of the thin-film battery takes place. In a further embodiment of the invention, furthermore, a getter material for fluids, for example a getter material in the form of a metal, preferably a base metal, for example an alkali or

Alkaline earth metal and / or mixtures and alloys of metals is formed, or a getter material in the form of an adsorbent, applied to the substrate.

In a further embodiment of the invention, the getter is doing before the implementation of the

fluid-reducing process, so for example, before annealing, applied, and removes the getter after its implementation.

Examples

In the following tables are some exemplary

Compositions of inorganic, silicon-containing,

in particular silicate, essentially fluid-free materials.

Embodiment 1 A composition of an inorganic, silicon-containing, in particular silicate, essentially fluid-free material is furthermore given by way of example by the following composition in% by weight:

Si0 ₂ 30 to 85

B ₂ 0 ₃ 3 to 20

AI2O3 0 to 15

Na ₂ 0 3 to 15

K ₂ 0 3 to 15

ZnO 0 to 12

Ti0 ₂ 0.5 to 10

CaO 0 to 0, 1 embodiment 2

Another composition of an inorganic,

siliceous, in particular silicate, im

Substantially fluid-free material is still

exemplified by the following composition in wt .-%:

Si0 ₂ 58 to 65

B ₂ 0 ₃ 6 to 10.5

A1 ₂ 0 ₃ 14 to 25

MgO 0 to 3

CaO 0 to 9

BaO 0 to 8, preferably 3 to 8

ZnO 0 to 2,

it being understood that the sum of the content of MgO, CaO and BaO is characterized by being in the range of 8 to 18% by weight. Embodiment 3

Yet another composition of an inorganic, silicon-containing, in particular silicate, im

Substantially fluid-free material is still

exemplified by the following composition in

Gew. -%:

Si0 ₂ 55 to 75

Na ₂ 0 0 to 15

K ₂ 0 0 to 14, preferably 2 to 14

A1 ₂ 0 ₃ 0 to 15

MgO 0 to 4

CaO 3 to 12

BaO 0 to 15

ZnO 0 to 5

Ti0 ₂ 0 to 2

Embodiment 4

Substantially fluid-free material is still

exemplified by the following composition in wt. -%: Si0 ₂ 61

B ₂ 0 ₃ 10

A1 ₂ 0 ₃ 18

MgO 2, 8

CaO 4.8

BaO 3.3 With this composition, the following properties are obtained:

«(20-300) 3, 2 · 10 ^{" 6} / Κ

T _g 717 ° C

Density 2.43 g / cm 3

Embodiment 5

Substantially fluid-free material is still

exemplified by the following composition in

Si0 ₂ 64, 0

B ₂ 0 ₃ 8,3

A1 ₂ 0 ₃ 4.0

Na ₂ 0 6, 5

K ₂ 0 7.0

ZnO 5.5

Ti0 ₂ 4.0

Sb ₂ 0 ₃ 0, 6

Cl ^~ 0.1

With this composition, the following properties are obtained:

a ₍₂ o-3oo) 7.2 · 10 ^"6 / Κ

T _g 557 ° C

Density 2.5 g / cm 3 Embodiment 6

Another disk-shaped discrete element is exemplified by the following composition in weight:

Si0 ₂ 69 +/- 5

Na ₂ 0 8 +/- 2

K ₂ 0 8 +/- 2

CaO 7 +/- 2

BaO 2 +/- 2

ZnO 4 +/- 2

Ti0 ₂ 1 +/- 1

With this composition, the following properties are obtained:

a ₍₂ o-3oo) 9.4 · 10 ^"6 / Κ

T _g 533 ° C

Density 2.55 g / cm 3

Embodiment 7

Substantially fluid-free material is still

exemplified by the following composition in

Si0 ₂ 80 +/-

B ₂ 0 ₃ 13 +/-

A1 ₂ 0 ₃ 2.5 +/-

Na ₂ 0 3.5 +/-

K ₂ 0 1 +/- 1 With this composition, the following properties

Elements received:

«(20-300) 3, 25 · 10 ^{" 6} / Κ

T _g 525 ° C

Density 2.2 g / cm ³

Embodiment 8

Substantially fluid-free material is still

exemplified by the following composition in

Si0 ₂ 62.3

A1 ₂ 0 ₃ 16.7

Na ₂ 0 11.8

K ₂ 0 3.8

MgO 3, 7

Zr0 ₂ 0.1

Ce0 ₂ 0.1

Ti0 ₂ 0.8

As ₂ 0 ₃ 0.7

With this composition, the following properties are obtained:

«(20-300) 8, 6 · 10 ^{" 6} / Κ

T _g 607 ° C

Density 2.4 g / cm ³

Embodiment 9 Yet another composition of an inorganic, silicon-containing, in particular silicate, im

Substantially fluid-free material is still

exemplified by the following composition in wt .-%:

Si0 ₂ 62.2

A1 ₂ 0 ₃ 18,1

B2O3 0.2

P2O5 0.1

Li ₂ 0 5.2

Na ₂ 0 9.7

K ₂ 0 0.1

CaO 0.6

SrO 0.1

ZnO 0.1

Zr0 ₂ 3.6

With this composition, the following properties are obtained:

«(20-300) 8, 5 · 10 ^{" 6} / Κ

T _g 505 ° C

Density 2.5 g / cm ³ Embodiment 10

Substantially fluid-free material is still

exemplified by the following composition in wt .-%:

Si0 ₂ 52 A1 ₂ 0 ₃ 17

Na ₂ 0 12

K ₂ 0 4

MgO 4

CaO 6

ZnO 3,5

Zr0 ₂ 1.5

With this composition, the following properties are obtained:

«(20-300) 9, 7 · 10 ^{" 6} / Κ

T _g 556 ° C

Density 2.6 g / cm ³

Embodiment 11

Substantially fluid-free material is still

exemplified by the following composition in wt. -%:

Si0 ₂ 62

AI2O3 17

Na ₂ 0 13

K ₂ 0 3.5

MgO 3, 5

CaO 0.3

Sn0 ₂ 0.1

Ti0 ₂ 0.6 With this composition, the following properties are obtained:

«(20-300) 8, 3 · 10 ^{" 6} / Κ

T _g 623 ° C

Density 2.4 g / cm 3

Embodiment 12

Substantially fluid-free material is still

exemplified by the following composition in wt. -%:

Si0 ₂ 61,1

A1 ₂ 0 ₃ 19.6

B ₂ 0 ₃ 4,5

Na ₂ 0 12,1

K ₂ 0 0.9

MgO 1, 2

CaO 0.1

Sn0 ₂ 0.2

Ce0 ₂ 0.3

With this composition, the following properties are obtained:

«(20-300) 8, 9 · 10 ^{" 6} / Κ

T _g 600 ° C

Density 2.4 g / cm ³

Embodiment 13 Yet another composition of an inorganic, silicon-containing, in particular silicate, im

Substantially fluid-free material is still

exemplified by the following composition in wt .-%:

Si0 ₂ 50 to 65

A1 ₂ 0 ₃ 15 to 20

B ₂ 0 ₃ 0 to 6

Li ₂ 0 0 to 6

Na ₂ 0 8 to 15

K ₂ 0 0 to 5

MgO 0 to 5

CaO 0 to 7, preferably 0 to 1

ZnO 0 to 4, preferably 0 to 1

Zr0 ₂ 0 to 4

Ti0 ₂ 0 to 1, preferably essentially Ti0 ₂ -free

Further, in the glass may be contained at 0 to 1 wt .-%: P ₂ 0 ₅ , SrO, BaO; and a refining agent 0 to 1 wt .-% Sn0 _2, Ce0 ₂ or As ₂ C> 3 or other refining agents.

Embodiment 14

Substantially fluid-free material is still

exemplified by the following composition in

Si0 ₂ 58 to 65

B ₂ 0 ₃ 6 to 10.5

A1 ₂ 0 ₃ 14 to 25 MgO to 5

CaO to 9

BaO to 8

SrO to 8

ZnO to 2

Embodiment 15

Substantially fluid-free material is still

exemplified by the following composition in

Gew. -%:

Si0 ₂ 59, 7

A1 ₂ 0 ₃ 17, 1

B ₂ 0 ₃ 7,8

MgO 3,4

CaO 4.2

SrO 7,7

BaO 0.1

With this composition, the following characteristics are obtained: ₍₂₀ -3oo) 3.8 x 10 ^"6 / Κ

T _g 719 ° C

Density 2.51 g / cm ³

Embodiment 16

Substantially fluid-free material is still exemplified by the following composition in wt. -%:

Si0 ₂ 59.6

A1 ₂ 0 ₃ 15,1

B2O3 9.7

CaO 5.4

SrO 6.0

BaO 2,3

ZnO 0.5

Sb ₂ 0 ₃ 0.4

AS2O3 0.7

With this composition, the following properties are obtained:

«(20-300) 3, 8 · 10 ^{" 6} / Κ

Density 2.5 g / cm ³

Embodiment 17

Substantially fluid-free material is still

exemplified by the following composition in

Gew. -%:

Si0 ₂ 58.8

AI2O3 14, 6

B ₂ 0 ₃ 10.3

MgO 1,2

CaO 4.7

SrO 3, 8

BaO 5.7

Sb ₂ 0 ₃ 0.2 As ₂ 0 ₃ 0.7

With this composition, the following properties are obtained:

«(20-300) 3, 73 · 10 ^{" 6} / Κ

T _g 705 ° C

Density 2.49 g / cm ³

Embodiment 18

Substantially fluid-free material is still

exemplified by the following composition in

Si0 ₂ 62.5

B ₂ 0 ₃ 10.3

AI2O3 17.5

MgO 1, 4

CaO 7.6

SrO 0.7

With this composition, the following properties are obtained element: oi ₍ 2o-3oo) 3.2 ppm / K

Density: 2.38 g / cc

Embodiment 19

Substantially fluid-free material is still exemplified by the following composition in

Gew. -%:

Si0 ₂ 55 to 75

Na ₂ 0 0 to 15

K ₂ 0 0 to 14

A1 ₂ 0 ₃ 0 to 15

MgO 0 to 4

CaO 3 to 12

BaO 0 to 15

ZnO 0 to 5

Embodiment 20

Substantially fluid-free material is still

exemplified by the following composition in wt. -%:

Si0 ₂ 74.3

Na ₂ 0 13.2

K ₂ 0 0.3

A1 ₂ 0 ₃ 1.3

MgO 0, 2

CaO 10.7 With this composition, the following properties are obtained:

Oi ₍₂₀ -3oo) 9, 0 ppm / K

Tg: 573 ° C

Embodiment 21 Yet another composition of an inorganic, silicon-containing, in particular silicate, im

Substantially fluid-free material is still

exemplified by the following composition in wt .-%:

Si0 ₂ 72.8

Na ₂ 0 13.9

K ₂ 0 0.1

A1 ₂ 0 ₃ 0.2

MgO 4, 0

CaO 9.0

With this composition, the following properties are obtained: oi ₍ 2o-3oo) 9.5 ppm / K

Tg: 564 ° C Embodiment 22

Si0 ₂ 60, 7

AI2O3 16, 9

Na ₂ 0 12.2

K ₂ 0 4.1

MgO 3, 9

Zr0 ₂ 1.5

Sn0 ₂ 0.4

Ce0 ₂ 0.3

Embodiment 23 Another composition of an inorganic,

siliceous, in particular silicate, im

Substantially fluid-free material is still

exemplified by the following composition in wt .-%:

Si0 ₂ 84.1

B ₂ 0 ₃ 11.0

R ₂ 0 3,3

AI2O3 0.5,

where R ₂ O means the sum of the alkali ions present in the material and further preferably comprises Na ₂ <0, Li ₂ <0 and K ₂ O. In all the above embodiments, may be included if not already listed, optionally refining agents to 0 to 1 wt .-%, such as Sn0 _2, Ce0 _2, As ₂ 0 _3, Cl ^~, F ^~, sulfates. Furthermore, it is possible that the inorganic,

silicon-containing, in particular silicate, substantially fluid-free material having a special, the strength of the material enhancing treatment was provided. If the material is a glass, such a treatment is in particular a prestress,

for example, a thermal and / or chemical

Bias, in particular a chemical bias.

The chemical bias of a glass is obtained by an ion exchange in a transfer bath. If a toughened glass is used, this is prior to the application of functional layers of an electrical Storage system characterized in that it has a chemical bias, which is characterized by a thickness of the ion-exchanged layer L _DO L of at least 10 ym, preferably at least 15 ym and on

most preferably at least 25 ym and one

Compressive stress at the surface (Oes) of the glass of preferably at least 100 MPa, preferably at least 200 MPa, more preferably at least 300 MPa and most preferably 480 MPa or more.

During the application and after-treatment of

Functional layers of an electrical storage system may, depending on the process, result in a change in the state of stress of the glass used as the substrate. It has surprisingly been found that the bias of

Glass is not set to zero, but rather a residual stress is maintained in the glass, so that

Overall, the strength of the substrate used

Glass is increased compared to a conventional, non-tempered glass.

The present in the final energy storage glass as a substrate may be characterized in that it is present as at least partially chemically tempered glass, wherein the at least partially chemical

Preload is obtained by an ion exchange in a transfer bath and a subsequent thermal

Stress and characterized by a thickness of the ion-exchanged layer (L _DO L) of at least 10 ym, preferably at least 15 ym and most preferably at least 25 ym and a compressive stress at the surface (Oes) of the glass of at least 100 MPa, preferably at least 200 MPa, more preferably at least 300 MPa and most preferably 480 MPa or more, wherein the thickness of the ion-exchanged layer before thermal stress is less than the thickness of the

ion-exchanged layer after thermal stress and the compressive stress on the surface of the glass before

thermal load is greater than the compressive stress on the glass surface after thermal stress. In one embodiment of the invention, the chemical

Pretension of the glass obtained in a barter in which lithium ions are contained. For example, a swap bath containing various alkali ions, e.g. Potassium and low to lowest levels of lithium. Also, a step-shaped process, e.g. Exchange with potassium and a quick further exchange with lithium-containing bath.

Furthermore, it is possible to listed

Embodiments to modify such that, if not already a content of Li ₂ 0 in the

Containing a significant, beyond the proportion of unavoidable traces beyond content of Li ₂ 0 included. Such a proportion is given from a content of Li ₂ 0 greater than or equal to 0.1 wt .-%.

The modification with the compositions of

disc-shaped discrete element can be such that any existing other alkali metal oxides are proportionally reduced in the composition of the disc-shaped discrete element, so that the content of the other components relative to the alkali metal oxides remains the same, or else the Li ₂ 0 is added additively to the other components, so that their proportion is reduced accordingly. Unless L1 ₂ O is contained in a disk-shaped discrete element, is its content at least 0.1 wt .-%, and is still smaller than 7.0 wt .-%, preferably less than 5.2 wt .-%, more preferably less as 2.5 wt .-%, most preferably less than 0.5 wt .-%, and most preferably less than 0.2 wt .-%, particularly preferably <0.1% by weight.

DESCRIPTION OF THE DRAWINGS FIG

Fig. 1 is a schematic representation of a

2 shows a schematic representation of a further thin film battery according to the invention

thin-film battery according to the invention, as well

Fig. 3 is a schematic representation of a

disc-shaped formation of a

inorganic,

silicon-containing, in particular silicate, substantially fluid-free material.

FIG. 1 schematically shows a thin-film battery 1 according to the present invention. It comprises a substrate 2, which consists of an inorganic,

siliceous, in particular silicate, im Substantially fluid-free material. Applied to the substrate is a sequence of different layers. By way of example and without limitation to the present example, the two drainage layers 3 for the cathode and 4 for the anode are first applied to the substrate 2. Such arrester layers are usually a few microns thick and consist of a metal, such as copper, platinum, aluminum or titanium. If the thin-film battery 1 is a lithium-based thin-film battery, the cathode is formed from a lithium transition metal compound, preferably an oxide, for example LiCoC> ₂ , from LiMnO ₂ or also from LiFePC. Furthermore, on the substrate and at least partially overlapping with the

Cathode layer 5, the electrolyte 6 is applied, this electrolyte is in the case of the presence of a lithium-based thin-film battery is usually LiPON, a compound as lithium with oxygen,

Phosphorus and nitrogen. Furthermore, the battery 1 comprises an anode 7, which may for example be lithium titanium oxide or even metallic lithium. The anode layer 7 at least partially overlaps that with the electrolyte layer 6 and the arrester layer 4. Furthermore, the battery 1 comprises an encapsulation layer 8.

At least the substrate 2 is in this case inorganic, silicon-containing, in particular silicate,

Substantially fluid-free material is formed, wherein as substantially fluid-free in the context of the present invention, a material is understood if it is less than 2 Wt .-%, preferably less than 0.5 wt .-% and especially less than 0.2 wt .-% fluids. Also the

Encapsulation layer 8 can be used as an inorganic, silicon-containing, in particular silicate,, im

Substantially fluid-free material may be formed.

As encapsulation or sealing of the thin-film battery 1 is in the context of the present invention, each

Material understood that the attack of fluids or other corrosive materials on the battery. 1

prevented or at least greatly reduced. Such encapsulation is characterized by the fact that

at least partially at least one interface of at least one functional layer of the thin-film battery of her

is sealed or sealed, for example, by being covered by the material.

In Fig. 2 is another embodiment of a

thin-film battery 1 according to the invention. Here, the structure of the thin-film battery 1 corresponds to

Essentially that of the thin film battery in Fig. 1, however, the encapsulation is formed differently. So here is the

Encapsulation layer 8 is formed such that it encloses the entire layer structure of the thin-film battery 1. On the encapsulation layer 8, a superstrate 9 is further arranged, which, for example, also from the inorganic, silicon-containing, in particular

silicate, substantially fluid-free material of the present invention may be formed. If the encapsulation layer 8 of an organic or

formed semi-organic material, the superstrate provides for an additional permeation barrier to fluids. Fig. 3 shows the schematic illustration of the inorganic, silicon-containing, in particular silicate, im

Substantially fluid-free material of the present

In the context of the present invention, a shaped body in the context of the present invention is then referred to as a disk-shaped or disk if its extent in a spatial direction is at most half as large as in the other two spatial directions. A tape in the present invention is referred to as tape when the following relationship exists between its length, its width and its thickness: its length is at least ten times greater than its width and this in turn is at least twice as large as its thickness.

Reference sign list

1 - thin film battery

2 - Substrate

3 - arrester layer for the cathode

4 - arrester layer for the anode

5 - cathode

6 - electrolyte

7 - anode

8 - encapsulation layer

9 - Superstrat

10 - disk-shaped molded body

Claims

Thin-film battery, especially lithium-based

Thin film battery, which has a long life

wherein the life is specified by at least one of the following characteristics:

- The thin-film battery has a cycle life of at least 5000 cycles, preferably from

at least 10,000 cycles and more preferably at least 15,000 cycles, one cycle comprising a discharge and a charge of the thin film battery and the cycle life the number of

Cycles, which at least for the

Thin-film battery can be performed without causing a failure,

- The thin-film battery can be stored under normal atmosphere for at least 1 year, preferably at least 2 years and more preferably at least 5 years, without causing a failure of the

Thin-film battery comes in such a way that electrical energy in the battery can no longer be stored or removed, and

- The thin-film battery has a

Continuous operating life of at least 5000 h, preferably of at least 10000 h, terming continuous operation time the time during which the battery is actively drawn or supplied with electrical energy,

and wherein the thin-film battery is still a

has low content of fluids, wherein as fluids liquid and / or gaseous substances and their chemical and physical adsorbates and / or their Derivatives, wherein the total content of these fluids is 2000 ppm or less, preferably 500 ppm or less, and more preferably 200 ppm or less and most preferably 50 ppm and less by weight of the thin film battery, and wherein the thin film battery further has at least one element which consists of an inorganic silicon-containing, in particular

silicate, substantially fluid-free material.

A thin film battery according to claim 1, wherein the fluids are H ₂ O, O ₂ , N ₂ , CO ₂ and / or hydrogen halides

and / or their chemical and / or physical

Adsorbates and / or derivatives include.

Thin-film battery according to one of claims 1 or 2, wherein the inorganic silicon-containing, in particular silicate, substantially fluid-free material, a fluid content, in particular a H ₂ 0 content, of less than 2 wt .-%, preferably less than 0.5 wt. -% and more preferably less than 0.2 wt .-% and most preferably less than 0.05 wt .-%, wherein the fluid content and within the chemical structure of the material bound fluid substances, for example in the form of water of crystallization or hydrates or OH groups.

A thin film battery according to any one of claims 1 to 3, wherein the thin film battery further comprises at least one encapsulant, the encapsulant

at least partially at least one interface at least one functional layer of the thin-film battery seals.

Thin-film battery according to claim 4, wherein the at least one encapsulation at least partially in the form of the inorganic, silicon-containing, in particular

silicate, substantially fluid-free material is formed.

Thin-film battery according to one of claims 4 or 5, wherein the at least one encapsulation at least partially in the form of an organic and / or

semi-organic material is formed.

A thin-film battery according to any one of claims 1 to 6, wherein the inorganic, silicon-containing, in particular silicate, substantially fluid-free material has a permeation rate for fluids of <10 ^-3 g / (m ² -d), preferably <10 ^-5 g / (m ² -d) and more preferably of <10 ^{~ 6} g / (m ² -d).

A thin-film battery according to any one of claims 1 to 7, wherein the inorganic, silicon-containing, in particular silicate, substantially fluid-free material further has an electrical resistivity at a temperature of 350 ° C and an alternating current with a frequency of 50 Hz greater than 1.0. 10 ⁶ ohmcm. Thin-film battery according to one of claims 1 to 8, wherein the inorganic silicon-containing, in particular silicate, substantially fluid-free material a maximum load temperature 9 _Max of at least 300 ° C, preferably of at least 400 ° C, more preferably of at least 500 ° C and most preferably of at least 600 ° C.

10 thin-film battery according to one of claims 1 to 9, wherein the inorganic silicon-containing, in particular silicate, substantially fluid-free material has a linear thermal expansion coefficient in the range of 2.0 x 10 ^-6 / Κ to 10 x 10 ^-6 / Κ, preferably from 2.5 10 ^-6 / K to 9.5 10 ^-6 / K and particularly preferably from 3.0 x 10 ^"6 / Κ to 9.5 x ^{10" 6} / Κ has.

11. Thin-film battery according to one of claims 1 to 10, wherein the inorganic, silicon-containing, in particular silicate, substantially fluid-free material contains network formers and separation point formers and wherein the molar ratio of

Separation point formers to network formers is less than or equal to 0.25, preferably less than or equal to 0.2 and particularly preferably between 0.015 and 0.16.

12. Thin-film battery according to one of claims 1 to 11, wherein the inorganic, silicon-containing, in particular silicate, substantially fluid-free material is formed isotropically.

13. Thin-film battery according to one of claims 1 to 12, wherein the inorganic, silicon-containing, in particular silicate, substantially fluid-free material is formed amorphous.

14. A thin film battery according to claim 13, wherein the

inorganic silicon-containing, in particular

silicate, substantially fluid-free material is a glass.

15. Thin-film battery according to one of claims 1 to 14, wherein the inorganic, silicon-containing, in particular silicate, substantially fluid-free material is present as a substrate and / or as a superstrate.

16. A thin film battery according to claim 15, wherein the

inorganic, silicon-containing, in particular

silicate, substantially fluid-free material by a melting process with subsequent

Shaping is obtained, wherein the material is preferably formed as a belt or disc and wherein the shaping inline as hot forming, for example in a float process, an overflow fusion process or a down-draw process, or offline by separately heating a previously cooled glassy Shaped body is done in a re-draw process.

Thin-film battery according to one of claims 1 to 14, wherein the inorganic, silicon-containing, in particular silicate, substantially fluid-free material is present as a layer.

A thin film battery according to claim 17, wherein said layer is obtained by a vapor deposition process, preferably by an electron beam evaporation process.

19. A thin film battery according to any one of claims 1 to 18, wherein the battery further comprises at least one getter for fluids. The thin-film battery according to claim 19, wherein the getter is formed as a reaction and / or sacrificial material which is insoluble or sparingly soluble

Compounds with fluids forms. 21. A thin film battery according to any one of claims 19 to 20, wherein the getter is a metal, for example a non-noble metal, preferably an alkali or

Alkaline earth metal or a mixture or alloy of metals, for example of alkali and / or

Alkaline earth metals, and / or an adsorbent.

22. Inorganic, silicon-containing, in particular

silicate, substantially fluid-free material for a thin film battery with increased life, said material having a fluid content, in particular a H ₂ 0 content, of less than 2 wt .-%, preferably less than 0.5 wt .-% and especially preferably less than 0.2% by weight and most preferably less than 0.05% by weight, wherein

Fluid content also within the chemical structure of the

Material-bound fluid substances, for example in the form of water of crystallization or hydrates or OH groups, count, and wherein the fluid content is determined by thermal analysis, in particular by a

Differential thermal analysis or thermogravimetry or differential scanning calorimetry, and wherein the material continues to network in its structure corner-sharing structural units formed from the oxygen coordination polyhedra

network-forming elements, in particular a network corner-connected tetrahedra of the general formula

[XO ₄ ], wherein X comprises at least silicon and / or aluminum, and wherein the material further contains in its structure elements acting as a separating agent, wherein the

Substance ratio of separation-forming elements to network-forming elements is less than or equal to 0.25, preferably less than or equal to 0.2 and more preferably between 0.015 and 0.16.

23. Inorganic, silicon-containing, in particular

A silicate, substantially fluid-free material according to claim 22, wherein the material is further formed isotropic.

24. Inorganic, silicon-containing, in particular

A silicate, substantially fluid-free material according to any of claims 22 or 23, wherein the internal structure of the material is three-dimensional

linked, dense network is designed such that a substantially random, not

remote-ordered linkage of the coordination polyhedron forming the material is present.

25. Inorganic, silicon-containing, in particular

silicate, substantially fluid-free material according to any one of claims 22 to 24, wherein the material has a Li ₂ 0 content of 7 wt .-% or less, preferably from 5.2 wt .-% or less, more preferably from Has 2.5 wt .-% or less, more preferably of 0.5 wt .-% or less, and most preferably of 0.2 wt .-% or less, wherein the content of L1 ₂ O at least 0.1 wt .-% and further wherein the Kontaktration of lithium over the cross-section of inorganic, silicon-containing, in particular

silicate, substantially fluid-free material can vary. 26. Inorganic, silicon-containing, in particular

silicate, substantially fluid-free material according to any one of claims 22 to 25, wherein the material has a permeation rate for fluids of <10 ^-3 g / (m ² -d), preferably of <10 ^{~ 5} g / (m ² -d) and most preferably <10 ^-6 g / (m ² d) comprises.

27. Inorganic, fluid-free, essentially

Fluid-free material according to one of claims 22 to 26, which has a maximum load temperature 9 _Max of at least 300 ° C, preferably of at least 400 ° C, more preferably of at least 500 ° C and most preferably of at least 600 ° C.

28. Inorganic, silicon-containing, in particular

A silicate, substantially fluid-free material according to any one of claims 22 to 27, wherein the material has a resistivity at a temperature of 350 ° C and an alternating current with a frequency of 50 Hz of greater than 1.0 -10 ⁶ ohmcm.

29. Inorganic, silicon-containing, in particular

silicate, substantially fluid-free material according to any one of claims 22 to 28, wherein the material has a linear thermal expansion coefficient in the range of 2.0 · 10 ^-6 / Κ to 10 · 10 ^-6 / Κ, preferably from

2.5 10 ^-6 / K to 9.5 10 ^-6 / K and particularly preferably from 3.0 x 10 ^"6 / Κ to 9.5 x ^{10" 6} / Κ comprising

30. Inorganic, silicon-containing, in particular

A silicate, substantially fluid-free material according to any one of claims 22 to 29, wherein the material is obtained by a melting process

subsequent hot forming, for example in a float process, a down-draw process or an overflow fusion process or combinations thereof

Process, or by heating and re-drawing a previously shaped molded body, wherein the material after completion of the molding process as a disk-shaped

Shaped body is present.

31. Inorganic, silicon-containing, in particular

A silicate, substantially fluid-free material according to any one of claims 22 to 30, wherein the material continues after or during molding

is formed fluid-reduced, wherein the

Fluid reduction is achieved in particular by a heat treatment at a maximum of 500 ° C and / or a flame treatment of the surfaces of the material.

Inorganic, silicon-containing, in particular

silicate, substantially fluid-free material according to any one of claims 22 to 31, wherein the material a thickness of less than 2 mm, preferably less than 1 mm, more preferably less than 500 ym, very particularly preferably less than or equal to 200 ym and most preferably not more than 100 ym.

33. Inorganic, silicon-containing, in particular

Silicate, substantially fluid-free material according to one of claims 22 to 29, wherein the material is present as a layer.

34. Inorganic, silicon-containing, in particular

The silicate, substantially fluid-free material according to claim 33, wherein the material is obtained by a vapor deposition process, preferably by an electron beam evaporation process.

35. Method for producing a thin-film battery

in particular a lithium-based thin-film battery with increased life, comprising at least the following steps:

Providing a substrate with a

Fluid content, in particular a H2 <0 content, of less than 2 wt .-%, preferably less than 0.5 wt .-% and particularly preferably less than 0.2 wt .-%, and most preferably less than 0.05 wt .-%, wherein the

Fluid content also within the chemical structure of the material bound fluid substances, for example in the form of water of crystallization or hydrates or OH groups, count,

Applying the functional layers of

Thin film battery, as well Applying at least one encapsulation of the functional layers of the thin-film battery, wherein the encapsulation at least partially at least one interface of at least one

Functional layer of the thin-film battery seals.

36. The method of claim 35, wherein the substrate

and / or at least one encapsulation of the

Thin film battery at least partially as

inorganic, silicon-containing, in particular

silicate, substantially fluid-free material is formed.

37. The method according to any one of claims 35 or 36, wherein the inorganic, silicon-containing, in particular silicate, substantially fluid-free material is present as a substrate in the form of a disc-shaped molding and wherein the substrate for generating the fluid freedom during or after the shaping of a heat treatment, in particular a Annealing at under

500 ° C, and / or is subjected to flame treatment, wherein the heat treatment is preferably carried out during the thermal aftertreatment of at least one of the functional layers of the thin-film battery.

38. The method according to any one of claims 35 to 37, further comprising a getter material for fluids,

For example, a getter in the form of a

Metal, preferably a base metal,

for example, an alkali or alkaline earth metal and / or mixtures and alloys of metals is formed, or a getter material in the form of an adsorbent, is applied to the substrate.

The method of claim 38, wherein the getter material is applied prior to performing the fluid reducing process, in particular prior to annealing, and wherein the getter material is removed after performing the fluid reducing process.