CN107534097A

CN107534097A - Electric storage system, plate shape discrete component, its manufacture method and its application with plate shape discrete component

Info

Publication number: CN107534097A
Application number: CN201580065279.4A
Authority: CN
Inventors: M·孔泽; U·普切尔特; N·舒尔茨; T·达姆; C·欧特曼
Original assignee: Schott AG
Current assignee: Schott AG
Priority date: 2014-12-01
Filing date: 2015-11-26
Publication date: 2018-01-02

Abstract

The present invention relates to the electric storage system that a kind of thickness is less than 2mm, it includes at least one plate shape discrete component, wherein, the plate shape discrete component has high to the ion of alkali metal or alkali metal, the tolerance of the especially erosion of lithium, wherein, the plate shape discrete component has relatively low TiO₂Content, wherein, preferably smaller than 2 weight % TiO₂Content, preferably smaller than 0.5 weight % TiO₂Content and preferably without TiO₂。

Description

Electric storage system, plate shape discrete component, its manufacture method with plate shape discrete component And its application

Technical field

The present invention relates to the electric storage system with plate shape discrete component, plate shape discrete component, its manufacture method and its answer With.

Background technology

For a long time, electric storage system is known that it especially includes battery, but is also included with high-energy-density Capacitor, it is also referred to as ultracapacitor.Especially so-called lithium ion battery due to high energy density can be realized by it, Therefore its application in emerging field as such as electric automobile was discussed, but also applied for example in recent years Discussion in portable set as smart phone or notebook computer.On the other hand, the lithium of this traditional repeatable charging from The principal character of sub- battery especially, uses the organically liquid electrolyte based on solvent.But the liquid electrolyte is flammable, and And therefore cause potential safety hazard when unrestrictedly using the lithium ion battery.A kind of possibility is taken with solid electrolyte For organic bath.But the conductibility of this solid electrolyte is generally significantly lower than corresponding liquid electrolyte, i.e. compares phase The low multiple orders of magnitude of liquid electrolyte answered.But in order to obtain acceptable conductibility and repeatable fill can be utilized The advantages of lithium ion battery of electricity, current this solid state battery are especially manufactured into so-called hull cell (TFB) or film storage Element versions.It is especially applied in mobile field, such as so-called smart card, medical technology and sensing technology and smart phone With other movable applications for requiring intelligent, miniaturization, the even flexible energy.

US2008/0001577 describes a kind of exemplary thin film memory element of lithium base, and it is generally by substrate structure Into in first coating step, being applied on substrate and be applied to the conductive colelctor electrodes of two electrodes.Then further manufacturing During, cathode material is deposited on the colelctor electrode for negative electrode (being usually lithium and cobalt oxides LCO) first.In next step In, solid electrolyte is deposited, it is typically the amorphous materials being made up of lithium, oxygen, nitrogen and phosphorus and turns into LiPON.Next Deposition anode material in step so that it is combined with substrate, the colelctor electrode for anode and solid electrolyte.As anode Material especially uses lithium metal.If two colelctor electrodes are conductively connected, lithium ion is led by solid ion in the energized state Body is vacillated from anode towards negative electrode, and this is conductively connected the electric current caused from cathode to anode by two colelctor electrodes.Conversely, not In the state of powered, by applying external voltage ion can be forced to be vacillated from negative electrode towards anode, thus battery is charged.

US2001/0032666A1 for example describes another thin film memory element, and it equally includes substrate, in substrate The different functional layer of upper deposition.

For this thin film memory element deposition the common thickness of layer in the scope less than or equal to 20 μm, typically smaller than 10 μm, be even less than 5 μm；On the other hand, the gross thickness of Rotating fields can be 100 μm or smaller.

In the framework of this application, thin film memory element for example refer to the lithium base of repeatable charging thin film memory element and Ultracapacitor；But the present invention is not limited only to this system, but be also applicable in other thin film memory elements, Such as repeatable charging and/or in printing film battery.

Thin film memory element is generally manufactured by the coating process of complexity herein, the coating process also includes to each material The structuring deposition of material.On the other hand, extremely complex structuring may be carried out to specific thin film memory element, such as can be from the U.S. Learned in patent US7494742B2.In addition, in by using thin film memory element of the lithium metal as the lithium base of anode material Because the very strong reactivity of lithium metal can cause special difficulty.It is thus necessary to handle metal under the conditions of as anhydrous as possible Lithium, because otherwise it can be reacted to lithium hydroxide and lose the function as anode.The thin film memory element of lithium base also must It must be protected accordingly by encapsulation, to prevent influence of moisture.

US7494742B2 is described for unstable part (such as lithium or the lithium of determination to thin film memory element Compound) this encapsulation protected.Existed by coating or the system with different coating come execute encapsulation function, the coating Other functions can also be met in the total of battery.

In addition, for example described in document US2010/0104942A1, in the manufacturing condition of the thin film memory element of lithium base Under, especially for formed suitable for the crystal structure of lithium Insertion action necessary to it is so-called anneal or tempering step can go out It is existing, mobile lithium ion and substrate undesirably side effect, because lithium has higher mobility and in common material It is easy to spread.

Another problem of thin film memory element is the baseplate material used.Prior art describes a variety of different substrates Material, such as silicon, mica, different metal and ceramic material.Also the application of glass is repeatedly referred to, but does not provide glass substantially The concrete composition or concrete property of glass.

US2001/0032666A1 describes a kind of accumulator of capacitor-like, and it may also be lithium ion battery.As base Plate material especially refers to semiconductor herein.

US6906436B2 describes a kind of solid state battery, and it for example can be used metallic film, semi-conducting material or plastics thin Film is as baseplate material.

US6906436B2 describes a variety of possible baseplate materials, such as metal or metal coating, semi-conducting material or such as Sapphire, ceramics or this insulator of plastics.The different geometries of substrate can be used to this.

US7494742B2 particularly depict metal, semiconductor, silicate and glass and inorganic or organic polymer is made For baseplate material.

Metal, semiconductor or insulating materials and combinations thereof are referred to as substrate by US7211351B2.

Semiconductor, metal and plastics are referred to as substrate by US2008/0001577A1.

Substrate in EP2434567A2 is conductive material, such as metal, insulating materials and example as ceramics or plastics The semi-conducting material as silicon, and the composition of semiconductor and conductor, or for adjusting the labyrinth of thermal coefficient of expansion. Them are equally referred in document US2008/0032236A1, US8228023B2 and US2010/0104942A1 or similar to material Material.

And US2010/0104942A1 is described and the substrate being made up of materials described below is referred to as to substrate important in practice Material：With dystectic metal or metal alloy and such as high quartz, silicon wafer, the dielectric material of aluminum oxide.This be because For, in the case of negative electrode is manufactured by usually used lithium and cobalt oxides (LCO), it is necessary to higher than 400 DEG C, it is average also above It is heat-treated at 500 DEG C or higher of temperature, to be storage Li⁺Ion and obtain particularly advantageous crystal within this material Structure, so as to use the material with relatively low softening temperature, such as polymer or inorganic material.But metal or metal alloy with And dielectric material has different difficult points：Such as dielectric material is generally crisp and cannot be used in the volume to volume technique of cost advantages, And another aspect metal and metal alloy are easy to aoxidize during the high-temperature process of cathode material.In order to overcome above-mentioned difficulties, The substrate being made up of different metal or silicon is proposed in US2010/0104942A1, wherein, the oxidation for the material being bonded to each other is also Former potential is thus coordinated with each other so that controllable oxidation occurs.

Required higher substrate temperature tolerance is also multiple in US2010/0104942A1 as stated above It is discussed in open source literature.Thus the substrate that for example by adjusting process conditions heat load intensity can be can be used to be 450 DEG C. But be deposition process to this precondition, substrate is heated wherein and/or by O₂The sputter gas mixture formed with Ar Optimization and/or be biased and/or be applied around the second plasma sputtering in substrate.To this for example in US2014/ 0030449A1, Tintignac et al., Journal of Power Sources 245 (2014), 76-82, or The photoelectron research of the electronic structure of Ensling, D. lithium and cobalt oxides thin layer, Darmstadt technology universities, 2006 Nian doctors Paper.But in general, this treatment technology regulation measure is costly and according to processing mode, especially in reply chip It is difficult to be realized with acceptable cost when carrying out continuous coated.

US2012/0040211A1 discloses a kind of glass film as substrate, its thickness maximum 300 μm and surface Roughness is not more thanRelatively low surface roughness is necessary, because the layer of thin film memory element is generally with very small Thickness.On the other hand, even if the surface irregularity of very little may also can make the functional layer of thin film memory element that catastrophe failure occur, because This causes battery global failure.This is equally applicable to document WO2014/062676A1.It is proposed uses Pyrex or calcium soda-lime glass Hull cell.Thickness change on substrate also seldom refers to herein.

Therefore, in conventional films memory element the problem of, is the susceptibility-to-corrosion of used material, is especially using metal In the case of lithium, this can cause the Rotating fields of complexity and therefore generally cause very high cost, and another problem is that substrate Type, substrate is especially nonconducting but is functional layer used flexible, resistant to elevated temperatures and relative to memory element It is as inert as possible, and layer as flawless as possible should be able to be deposited on substrate with good layer adhesive ability.But show Go out, also can be by even if the especially low substrate of surface roughness, for example in the glass film mentioned in US2012/0040211A1 Come off in crackle and/or layer and layer failure occur, such as described in US2014/0030449A1.But as it was previously stated, at that In the method that proposes, i.e. by being biased when manufacturing lithium and cobalt oxides layer to avoid high annealing temperature, it is difficult to be attached to It is commonly used in the online process of manufacture thin film memory element, thus with regard to technology aspect it should further be appreciated that using suitable The substrate of high-fire resistance (or temperature tolerance).

It is for another problem of all baseplate materials (regardless of its concrete composition), the possibility processing of ultra-thin glass Scheme.So-called bearer solution refers to, temporarily fixes ultra-thin glass before or during coating process or transfer process step On pad.This is alternatively carried out or realized by using organic strippable jointing material with electrostatic force.Especially exist In the case of the latter, it is necessary to ensured by appropriately selected substrate or carrier (it is generally made up of same material), can separated, Substrate is detached from the carrier.The separation typically results in there is distorting stress in a substrate, wherein, the stress can be also delivered to On the layer on substrate, this equally causes slabbing line and layer to come off, so as to thus be further exacerbated by the thickness ripple by substrate Layer deviation caused by dynamic.

It can also be implemented in principle by using the high power optical energy, such as excimer laser in film electricity memory element Manufacture in some procedure of processings.Here, in order to realize all processing schemes, for example by laser cut crystal or lead to Crossing UV sources solidifies organic adhesive material, and the UV that can be targetedly the modified transmissions of baseplate material are favourable.

The content of the invention

It is an object of the invention to provide one kind include plate shape discrete component (diskretes Element electric storage system), the plate shape discrete component and its manufacture and application.

Another object of the present invention is to provide a kind of electricity memory element, especially thin film memory element, it overcomes currently The problem of prior art and the low cost manufacture for realizing thin film memory element.It is a further object of the present invention to provide one kind to be applicable In the plate element and its manufacture that are used in electricity memory element and application.

Plate shape discrete component has 300 DEG C, preferably ＞ 400 DEG C of ＞ enough heat endurances, and with relative to by Enough tolerances of pollution caused by battery component, there is high barrier action and relative to UV relative to moisture in addition Radiation provides the optical transmittance or barrier matched with the manufacturing process and demand of respective specific battery design.In addition, the base Plate should contribute to the well attached of applied layer, i.e. especially for having for the deposition closest to layer (be usually LCO) The suitable coefficient of expansion.

In addition, the substrate or overhead plate of the present invention also should relative to the erosion of the ion of alkali metal, especially lithium or alkali metal With high tolerance.

It was unexpected that according to the purpose of the present invention can simple realization in the following manner, inserted in thin film memory element Plate shape discrete component, it has high tolerance relative to the erosion of the ion of alkali metal, especially lithium or alkali metal, wherein, plate Shape discrete component has following composition, and the composition characteristic is the weight % of highest 2 TiO₂Content, preferably up to 0.5 weight Measure % TiO₂Content and very particularly preferably without TiO₂。

In another embodiment of the present invention, there is low TiO₂At least one plate shape discrete component of content is configured to Comprising lithium or including lithium.Plate shape discrete component can be regarded as including lithium, lithium is located at material of main part (bulk material) wherein It is upper or in.Regard plate shape discrete component as comprising lithium wherein, lithium preferably is contained in material of main part (bulk Material in).On the other hand, lithium can exist in the form of the oxide or as metal, for example exist in plate shape discrete component Surface on.According to an embodiment of the invention, there is lower content TiO₂Plate shape discrete component have 7 weight % or Below, preferably 5.2 weight % or following and particularly preferred 2.5 weight % or following, very particularly preferably 0.5 weight % or Below and most preferably 0.2 weight % or following Li₂O content, wherein, Li₂O content is at least 0.1 weight %, wherein, lithium Concentration be able to also can also change on the cross section of plate shape discrete component.

In another preferred embodiment of the present invention, at least one surface structure of at least one plate shape discrete component Into it is directed to the permeability and/or be not that the material contacted with the surface is degree inert and/or with reduction as far as possible Permeable.

Preferably, at least one surface structure is into barrier or barrier layer.

In another embodiment of the present invention, barrier is configured to the barrier for metal diffusion.

In another preferred embodiment of the present invention, barrier layer is configured to the barrier for alkali metal diffusion.

Preferably, barrier layer has at least one alkali metal and/or alkaline-earth metal to be formed by doping or overdoping.

In another particularly preferred embodiment of the present invention, the barrier action at least one surface is for lithium.

In another embodiment of the present invention, at least one plate shape discrete component includes at least one oxide or a variety of Hopcalite or compound.

In a preferred embodiment of the present invention, plate shape discrete component includes SiO₂As oxide.

Preferably, plate shape discrete component, which has, includes following compositions, and the composition characteristic is the weight % of highest 2 TiO₂ Content, preferably up to 0.5 weight % TiO₂Content, and very particularly preferably without TiO₂。

Preferably, plate shape discrete component of the invention has following composition (unit is weight %)：

Wherein, MgO, CaO, SrO and BaO content and in 8 to 18 weight % scope, in addition, also may be present and be in The other elements of additive (such as fining agent) form needed for impurity or manufacturing technology, wherein, the summation of these elements is not high In 2 weight %.

In another embodiment of the present invention, relative to used chip or substrate size, relative to diameter in ＞ In 100mm scope, especially lateral dimension be 100mm100mm in the case of chip or substrate size, preferably with respect to Diameter in ＞ 200mm scope, especially lateral dimension be 200mm200mm in the case of chip or substrate size and Particularly preferably relative to diameter in ＞ 400mm scope, the crystalline substance especially in the case where lateral dimension is 400mm400mm Piece or substrate size, plate shape discrete component have in 25 μm, preferably ＜ 15 μm of ＜, 10 μm of particularly preferred ＜ and very especially excellent Select the total thickness variations (total thickness variation, ttv) in 5 μm of ＜ scope.Therefore, occurrence is typically It is related to diameter in the range of ＞ 100mm or 100mm100mm size, preferred diameter ＞ 200mm or 200mm200mm chi Chip or substrate size in the scope of very little, particularly preferred diameter ＞ 400mm or 400mm400mm size.

Formed body is interpreted as with plate shape in this application, wherein, size of the element along a direction in space compares another two The as low as not a half individual order of magnitude of direction in space.In this application if formed body can be separated from electric storage system under consideration, I.e. especially also can individualism, then the formed body be considered as discrete.

In order to maintain quality similar between battery and battery, the relatively high evenness of the thickness distribution of plate shape discrete component is Important.Hull cell is generally manufactured on the wafer scale comprising or not comprising covering, and is then cut.It is permanent in thickness Battery on the one wafer or at least chip has different-thickness with chip in the case of qualitative deficiency, and then for example in weight There is different size in terms of amount/energy density.This especially requires the product specification of electricity memory element high uniform in application It is unfavorable in the case of constant.Quality inspection cost can be saved by less total thickness variations and avoids producing waste product.

In addition, in the case where plate shape discrete component is used as the substrate for deposition film memory element, the discrete member of plate shape Another result of the relatively high evenness of the thickness distribution of part is multiple layers equally entirely and without the lateral wave of layer thickness distribution Deposit dynamicly on the substrate.This causes again, in follow-up processing step, for example completes to return LCO layers after depositing When fiery will not each layer in itself in or each layer between respective interface on, produce on interface that especially also will not be between layer and substrate Raw local stress.Crackle is efficiently avoid by this way and is come off.

I.e., it has been shown that, the failure of this layer that cracked especially in layer or layer comes off from substrate seldom due to The surface irregularity degree of substrate causes, and is due to the thickness fluctuation of substrate and is transmitted when substrate comes off from so-called carrier The combination of power on to substrate causes.

In addition, it was demonstrated that advantageously, plate shape discrete component can targetedly be adjusted in UV according to specifically chosen composition In the range of characteristic, i.e. absorption and transmission.

The transmittance targetedly adjusted realizes a series of to carry out simply by being handled with electromagnetic radiation Processing step, such as

The separation (debonding, unsticking) of-promotion substrate and carrier, because can particularly effectively divide by this way From organic adhesion layer,

- encapsulated layer is solidified, the encapsulated layer is used to protect memory element in order to avoid by Korrosionsmedium (such as oxygen And/or vapor) erosion, for example, see the 273A1 of DE10 2,012 206, and

- lithium and cobalt oxides layer is tempered by high-energy radiation, it is desired with high preferably quantitatively to provide The crystallization high-temperature-phase of particular memory density.

According to another embodiment of the present invention, according to the thickness of the plate shape discrete component of the present invention no more than 2mm, preferably Less than 1mm, it is particularly preferably less than 500 μm and very particularly preferably less than or equal to 200 μm.Most preferably, substrate thickness is most Greatly 100 μm.

Such as thus, it is possible to directly manufacture the plate shape discrete component of expectation thickness.But it also may be accomplished by mesh Mark thickness, i.e. for example by grind, etch and polish one in the processing step after manufacturing or being processed further process Or multiple techniques, thicker plate shape discrete component is thinning.

In another embodiment of the present invention, the vapor transmission rate (WVTR) of plate shape discrete component is ＜ 10^-3g/ (m²D), preferably ＜ 10^-5g/(m²D) and particularly preferably ＜ 10^-6g/(m²·d)。

In another embodiment, 350 DEG C temperature and frequency be 50Hz alternating current in the case of, plate shape is discrete The ratio resistance of element is more than 1.010⁶Ohm·cm。

In addition, plate shape discrete component preferably has at least 300 DEG C, preferably at least 400 DEG C and particularly preferably at least 500 DEG C maximum heat resistance (or temperature tolerance) or peak load temperature and 2.010^-6/ K to 1010^-6/ K, preferably 2.5·10^-6/ K to 9.510^-6/ K and particularly preferred 3.010^-6/ K to 9.510^-6Linear heat in/K scope is swollen Swollen factor alpha.To this it has been shown that particularly preferred layer quality can be realized in thin film memory element in a case where：Most Big load temperature θ_MaxFollowing relationship be present between thermal linear expansion coefficient α in (unit is DEG C)：600·10^-6≤θ_Max·α≤ 8000·10^-6, particularly preferred 80010^-6≤≤θ_Max·α≤5000·10^-6。

If on the other hand, not illustrating, thermal linear expansion coefficient α is provided in 20-300 DEG C of scope.In this hair In bright disclosure, α and α_(20-300)Synonymously use.The value provided be determined according to ISO7991 with static measurement it is specified Average thermal linear expansion coefficient.

In the context of this application, peak load temperature θ_MaxFor such temperature, at such a temperature, the material still can Its functional completeness is maintained completely and has not occurred decomposition reaction and/or degradation reaction.Certainly, according to the material used the temperature Degree definition is different.For crystalline oxide material, peak load temperature is generally given by fusion temperature；It is mostly for glass Glass transformation temperature T_g, wherein, decomposition temperature may be lower than T in the case of lucite_g, and closed for metal or metal Gold, the peak load temperature approx can be given by fusion temperature, unless metal or metal alloy in the fusion temperature to issue Raw degradation reaction.

Transition temperature T_gHanded over as the tangent line in the Liang Ge branches of the expansion curve measured by the rate of heat addition with 5K/min Point provides.This corresponds respectively to the measurement according to ISO7884-8 or DIN52324.

In another embodiment, at least one surface structure is into the barrier relative to basic ion and/or alkaline earth ion.

The metal is preferably lithium.

In another embodiment, construct barrier layer at least one surface of plate shape discrete component by doping or Overdoping has alkali metal and/or alkaline-earth metal (such as lithium) or transition metal and formed.Show, the lithium of very little content can be prevented Only layer material as such as LiPON or lithium metal of the element from electricity memory element is diffused into plate shape discrete component or at least Reduce the diffusion.

Preferably, plate shape discrete component is constructed so that plate shape discrete component includes lithium, wherein, lithium is in its manufacturing process Just precursor can be used as to add or be also just for example introduced into afterwards by diffusion process in plate shape discrete component.If plate Shape discrete component is made up of glass, therefore lithium can be used as raw material to be added in synthesis, or can pass through follow-up diffusion process, example Such as by exchanging the glass of the original no lithium of the introducing of the ion exchange in bathing during the process for carrying out chemical tempering to glass Glass.

In addition, these processes also can be combined according to another embodiment of the present invention.Thus wrapped in main body composition Plate shape discrete component containing lithium can yet subsequently be merged into extra lithium by suitable technique.

In an embodiment of the invention, lithium is evenly distributed in the whole volume of plate shape discrete component.But According to another embodiment of the present invention also it is possible that the concentration of lithium variable, i.e. example on the cross section of plate shape discrete component Such as reduce towards the surface lithium concentration of plate shape discrete component, so as to thus there is the concentration ladder of lithium distribution in plate shape discrete component Degree.

Realized according to for example this gradient of an embodiment of the invention by ion-exchange process, wherein, afterwards Lithium is introduced into plate shape discrete component or the lithium content of the plate shape discrete component of original included lithium improves.But in addition, root According to another embodiment of the present invention also it is possible that forming this gradient in itself by the manufacturing process of plate shape discrete component. This is for example realized by suitable temperature control in the mill, so as to for example due to lithium evaporation plate shape discrete component table Occurs the consumption of lithium on face.

Lithium ion diffuse into plate shape discrete component and therefore the change to its internal structure and/or it is unstable can be with Different modes occur.By being contacted with Li metals to make Li⁺Intrusion be by with multivalent ion, such as Ti in glass⁴⁺Carry What preceding redox reaction was carried out.Due to Ti⁴⁺It is reduced to Ti³⁺, and from Li⁰Form Li⁺, and be diffused into substrate and its tie Structure changes or unstable.This can be by not having the share-maintenance of multivalent ion or multivalent ion very in plate shape discrete component It is small and be doped with lithium or overdoping prevents.

In addition, by being in contact with it, lithium ion invades the discrete member of plate shape from the electrolyte, such as LiPON of battery system Damaged in part and to it.Simultaneously in Li⁺Basic ion and/or alkaline earth ion in the case of being diffused into plate shape discrete component It is diffused into from plate shape discrete component in the layer system of battery.In order to which anti-system is in both sides, i.e. on plate shape discrete component and battery Infringement, it is necessary to be doped with lithium or overdoping.But the basic ion and/or alkaline earth ion of the non-lithium in plate shape discrete component Extra share should be excessive, at least to prevent it from invading in battery layers.In principle, in order to using mixed alkali effect, it is necessary to Basic ion Li, Na, Ka proper ratio are set in plate shape discrete component, to prevent Li to be diffused into substrate and to make substrate Composition is moved in battery layers.Here, it is unessential for whether there is multivalent ion in plate shape discrete component.

Li is introduced into plate shape discrete component and can carried out by melting process for barrier action.Additionally due to plate shape The thickness of discrete component is small, and complete ion exchange can be carried out in the whole thickness of thin plate.

In order to examine plate shape discrete component to be directed to the contact stabilization of lithium ion, sample is introduced into liquid lithium nitrate (LiNO₃) in 10 minutes.Salting liquid has about 380 DEG C of temperature.Then take out sample and remove dry salt residue.Complete , can be by suitable analysis method, such as Time-of-Flight Secondary Ion Mass into after the cooling of sample Spectroscopy (ToF-SIMS, time flight SIMS) registered depth profile, it shows Li⁺Signal, which is used as, to be splashed Penetrate the curve of the function of the denudation depth of time and sample.ToF-SIMS is very sensitive analysis method, and it especially also may be used Detect very low concentration of lithium.

For inspection substrate relative to Li⁺Stability alternative approach be LiPON sputtering deposit.Under example Sexual behavior mode Row coating parameter, the thickness drawn at this is in 1.0 to 1.2 μm of scope：

Sputtering target material：Li₃PO₄

Reacting gas in the chamber：N₂

Process lasting time：30 minutes 4 hours

Operation pressure：5·10^-3mbar

By selecting nitrogen N₂As process gas, LiPON is formed in sputtering.

Due to sputtering technology, occur the temperature raising related to equipment or principle on the substrate of coating.It is quick by temperature The temperature of the label of sense and about 80 DEG C of signal temperature survey on bottom side.Now the temperature in coated side is in about 100 DEG C to 120 DEG C.

For the another method of contact stabilization of lithium metal it is to compress lithium metal band for examining plate shape discrete component Onto plate shape discrete component.Surface area of the lithium metal sample with 100 μm of thickness and 3mm3mm.By it in glove box (Glove-Box) be pressed into size be 20mm20mm sample on and next aeroseal and weld under vacuo Connect.Then put samples into press and be pressed on plate shape discrete component 1 point by lithium metal under 1.5bar pressure Clock, to improve the contact between two kinds of materials.

Entirely deposit one week at room temperature.Then, lithium metal with distilled water by reacting and from plate shape discrete component Remove and study the discoloration of plate shape discrete component.

For inspection substrate relative to metal Li⁰The alternative approach of stability be hot evaporation.

Following coating parameter is exemplarily selected, the thickness drawn at this is in 1.1 to 1.9 μm of scope：

Process lasting time：11 seconds 8 minutes

Basic pressure：2·10^-6mbar

Thickness sensor is used as by quartz oscillator and controls process lasting time.

Due to evaporation process, occurs the slight raising of the temperature related to system or principle on the substrate of coating.But It is less than in the case of LiPON coatings and estimates that the value is about 50 DEG C.

According to another embodiment of the present invention, according to the plate element of the present invention by least one oxide or a variety of oxygen The mixture of compound or compound group into.

In another embodiment of the present invention, at least one oxide is SiO₂。

In another embodiment of the present invention, plate element is made up of glass.Term glass in the context of this application Glass refers to this material, its be substantially inorganic in nature and mainly by metal and/or semimetallic compound group into, It includes periodic table of elements VA, VIA and VIIA races element, it is preferred that comprising oxygen, the material is characterized in amorphous state, i.e., non-week Phase property arrangement three-dimensional state and 350 DEG C temperature and frequency be 50Hz alternating current under conditions of have be more than 1.0106Ohmcm ratio resistance.Therefore, the non-crystalline material LiPON as solid state ionic conductor is not suitable as the application Glass in meaning.

According to another embodiment of the present invention, obtained according to the plate element of the present invention by melting process.

Preferably, plate element is caused to be configured to plate shape in the moulding process after melting process.On the other hand, the shaping can Immediately carry out (so-called thermoforming) after the melting.But substantially unformed solid can also be obtained first, it is in the case where connecing It is transformed into plate shape state with mechanically deform by reheating in the step come.

If being molded plate element by thermoforming process, it is related to pulling method in embodiments of the present invention, such as Glass tube down-drawing, upper daraf(reciprocal of farad) or overflow fusion method.But other thermoforming process are also possible, for example, carry out in float glass process into Type.

Plate shape discrete component can be especially used as the substrate of the functional layer for depositing storage energy in electric storage system.Root According to another embodiment of the present invention, also can using the plate shape discrete component come cover the functional layer structure of electric storage system or As overhead plate.This shielding part with overhead plate in itself can be by as relative to the region or object accordingly covered whereby The outermost layer of environment, such as the outermost layer of electric storage system, overhead plate limit in itself.

Example

Summarize and formed according to the exemplary partial of the plate element of the present invention in the following table.

As long as not referring to, the fining agent in following all embodiments all optionally containing 0 to 1 weight %, such as SnO₂、CeO₂、As₂O₃、Cl^-、F^-, sulfate.

Illustrative examples 1

The composition of plate shape discrete component, which exemplarily consists of, to be provided (unit is weight %)：

Wherein, MgO, CaO, SrO and BaO content summation are in 8 to 18 weight % scope, and in addition, other yuan Element can exist in the form of the additive needed for impurity or manufacturing technology, such as fining agent, wherein, the total amount of these components is not More than 2 weight %.

Illustrative examples 2

The composition of plate shape discrete component, which exemplarily also consists of, to be provided (unit is weight %)：

Illustrative examples 3

Illustrative examples 4

Illustrative examples 5

The composition of another plate shape discrete component, which exemplarily consists of, to be provided (unit is weight %)：

Illustrative examples 6

Illustrative examples 7

Illustrative examples 8

The following characteristic of plate shape discrete component is obtained by the composition：

α_(20-300) 3.8ppm/K

T_g 719℃

Density 2.51g/cm³

Illustrative examples 9

α_(20-300)3.8ppm/K

Density 2.5g/cm³

Illustrative examples 10

α_(20-300) 3.73ppm/K

T_g 705℃

Density 2.49g/cm³

Illustrative examples 11

α_(20-300) 3.2ppm/K

Density 2.38g/cm³

Illustrative examples 12

α_(20-300) 9.4·10^-6/K

T_g 533℃

Density 2.55g/cm³

Illustrative examples 13

α_(20-300) 8.6·10^-6/K

T_g 607℃

Density 2.4g/cm³

Illustrative examples 14

α_(20-300) 9.7·10^-6/K

T_g 556℃

Density 2.6g/cm³

Illustrative examples 15

α_(20-300) 8.3·10^-6/K

T_g 623℃

Density 2.4g/cm³

Illustrative examples 16

Illustrative examples 17

α_(20-300) 9.0ppm/K

T_g 573℃

Illustrative examples 18

α_(20-300) 9.5ppm/K

T_g 564℃

Listed in order to which preferably the present invention will be described, in table 1 below according to the present invention plate shape discrete component its His specific illustrative embodiment (AB), its contact stabilization for lithium is studied.For relative to lithium metal and lithium from The contact stabilization of son, equally list the comparative example (VB) of the plate shape discrete component not according to the present invention.

The occurrence of the composition for the example listed is provided with weight % respectively to this.In addition, in 20-300 DEG C of scope The value of thermalexpansioncoefficientα provided with ppm/K, transition temperature T_gDEG C to provide and density is with g/cm³Provide.

Plate shape discrete component is qualitatively assessed in table 1 relative to lithium metal or LiNO₃Contact stabilization.Assess specific Represent：

++ without visible change

+ it can be seen that minimum change

0 slight mist degree or discoloration, may not only on the surface

- obvious discoloration or mist degree

-- sample vigorous reaction/change is projected significantly in the certain depth of sample

Table 1

It can be seen that by research conditions, the example titanium oxide as the element of multivalence content in the composition of plate shape discrete component Content be unfavorable for contact for lithium metal.Element of multivalence is reduced by lithium metal, such as can according to comparative example 1 (VB1) Find out.In the composition of plate shape discrete component in addition to element of multivalence, such as titanium, basic ion, when especially also including lithium ion, It can be enhanced for the contact stabilization of lithium metal.This especially can be seen that from comparative example 2 and 3 (VB2 and VB3) comparison.Than Total content is included as 14.89 weight % alkali metal oxide and 3.9 weight % TiO compared with example 2₂Content, compared to comprising Total content is only 4.0 weight % alkali metal oxide and 2.5 weight % TiO₂Content comparative example 3, show to improve For the stability that is contacted with lithium metal.

By contrast, if not including TiO in the composition of plate shape discrete component₂, other also be present in addition to lithium Improve the stability (referring to embodiment 24) relative to lithium metal in the case of basic ion on the whole and by adding lithium also Further improve (referring to embodiment 25 and 27).

But the TiO of less content can be included in the composition of plate shape discrete component₂, without damaging relative to lithium metal Stability.On the other hand, in order to realize the desired inertia for being contacted with lithium metal of plate shape discrete component, content is less than or equal to 2.0 weight % TiO₂It is allowed.

Preferably, therefore plate shape discrete component has following compositions, and the composition characteristic is the weight % of highest 2 TiO₂ Content, preferably up to 0.5 weight % TiO₂Content, very particularly preferably without TiO₂。

According to a particularly preferred embodiment, plate shape discrete component is formed by glass, is the characteristics of the composition of glass The weight % of highest 2 TiO₂Content, preferably up to 0.5 weight % TiO₂Content, very particularly preferably without TiO₂。

Shown in terms of the stability for being contacted with lithium ion, seldom levels of base is being had no or only in addition to lithium Obtained in the plate shape discrete component of ion and be directed to the extraordinary contact stabilization of lithium ion.With very high sodium content and potassium oxidation In the plate shape discrete component of thing, it can further improve contact stabilization of the plate shape discrete component for lithium ion by adding lithium.

If in addition, there is no Li also in the composition₂O content, mentioned embodiment can be revised as including beyond not The Li of the obvious share content of trace can be avoided that₂O.This share is from the Li more than or equal to 0.1 weight %₂O content starts with regard to energy Realize.

On the other hand, modification of the completion to the composition of plate shape discrete component of such as getting off can be passed through：Proportionally reduce in plate shape point The share of otheralkali metal oxide that may be present in the composition of vertical element so that remaining component is relative to alkali metal oxide Content keep constant, or be additionally added Li in remaining component₂O, so as to correspondingly reduce its share.

If Li is included in plate shape discrete component₂O, its share are at least 0.1 weight %, in addition less than 7.0 weight %, Preferably smaller than 5.2 weight %, particularly preferably less than 2.5 weight %, very particularly preferably it is less than 0.5 weight % and most preferably Less than 0.2 weight %.

In accordance with another preferred embodiment of the present invention, plate shape discrete component is made up of glass, and it is formed except with trace Existing impurity is free of TiO₂, also with following characteristics, Li₂O content is less than or equal to 7.0 weight %, is preferably smaller than equal to 5.2 weights Amount %, particularly preferably less than it is equal to 0.2 weight equal to 0.5 weight %, more preferably less than equal to 2.5 weight %, particularly preferably less than % is measured, wherein, Li₂O content is at least 0.1 weight %.

In addition, can to it is inorganic, siliceous, especially silicate, substantially fluid free material carries out enabling in particular to improve The processing of the strength of materials.Case of materials that glass, this processing especially tempering, such as hot and/or chemical tempering is especially chemical Tempering.

On the other hand, the chemical tempering of glass exchanging the ion exchange in bathing by obtaining.If using the glass of tempering, It is characterized in that carried out before the functional layer of electric storage system is applied, it is characterised in that there is following chemical tempering, describedization The feature for learning tempering is the thickness L of ion exchange layer_DoLIt is at least 10 μm, preferably at least 15 μm, most preferably at least 25 μm and glass Compression (the σ on glass surface_CS) preferably at least 100MPa, preferably at least 200MPa, particularly preferably at least 300MPa, very especially excellent Select 480MPa or higher.

Coat and the subsequent functional layer for handling electric storage system during may technique it is related due to and produce The change of the stress state of the raw glass as substrate.This is astoundingly shown, the prestressing force of this glass will not be dropped It is as low as zero, but saves residual stress in glass, so as to relative to traditional glass without rigidifying, improves on the whole The intensity of glass as substrate.

Glass as substrate in finished product accumulator is characterized in that it is at least partly glass through chemical tempering to this Glass, wherein, at least partly through chemical tempering at this by exchanging ion exchange and follow-up heat treatment acquisition in bathing, and And it is characterised by, the thickness (L of ion exchange layer_DoL) it is at least 10 μm, preferably at least 15 μm, most preferably at least 25 μm and glass Compression (the σ on glass surface_CS) it is at least 100MPa, preferably at least 200MPa, particularly preferably at least 300MPa, very particularly preferably 480MPa or higher, wherein, thickness of the thickness of ion exchange layer less than the ion exchange layer after thermal stress before thermal stress Degree, and the compression of glass surface is more than the compression of the glass surface after thermal stress before thermal stress.

In an embodiment of the invention, glass realizes chemical tempering in the exchange bath comprising lithium ion.Thus Such as it can also be used with different basic ions, such as potassium and the as little as exchange bath of the lithium of minimized content.Also tandem type work can be carried out Skill, such as exchanged with potassium and continue rapidly to swap using the bath containing lithium.

Brief description of the drawings

Fig. 1 shows the schematic diagram of electricity memory element,

Fig. 2 shows the schematic diagram of plate shape discrete component,

Fig. 3 to Fig. 5 shows the scanning electron micrograph of plate shape discrete component,

Fig. 6 shown after lithium metal, the photo of plate shape discrete component.

Embodiment

Fig. 1 schematically shows the electric storage system 1 according to the present invention.It includes plate shape discrete component 2, and it is used as base Plate.A series of different layers are coated on substrate.Exemplarily and the example is not limited to, herein on plate shape discrete component 2 Two collector layers, cathode current collector layer 3 and anode collector layer 4 are coated first.This collector layer is usually thick a few micrometers And it is made of metal, such as is made up of copper, aluminium or titanium.Deposition has cathode layer 5 on collector layer 3.If electric storage system 1 It is lithium base film battery, negative electrode is made up of lithium-transistion metal compound, is preferably made up of oxide, such as by LiCoO₂、 LiMnO₂Or LiFePO₄It is made.In addition, on substrate and at least in part with overlappingly coated electrolyte 6 of cathode layer 5, wherein Electrolyte is mostly LiPON in the case of lithium base film battery, i.e. lithium and oxygen, phosphorus and nitrogen compound.In addition, electricity storage system System 1 includes anode 7, and it can for example be made up of Li-Ti oxide or lithium metal.Anode layer 7 at least in part with dielectric substrate 6 with And collector layer 4 is overlapping.In addition, battery 1 includes encapsulated layer 8.

On the other hand, in the present invention, the encapsulation or sealing of electric storage system 1 refer to prevent significantly reduce fluid or other The material that corrosion material is corroded electric storage system 1.

Fig. 2 shows the schematic diagram of the plate shape discrete component of the present invention, is configured to the form of plate shape formed body 10 herein. In the present invention, if being not more than the half in another two direction in space size in its size along a direction in space, formed body claims For plate shape or thin plate.In the present invention, it is referred to as when formed body has following relation between its length, width and its thickness Band：For width at least ten times, width is at least twice of thickness to its length.

Fig. 3 shows the plate shape discrete component of the composition with embodiment 5 (AB5) in plate in scanning electron micrograph The surface of shape discrete component contacted with lithium metal after cut edge.The cut edge of plate shape discrete component is not only formed uniformly on surface Above and in material of main part.Therefore without the surface that the caused plate shape discrete component due to the contact with lithium metal occurs Degraded.

Fig. 4 shows table of the plate shape discrete component before being contacted with lithium metal corresponding to the composition of comparative example 1 (VB1) Face.

Fig. 5 shows table of the plate shape discrete component after being contacted with lithium metal corresponding to the composition of comparative example 1 (VB1) Face.It will be evident that the surface obvious degradation of plate shape discrete component, it causes surface to come off and the obvious roughening on surface.

The different photos of different plate shape discrete components after stress test are can be seen that in figure 6, wherein, plate shape point The surface of vertical element is coated with lithium metal by evaporation.After lithium metal is coated with by evaporation, respective sample is stored in Under inert gas in glove box.Lithium layer is wiped after storage.

In the sample photo on Fig. 6 left sides, its have corresponding to comparative example (VB) 1 and 3 composition, it shows, except Go after lithium metal, the surface of sample changes, and especially it shows mist degree or discoloration.By contrast, at embodiment (AB) 28th, there is no this change in the sample of 21 and 32 detection, typically without changing colour.According to inventor, compared to than Compared with example 1 and 3, due to lacking Ti content in sample without changing colour.

Reference numerals list

1 electric storage system

The 2 plate shape discrete component as substrate

3 are used for the collector layer of negative electrode

4 are used for the collector layer of anode

5 negative electrodes

6 electrolyte

7 anodes

8 encapsulated layers

The plate shape discrete component of 10 plate shape formed body forms

Claims (according to the 19th article of modification of treaty)

1. a kind of thickness is less than 2mm electric storage system, it includes at least one plate shape discrete component made of glass, its In, the plate shape discrete component have it is high to the ion of alkali metal or alkali metal, the tolerance of the especially erosion of lithium, wherein, The plate shape discrete component has following compositions, and the composition is characterised by containing up to 2 weight % TiO₂Content, preferably The weight % of highest 0.5 TiO₂Content and very particularly preferably without TiO₂, and with selected from any one of following scope with The composition of weight % meters：

Wherein, scope of the summation of the content of MgO, CaO, SrO and BaO in the range of No.1 in 8 weight % to 18 weight % In, and wherein, can extraly include in impurity or the necessary additive related to technique, such as refining agent form other Component, wherein, the summation of these components is not more than 2 weight %.

2. thickness according to claim 1 is less than 2mm electric storage system, it includes at least one plate shape discrete component, Wherein, the plate shape discrete component includes composition in the range of No.1 and wherein, and BaO contents are in 3 weight % and 8 weights Between amount %.

3. thickness according to claim 1 or 2 is less than 2mm electric storage system, it includes the discrete member of at least one plate shape Part, wherein, the plate shape discrete component have it is high to the ion of alkali metal or alkali metal, the tolerance of the especially erosion of lithium, Wherein, the Li of at least one plate shape discrete component₂O content be 7.0 weight % or following, be preferably 5.2 weight % or with Under, particularly preferably 2.5 weight % or following, very particularly preferably 0.5 weight % or following, be most preferably 0.2 weight % Or it is following, wherein, Li₂O content is at least 0.1 weight %, and wherein, lithium concentration can be in the transversal of the plate shape discrete component Change on face.

4. preferred electric storage system according to any one of claim 1 to 3, wherein, at least one plate shape is discrete At least one surface structure of element is at least one surface pair is inert with the material that the surface contacts and/or had There is the permeable of reduction and/or be impermeable.

5. electric storage system according to claim 4, wherein, at least one surface structure is into barrier or barrier layer.

6. electric storage system according to claim 5, wherein, the barrier is configured to the barrier for metal diffusion.

7. electric storage system according to claim 6, wherein, the barrier layer is configured to the screen for alkali metal diffusion Barrier.

8. electric storage system according to claim 7, wherein, the barrier layer has at least one by doping or overdoping Alkali metal and formed.

9. the electric storage system according to any one of claim 4 to 8, wherein, the barrier at least one surface is made With being configured to be directed to lithium.

10. in particular according to the electric storage system any one of claim 1 to 9, wherein, relative to diameter in ＞ 100mm Scope in, especially lateral dimension be 100mm100mm chip or substrate size, preferably with respect to diameter ＞ 200mm's In scope, especially lateral dimension be 200mm200mm chip or substrate size, particularly preferably relative to diameter in ＞ 400mm Scope in, chip or substrate size when especially lateral dimension is 400mm400mm, the element have no more than 25 μm, Preferably no greater than 15 μm, the thickness change for being especially preferably no more than 10 μm and being very particularly preferably not more than 5 μm.

11. electric storage system according to any one of claim 1 to 10, it is characterised in that at least one plate shape The vapor transmission rate (WVTR) of discrete component is ＜ 10^-3g/(m²D), preferably ＜ 10^-5g/(m²D) and particularly preferably ＜ 10^-6g/(m²·d)。

12. the electric storage system according to any one of claim 1 to 11, wherein, at least one discrete member of plate shape The thickness of part is less than 2mm, preferably smaller than 1mm, particularly preferably less than 500 μm, is very particularly preferably less than or equal to 200 μ M, and most preferably no greater than 100 μm.

13. the electric storage system according to any one of claim 1 to 12, wherein, it is in 350 DEG C of temperature and frequency In the case of 50Hz alternating current, the ratio resistance of at least one plate shape discrete component is more than 1.010⁶Ohm·cm。

14. the electric storage system according to any one of claim 1 to 13, wherein, at least one discrete member of plate shape The peak load temperature θ of part_MaxIt is at least 300 DEG C, preferably at least 400 DEG C, very particularly preferably at least 500 DEG C.

15. the electric storage system according to any one of claim 1 to 14, wherein, at least one discrete member of plate shape The thermal linear expansion coefficient α of part is 2.010^-6/ K to 1010^-6/ K, preferably 2.510^-6/ K to 9.510^-6/ K and especially It is preferred that 3.010^-6/ K to 9.510^-6In/K scope.

16. the electric storage system according to any one of claim 1 to 15, wherein, at least one discrete member of plate shape The peak load temperature θ of part_MaxMeet following relation with thermal linear expansion coefficient α product：600·10^-6≤θ_Max·α≤ 8000·10^-6, particularly preferred 80010^-6≤θ_Max·α≤5000·10^-6。

17. the electric storage system according to any one of claim 1-16, wherein, at least one plate shape discrete component Plate shape is formed by melting process and subsequent moulding process.

18. electric storage system according to claim 17, wherein, subsequent moulding process is pulling method.

19. a kind of plate shape discrete component made of glass suitable for being used electric storage system, wherein, the plate shape point Vertical element have it is high to the ion of alkali metal or alkali metal, the tolerance of the especially erosion of lithium, wherein, the discrete member of plate shape Part has following compositions, and the composition is characterised by the weight % of highest 2 TiO₂Content, preferably up to 0.5 weight % TiO₂ Content and very particularly preferably without TiO₂, and with being formed with what weight % was counted selected from any one of following scope：

20. the plate shape discrete component according to claim 19 suitable for being used electric storage system, wherein, the plate Shape discrete component have it is high to the ion of alkali metal or alkali metal, the tolerance of the especially erosion of lithium, wherein, the plate shape point Vertical element is including the composition in the range of No.1 and wherein, and BaO contents are between 3 weight % and 8 weight %.

21. according to claim 19 or 20 suitable for the plate shape discrete component that is used electric storage system, wherein, institute State plate shape discrete component have it is high to the ion of alkali metal or alkali metal, the tolerance of the especially erosion of lithium, wherein, the plate The Li of shape discrete component₂O content is 7.0 weight % or following, is preferably 5.2 weight % or following, particularly preferably 2.5 weights Measure % or following, very particularly preferably 0.5 weight % or following, be most preferably 0.2 weight % or following, wherein, Li₂O's Content is at least 0.1 weight %, and wherein, and lithium concentration can change on the cross section of the plate shape discrete component.

It is 22. discrete suitable for the plate shape used electric storage system preferably according to any one of claim 19 to 21 Element, wherein, the surface structure is into being lazy for the material contacted with the surface at least one surface of the element Property and/or with reduction degree permeable and/or be impermeable.

23. the plate shape discrete component according to claim 22 suitable for being used electric storage system, wherein, it is described extremely Lack a surface structure into barrier.

24. the plate shape discrete component according to claim 23 suitable for being used electric storage system, wherein, the screen Barrier layer is configured to the barrier for metal diffusion.

25. the plate shape discrete component according to claim 24 suitable for being used electric storage system, wherein, the screen Barrier layer is configured to the barrier for alkali metal diffusion.

26. the plate shape discrete component according to claim 25 suitable for being used electric storage system, wherein, the screen Barrier layer has at least one alkali metal to be formed by doping or overdoping.

27. according to any one of claim 19 to 26 suitable for the discrete member of the plate shape used electric storage system Part, wherein, relative to diameter in ＞ 100mm scope, especially lateral dimension be 100mm100mm chip or substrate chi It is very little, preferably with respect to diameter in ＞ 200mm scope, especially lateral dimension be 200mm200mm chip or substrate chi It is very little, particularly preferably relative to diameter in ＞ 400mm scope, especially lateral dimension be 400mm400mm chip or substrate Size, the thickness change of the element are no more than 25 μm, preferably no greater than 15 μm, especially preferably no more than 10 μm and very special You Xuanbu great Yu not be 5 μm.

28. the plate shape discrete component according to any one of claim 19 to 27, wherein, the thickness of the element is less than 2mm, preferably smaller than 1mm, it is particularly preferably less than 500 μm, is very particularly preferably less than or equal to 200 μm, and most preferably not More than 100 μm.

29. according to any one of claim 19 to 28 suitable for the discrete member of the plate shape used electric storage system Part, wherein, vapor transmission rate (WVTR) is ＜ 10^-3g/(m²D), preferably ＜ 10^-5g/(m²And particularly preferred ＜ d) 10^-6g/(m²·d)。

30. according to any one of claim 19 to 29 suitable for the discrete member of the plate shape used electric storage system Part, wherein, in the case of the alternating current of 350 DEG C of temperature and frequency for 50Hz, ratio resistance is more than 1.010⁶Ohm· cm。

31. according to any one of claim 19 to 30 suitable for the discrete member of the plate shape used electric storage system Part, wherein, peak load temperature θ_MaxIt is at least 300 DEG C, preferably at least 400 DEG C and very particularly preferably at least 500 ℃。

32. according to any one of claim 19 to 31 suitable for the discrete member of the plate shape used electric storage system Part, wherein, thermal linear expansion coefficient α is 210^-6/ K to 1010^-6/ K, preferably 2.510^-6/ K to 9.510^-6/ K, He Te Not preferably 3.010^-6/ K to 9.510^-6In/K scope.

33. according to any one of claim 19 to 32 suitable for the discrete member of the plate shape used electric storage system Part, wherein, peak load temperature θ_MaxMeet following relation with thermal linear expansion coefficient α products：

600·10^-6≤θ_Max·α≤8000·10^-6, particularly preferred 80010^-6≤θ_Max·α≤5000·10^-6。

It is 34. a kind of discrete suitable for the plate shape used electric storage system according to any one of claim 19 to 33 The manufacture method of element, it includes, and carries out melting process and subsequent thermoforming process.

35. it is according to claim 34 suitable for the manufacture method of the plate shape discrete component used electric storage system, Characterized in that, the thermoforming process is pulling method.

36. the plate shape discrete component according to any one of claim 19 to 33 is used as the use of substrate in electric storage system On the way.

37. the plate shape discrete component according to any one of claim 19 to 33 is used as overhead plate in electric storage system Purposes.

38. the plate shape discrete component according to any one of claim 19 to 33 is used as overcover in electric storage system Purposes.

Claims

1. a kind of thickness is less than 2mm electric storage system, it includes at least one plate shape discrete component, wherein, the plate shape point Vertical element have it is high to the ion of alkali metal or alkali metal, the tolerance of the especially erosion of lithium, wherein, the discrete member of plate shape Part has following compositions, and the composition is characterised by containing up to 2 weight % TiO₂Content, preferably up to 0.5 weight % TiO₂Content and very particularly preferably without TiO₂。

2. being less than 2mm electric storage system in particular according to the thickness described in claim 1, it includes the discrete member of at least one plate shape Part, wherein, the plate shape discrete component have it is high to the ion of alkali metal or alkali metal, the tolerance of the especially erosion of lithium, Wherein, at least one plate shape discrete component contains or comprises lithium.

3. being less than 2mm electric storage system in particular according to the thickness described in claim 1 or 2, it includes at least one plate shape point Vertical element, wherein, the plate shape discrete component has high to the ion of alkali metal or alkali metal, the tolerance of the especially erosion of lithium Property, wherein, the Li of at least one plate shape discrete component₂O content be 7.0 weight % or following, be preferably 5.2 weight % or Below, 2.5 weight % or following, very particularly preferably 0.5 weight % or following are particularly preferably, are most preferably 0.2 weight % or following is measured, wherein, Li₂O content is at least 0.1 weight %, and wherein, lithium concentration can be in the plate shape discrete component Change on cross section.

10. electric storage system according to any one of claim 1 to 9, wherein, at least one plate shape discrete component Mixture or compound including at least one oxide or including many oxide.

11. electric storage system according to any one of claim 1 to 10, wherein, at least one discrete member of plate shape Part includes SiO₂As oxide.

12. in particular according to the electric storage system any one of claim 1 to 11, wherein, at least one plate shape point Vertical element has to be formed with what weight % was counted below：

Wherein, MgO, CaO, SrO and BaO content and in 8 weight % into 18 weight % scope, and wherein, may be used also Including in impurity or the necessary additive related to technique, the other components of such as fining agent form, wherein, these components Summation is not higher than 2 weight %.

13. in particular according to the electric storage system any one of claim 1 to 12, wherein, relative to diameter in ＞ 100mm Scope in, especially lateral dimension be 100mm100mm chip or substrate size, preferably with respect to diameter ＞ 200mm's In scope, especially lateral dimension be 200mm200mm chip or substrate size, particularly preferably relative to diameter in ＞ 400mm Scope in, chip or substrate size when especially lateral dimension is 400mm400mm, the element have no more than 25 μm, Preferably no greater than 15 μm, the thickness change for being especially preferably no more than 10 μm and being very particularly preferably not more than 5 μm.

14. the electric storage system according to any one of claim 1 to 13, it is characterised in that at least one plate shape The vapor transmission rate (WVTR) of discrete component is ＜ 10^-3g/(m²D), preferably ＜ 10^-5g/(m²D) and particularly preferably ＜ 10^-6g/(m²·d)。

15. the electric storage system according to any one of claim 1 to 14, wherein, at least one discrete member of plate shape The thickness of part is less than 2mm, preferably smaller than 1mm, particularly preferably less than 500 μm, is very particularly preferably less than or equal to 200 μ M, and most preferably no greater than 100 μm.

16. the electric storage system according to any one of claim 1 to 15, wherein, it is in 350 DEG C of temperature and frequency In the case of 50Hz alternating current, the ratio resistance of at least one plate shape discrete component is more than 1.010⁶Ohm·cm。

17. the electric storage system according to any one of claim 1 to 16, wherein, at least one discrete member of plate shape The peak load temperature θ of part_MaxIt is at least 300 DEG C, preferably at least 400 DEG C, very particularly preferably at least 500 DEG C.

18. the electric storage system according to any one of claim 1 to 17, wherein, at least one discrete member of plate shape The thermal linear expansion coefficient α of part is 2.010^-6/ K to 1010^-6/ K, preferably 2.510^-6/ K to 9.510^-6/ K and especially It is preferred that 3.010^-6/ K to 9.510^-6In/K scope.

19. the electric storage system according to any one of claim 1 to 18, wherein, at least one discrete member of plate shape The peak load temperature θ of part_MaxMeet following relation with thermal linear expansion coefficient α product：600·10^-6≤θ_Max·α≤ 8000·10^-6, particularly preferred 80010^-6≤θ_Max·α≤5000·10^-6。

20. the electric storage system according to any one of claim 1 to 19, wherein, at least one discrete member of plate shape Part is glass.

21. electric storage system according to claim 20, wherein, at least one plate shape discrete component passes through smelter Skill and subsequent moulding process and form plate shape.

22. electric storage system according to claim 21, wherein, subsequent moulding process is pulling method.

23. a kind of plate shape discrete component suitable for being used electric storage system, wherein, the plate shape discrete component has height To the ion of alkali metal or alkali metal, the tolerance of the especially erosion of lithium, wherein, the plate shape discrete component has following groups Into the composition is characterised by the weight % of highest 2 TiO₂Content, preferably up to 0.5 weight % TiO₂Content, Yi Jifei Often particularly preferably without TiO₂。

24. in particular according to described in claim 23 suitable for the plate shape discrete component used electric storage system, wherein, institute State plate shape discrete component have it is high to the ion of alkali metal or alkali metal, the tolerance of the especially erosion of lithium, wherein, the plate Shape discrete component includes lithium or including lithium.

25. in particular according to described in claim 23 or 24 suitable for the plate shape discrete component used electric storage system, its In, the plate shape discrete component have it is high to the ion of alkali metal or alkali metal, the tolerance of the especially erosion of lithium, wherein, The Li of the plate shape discrete component₂O content is 7.0 weight % or following, is preferably 5.2 weight % or following, particularly preferably 2.5 weight % or following, very particularly preferably 0.5 weight % or following, it is most preferably 0.2 weight % or following, wherein, Li₂O content is at least 0.1 weight %, and wherein, in addition, lithium concentration can be on the cross section of the plate shape discrete component Change.

It is 26. discrete suitable for the plate shape used electric storage system preferably according to any one of claim 23 to 25 Element, wherein, the surface structure is into being lazy for the material contacted with the surface at least one surface of the element Property and/or with reduction degree permeable and/or be impermeable.

27. the plate shape discrete component according to claim 26 suitable for being used electric storage system, wherein, it is described extremely Lack a surface structure into barrier.

28. the plate shape discrete component according to claim 27 suitable for being used electric storage system, wherein, the screen Barrier layer is configured to the barrier for metal diffusion.

29. the plate shape discrete component according to claim 28 suitable for being used electric storage system, wherein, the screen Barrier layer is configured to the barrier for alkali metal diffusion.

30. the plate shape discrete component according to claim 29 suitable for being used electric storage system, wherein, the screen Barrier layer has at least one alkali metal to be formed by doping or overdoping.

31. according to any one of claim 23 to 30 suitable for the discrete member of the plate shape used electric storage system Part, wherein, the element includes the mixture or compound of at least one oxide or many oxide.

32. the plate shape discrete component according to claim 31 suitable for being used electric storage system, wherein, it is described extremely A kind of few oxide is SiO₂。

33. according to any one of claim 23 to 32 suitable for the discrete member of the plate shape used electric storage system Part, wherein, at least one plate shape discrete component has to be formed with what weight % was counted below：

Wherein, MgO, CaO, SrO and BaO content and in 8 weight % into 18 weight % scope, and wherein, may be used also Including the other components in the related additive of impurity or necessary technique, such as fining agent form, wherein, these components it is total With not higher than 2 weight %.

34. according to any one of claim 23 to 33 suitable for the discrete member of the plate shape used electric storage system Part, wherein, relative to diameter in ＞ 100mm scope, especially lateral dimension be 100mm100mm chip or substrate chi It is very little, preferably with respect to diameter in ＞ 200mm scope, especially lateral dimension be 200mm200mm chip or substrate chi It is very little, particularly preferably relative to diameter in ＞ 400mm scope, especially lateral dimension be 400mm400mm chip or substrate Size, the thickness change of the element are no more than 25 μm, preferably no greater than 15 μm, especially preferably no more than 10 μm and very special You Xuanbu great Yu not be 5 μm.

35. the plate shape discrete component according to any one of claim 23 to 34, wherein, the thickness of the element is less than 2mm, preferably smaller than 1mm, it is particularly preferably less than 500 μm, is very particularly preferably less than or equal to 200 μm, and most preferably not More than 100 μm.

36. according to any one of claim 23 to 35 suitable for the discrete member of the plate shape used electric storage system Part, wherein, vapor transmission rate (WVTR) is ＜ 10^-3g/(m²D), preferably ＜ 10^-5g/(m²And particularly preferred ＜ d) 10^-6g/(m²·d)。

37. according to any one of claim 23 to 36 suitable for the discrete member of the plate shape used electric storage system Part, wherein, in the case of the alternating current of 350 DEG C of temperature and frequency for 50Hz, ratio resistance is more than 1.010⁶Ohm· cm。

38. according to any one of claim 23 to 37 suitable for the discrete member of the plate shape used electric storage system Part, wherein, peak load temperature θ_MaxIt is at least 300 DEG C, preferably at least 400 DEG C and very particularly preferably at least 500 ℃。

39. according to any one of claim 23 to 38 suitable for the discrete member of the plate shape used electric storage system Part, wherein, thermal linear expansion coefficient α is 210^-6/ K to 1010^-6/ K, preferably 2.510^-6/ K to 9.510^-6/ K, He Te Not preferably 3.010^-6/ K to 9.510^-6In/K scope.

40. according to any one of claim 23 to 39 suitable for the discrete member of the plate shape used electric storage system Part, wherein, peak load temperature θ_MaxMeet following relation with thermal linear expansion coefficient α products：

41. according to any one of claim 23 to 40 suitable for the discrete member of the plate shape used electric storage system Part, wherein, the element is glass.

It is 42. a kind of discrete suitable for the plate shape used electric storage system according to any one of claim 23 to 41 The manufacture method of element, it includes, and carries out melting process and subsequent thermoforming process.

43. it is according to claim 42 suitable for the manufacture method of the plate shape discrete component used electric storage system, Characterized in that, the thermoforming process is pulling method.

44. the plate shape discrete component according to any one of claim 23 to 41 is used as the use of substrate in electric storage system On the way.

45. the plate shape discrete component according to any one of claim 23 to 41 is used as overhead plate in electric storage system Purposes.

46. the plate shape discrete component according to any one of claim 23 to 41 is used as overcover in electric storage system Purposes.

47. a kind of glass suitable for applying the plate shape discrete component electric storage system, wherein, the glass has as follows Composition, the composition include low TiO₂Content, wherein, the TiO₂Content is preferably smaller than 2.0 weight %, preferably smaller than 0.5 weight Measure % and preferably without TiO₂。

48. in particular according to the glass suitable for applying the plate shape discrete component electric storage system described in claim 47, Wherein, the glass has following composition, and the composition is comprising lithium or including lithium.

49. in particular according to the glass suitable for applying the plate shape discrete component electric storage system described in claim 47 or 48 Glass, wherein, Li₂O content be 7.0 weight % or following, be preferably 5.2 weight % or following, particularly preferably 2.5 weight % or Below, 0.5 weight % or following and most preferably 0.2 weight % or following is very particularly preferably, wherein, Li₂O content is extremely Few 0.1 weight %, and wherein, lithium concentration can change on the cross section of the plate shape discrete component.