KR20130130056A - Lithium-ion rechargeable battery comprising a glass-based material for targeted leaching of getter substances - Google Patents

Abstract

Lithium ion rechargeable batteries are specified that include at least one positive electrode, a negative electrode, a separator, and an electrolyte, and include at least one glass-based material that is filterable upon contact with the electrolyte while substantially maintaining cell function. In this way, it is possible in particular to release substances suitable for HF gettering.

Description

LITHIUM-ION RECHARGEABLE BATTERY COMPRISING A GLASS-BASED MATERIAL FOR TARGETED LEACHING OF GETTER SUBSTANCES}

The present invention relates to a lithium ion rechargeable battery having at least a positive electrode, a negative electrode, a separator and at least one cell in which an electrolyte is contained.

The lithium ion rechargeable battery includes a positive electrode and an electrode (anode / cathode), a separator for preventing an electric short circuit, and at least one cell in which an electrolyte is contained therein. The electrolyte is usually a liquid electrolyte, more rarely a polymer electrolyte, and these electrolytes allow for Li ion ion migration.

Lithium ion cells are in fact beneficial energy stores with long life, low self-discharge, high specific storage capacity, and operating ranges from about -20 ° C to + 85 ° C under normal conditions.

Other uses of lithium ion rechargeable batteries require improvements in rechargeable batteries with regard to safety, cost and weight. The latter is particularly necessary in view of increasing specific energy or power density.

The lifetime of lithium ion rechargeable batteries during cycling and also with respect to the general operating life (calendar life) also plays an important role. An effect of deteriorating the life is an increase in the formation of a surface layer (SEI layer), for example, on the anode, in particular due to increasingly high internal resistance.

Moreover, deterioration of cell materials or components by the HF formed is an important mechanism that deteriorates lifespan. The formation of HF depends in particular on the water content in the cell, which reacts with the fluorine-containing electrolyte salt. Moisture can be introduced through the cell manufacturing process or by uncontrolled diffusion of moisture through the cell housing. Fluorine can cause damage in the form of HF to be formed, as well as the formation of sparingly soluble LiF. Due to the precipitation of LiF, lithium in the electrolyte is no longer available for charge transport in the cell, which results in minimization of conductivity and thus also in cell performance.

Exemplary reactions or reaction equilibria for electrolyte salts are

to be.

Generally, additives are added to the liquid electrolyte to also inhibit these and other interfering cell-chemical processes. Thus, in particular, low temperature additives, SEI formation promoters or control agents, flame retardant additives, wetting agents, anion receptors, overcharge additives, water / acid scavengers, additives for smooth Li deposition, and the like are added. . The additive is in fact an organic, aromatic or organometallic compound or molecule that usually comprises only halogen or sulfur groups. In addition, additives with organic components are sometimes toxic during handling and during production and uncontrolled use. Such additives are also expensive, flammable, at least only have very low temperature resistance, or are insoluble. Examples that may be mentioned in this regard are heptamethyldisilazane, an additive for preventing hydrogen fluoride (HF) that dissolves as a fluorinated salt even at 85 ° C. (J. of Power Source, 189 (2009) 685-688).

In some cases, oxide additives such as TiO ₂ are mentioned, but so far they were unacceptable in use due to their electrochemical instability.

Another disadvantage of current additive solutions is the lack of flexibility with regard to the inclusion of the additives mentioned. In the form of a liquid component or alternatively in solid form completely dissolved in the electrolyte, it is not possible to limit the effect to the location of use or to make it stronger at the location of use if necessary. One example is the use of a processable, ie incorporable, solid functional additive for the local protection of the HF sensitive cathode material LiMn ₂ O ₄ (abbreviated as LMO) for HF. Electrochimica Acta No. 51 (November 2006), 2912-2919, S. Myung-T such as a low, "Imprevement of cycling performance of Li 1 .1 Mn 1 .9 O 4 at 60 ℃ by NiO Addition for Li-ion Secondary battery" NiO is added for this purpose as described in. This may be included in the assembly, if desired, by coating the electrode particles or the entire electrode, or by mixing to the cathode material. HF-stable coating materials have the disadvantage of containing transition metals, thus increasing costs.

Electrochemistry Communications 4 (2002), 344-348, Y.-K.Sun such as low, "Electrochemical performance of nano-sized ZnO-Coated LiNi 0 .5 Mn 1 .5 O 4 spinel as 5 V materials at elevated temperatures Discloses the addition of ZnO as a coating material on a cathode, for example for the purpose of scavenging (HF). In contrast to pure inert coatings, ZnO apparently acts as a functional additive, ie reacts with HF present.

It is also known from EP 0 903 798 A1 to use BF ₃ as a reaction additive to improve the electrochemical properties. EP 1 567 452 B1 and DE 69700312 T2 describe the addition of B ₂ O ₃ as an additive to Li ion rechargeable batteries. The above addition increases the lifetime with respect to dose maintenance, but the cause is still unknown. Inclusion of B ₂ O ₃ can be effected by the addition of a liquid electrolyte or by inclusion in an anode or cathode or separator compound. Thus the material can be included at any location in the cell as long as it is exposed to the electrolyte. The relationship with scavenging of HF is not presented. A disadvantage of the use of pure boron oxide is the influx of significant amounts of water adhesively bonded to the surface. This hygroscopicity should be reduced to a minimum by an appropriate and costly drying step, because otherwise the life of the cell is significantly reduced.

As an alternative, the LMO can also be coated with type Li ₂ OB ₂ O ₃ (LBO) glass (Electrochimica Acta 51 (2006), 3872-3883, C. Li et al., Et al., “Cathode materials modified by surface coating for lithium ion Batteries "). The glass has the advantages of good wettability, low viscosity in the molten state and good ionic conductivity, and provides protection against reactive attack by liquid electrolytes.

The solutions described here are passivating protection solutions for batteries, and are not, for example, HF free problems in cathode material environments. Thus, the coating material must be ion conductive as long as it completely encloses the particles.

In view of this background, it is an object of the present invention to provide an improved lithium ion rechargeable battery with additives which are inexpensive, non-toxic and thermally stable for improved performance. Preferably, it should also be possible to make HF free of problems.

This object comprises lithium ions having at least one cell, containing at least a positive electrode, a negative electrode, a separator and an electrolyte, and having a glass-based material which is filterable upon contact with the electrolyte while keeping the cell function basically maintained. Achieved by a rechargeable battery.

The object of the present invention is achieved perfectly in this way.

According to the present invention, the addition of the filterable glass-based material upon contact with the electrolyte enables the active effective material to be released into the electrolyte, as a result of which cell performance can be increased. For the purposes of the present patent application, glass-based materials are glass or glass-ceramic, ie glass crystalline microstructures made through controlled heat treatment during the melting process and cooling of the melt or in subsequent process steps. The preparation of glass or glass-ceramic by sol-gel process is also contemplated.

The use of glass-based materials means inorganic additives that are nontoxic and thermally stable over a long period of time. In addition, low cost solutions can also be achieved. The material can be tailored for each use to enable the release of specific products into the electrolyte.

In this context, the term " leachable " means that the material has a certain loss of mass units per unit time upon contact with the electrolyte. Here, the filtration rate upon contact with the electrolyte may initially be at least about 1 μg / h, in particular at least 10 μg / h or at least 25 μg / h. The above filtration takes place during normal operation of the cell, ie even under normal operating conditions (ambient temperature) with no generation of current. The maximum filtration rate upon contact with the electrolyte is 3000 μg / h or less, in particular 2000 μg / h or less, preferably 1000 μg / h or less.

In fact, the filtration process can be configured such that the composition of the mass depleting material does not change by filtration. In such a case, the same filtration of the material takes place.

However, if the composition of the solid changes due to filtration or if the chemical composition of the filtered material does not correspond to the chemical composition of the starting material, this will hereinafter be referred to as non-identical filtration or selective filtration. This means that one or more components preferentially dissolve from the material.

Selective filtration of the material allows components that perform a particular function in the cell's chemistry to preferentially enter the electrolyte. Here, the functional effectiveness may be increased or adjusted by selective filtration of the material.

Depending on the material used, the filtration rate may remain nearly constant over a defined period of time, and may change with time, in particular with time.

In another aspect of the invention, the material releases a getter substance to scaveng HF when in contact with the electrolyte. In this application, "scavenging" means that the undesirable or damaging material is not withdrawn from the system or inert or problematic. However, the cell continues to function. In particular, the material may be of a configuration that combines with fluorine to form a species that is inert with respect to the electrolyte.

Thus, it is not necessarily essential that the getter material be first released from the material. Direct bonding of fluorine with the glass material can also occur, which forms a species or material that is inert to the electrolyte.

In this way fluorine, which is detrimental to the performance of the cell, is bound to or converted into a species which is not a problem.

In this regard, Japanese Patent Publication No. JP 2005-11614 can be referred to. This describes, for example, immobilization of Li by reaction with SiO ₂ containing glass in case of excessive HF production at excessively high operating temperatures. In the above case, the separator consists of 50 to 90% by weight of glass, which comprises 40 to 90% by weight of SiO ₂ , ie mainly consisting of SiO ₂ . In the case of excess glass of HF, SiO ₂ reacts directly with HF to form poorly soluble Li ₂ SiF ₆ . Electrochemical cell activity is irreversibly suppressed in this way, ie the electrochemical cell will not function. In addition, the provided glass is not “filterable” glass in the sense of the present application since the glass according to JP 2005-11614 does not show weight loss during normal operation.

In a further embodiment of the invention, the material liberates the boron containing material upon contact with the electrolyte, in particular oxygen bonded boron.

The glass of boron has been found to be very suitable for scavenging HF, or the presence of boron in the glass has been found to promote the binding of harmful fluorine.

In another aspect of this embodiment, the material releases B ₂ O ₃ upon contact with the electrolyte, and then this B ₂ O ₃ is present in complex form as cell compatible boron-fluorine species in the electrolyte. The initial filtration rate upon contact with the electrolyte may be about at least 3 μg / h, in particular at least 5 μg / h.

The glass of B ₂ O ₃ at the above filtration rate has been found to enable complete scavenging of HF, thus ensuring a significant improvement in cell performance.

In another aspect of this embodiment, the material releases Al ₂ O ₃ upon contact with the electrolyte. Here, the initial filtration rate upon contact with the electrolyte may be about at least 1 μg / h, in particular 2.5 μg / h.

In another embodiment of the invention, the material has a phase-demixed region. The phase separation zone is preferably filterable. It is also possible to use glass ceramics, ie glass-crystallite microstructures made through the melting process and controlled heat treatment.

In this way, filtration of the material can be simplified or more selective. The use of phase-separated glass or phase-separated glass-ceramic makes it very good to meet a variety of requirements. A suitable T-t profile during the cooling of the gas and / or after the cooling of the gas makes the component unstable to electrolyte attack particularly applicable in the solid.

The filterable material according to the invention is included in the cell in virtually any manner.

Accordingly, the material may be included in the cell, for example as a powder additive. The material may be included, for example, alone or as a coating on the polymer membrane in the zone of the separator. The material may also be included as a component of the filler / composite mixture. The material may also be included as a coating of the electrode. Mixing of particles into the electrode material and bonding coating on the powder outflow lead foil are also contemplated. In addition, coating of the cell enclosure housing is also contemplated. Other variations can be considered.

Accordingly, the material may also be a component of the separator membrane, a component of the nonwoven separator, or a component of the separator composite. In this context, a "nonwoven" is a fiber felt filter. The term "membrane" refers to a porous polymer component produced by a wet or dry fabrication process. The separator composite is an intimate mixture of polymer and filler that is applied to the auxiliary film as a slurry and cured as the pores are formed.

In a preferred embodiment of the invention, after filtration of the material, a thermally stable remaining phase, in particular the remaining glass phase, which is resistant to the electrolyte remains.

This is for example the remainder of the porous or thermally stable phase, which phase remains for example as a material for the heat resistant coating, as a wetting agent or as an additive to the composite.

Thus, the remaining phase can be, for example, a very lightweight porous skeleton shaped structure. This structure thus remains in place once bound to the support by a binder or the like. The remaining material or remaining phase after filtration can thus be, for example, components of the separator or electrodes, coating of the housing, and the like.

The material according to the invention preferably has a certain degree of reactivity to the solvent component of the electrolyte or to the Li electrolyte salt. The solvent component can be, for example, a carbonate such as ethylene carbonate, dimethyl carbonate or diethyl carbonate.

In another embodiment of the invention, the material comprises at least 1% by weight of B ₂ O ₃ , Preferably greater than 3% by weight B ₂ O ₃ , very preferably greater than 4.5 wt% B ₂ O ₃ .

The glass of B ₂ O ₃ from the material Preferably it makes it possible to achieve HF scavenging.

The material preferably comprises at least SiO ₂ in addition to boron.

Possible materials suitable for the purposes of the present invention have, for example, at least the following composition (in weight% relative to oxide base).

SiO ₂ 45 to 60,

B ₂ O ₃ 5-30,

Al ₂ O ₃ 5 to 30.

In addition, the material may comprise, for example, 20-30% by weight of BaO. The material may also comprise 0 to 10 wt% ZrO ₂ , in particular at least 0.1 wt% ZrO ₂ , in particular at least 1 wt% ZrO ₂ .

One material suitable for the purposes of the present invention has, in particular, the following composition (in weight% relative to oxide base).

SiO ₂ 48 to 58,

B ₂ O ₃ 7 to 13,

Al ₂ O ₃ 7 to 13,

BaO 22-28,

ZrO ₂ 0.1 to 8.

The material substantially comprises alkali metal oxides, but preferably does not contain alkali metal oxides, except for incidental impurities and Li ₂ O. Accordingly, the material may comprise Li ₂ O, but preferably does not include Na ₂ O, K ₂ O, Rb ₂ O, Cs ₂ O. In this regard, incidental impurities are incidental impurities present in amounts of less than 0.5% by weight, in particular less than 0.1% by weight, in particular less than 0.05% or even less than 0.01% by weight.

Otherwise, the life of the cell may be shortened due to the irreversible inclusion of Na or K, Rb or Cs in the crystal structure of the electrode material.

For the purposes of the present invention, if a composition is given to include or have certain components, it can be interpreted to mean that there may always be any other components present (open composition).

However, in another embodiment of the present invention, a given composition is to be interpreted to mean that in each case only certain components are present (closed composition), except for the inevitable impurities due to the nature of the glass making. Depending on the purity of the raw materials used, the aforementioned unavoidable impurities are limited to 1% by weight or less, preferably 0.5% by weight, more preferably 0.1% by weight or even 0.05% by weight.

For the purposes of the present invention, if the composition is given in the form of specific components, such a composition will always contain only certain components (closed composition), but may contain unavoidable impurities due to the nature of the glass fabrication. Is interpreted to mean that the. Depending on the purity of the raw materials used, the aforementioned unavoidable impurities are limited to 1% by weight or less, preferably 0.5% by weight, more preferably 0.1% by weight or even 0.05% by weight.

For the purposes of the present invention, if a particular component is listed in the examples, this enumeration is to be interpreted as a closed composition, but at this point the clue that there may be unavoidable impurities due to the glass fabrication properties. Depending on the purity of the raw materials used, the aforementioned unavoidable impurities are limited to 1% by weight or less, preferably 0.5% by weight, more preferably 0.1% by weight or even 0.05% by weight.

Moreover, the above-described features of the present invention and the features of the present invention described below can be used not only in the combinations shown in each case but also in other combinations or for the purposes of the present invention without departing from the scope of the present invention. Of course.

The invention will be explained below by way of example and with reference to the drawings.

According to the present invention there is provided an improved lithium ion rechargeable battery with additives which are inexpensive, non-toxic and thermally stable, and it is also possible to make HF trouble free in such rechargeable batteries.

1 is a view schematically showing a lithium ion rechargeable battery according to the present invention.
2 shows a cyclic current voltage measurement of materials according to the invention compared with a comparative example.
3 shows NMR measurements for materials according to the invention in comparison with comparative examples.
FIG. 4 shows an abrasive sample of phase separation material (AB3) with a clearly recognizable zone of spinodal separated Li borate.

1 schematically shows an exemplary lithium ion rechargeable battery, generally indicated at 10 . The lithium ion rechargeable battery 10 has a housing 18 having two electrode lead-throughs 12. The electrode leadthrough 12 is connected to a first electrode 14 made of Cu and coated with an anode material and a second electrode 16 which may be an Al power outlet foil coated with a cathode material. Exemplary anode materials are hard carbon, carbon-containing phases such as graphite or Li titanate, examples of cathode materials are sheet oxides such as LiCoO ₂ , spinels such as LiMn ₂ O ₄ or olivine phases or other transition metals such as LiFePO ₄ Mixed crystal phases or mixtures thereof with cations. Between the electrodes 14, 16 is a separator 22, which may be a polymer membrane or a nonwoven polymer with (co) coated or (co) penetrated glass particles. In this case, the lithium ion rechargeable battery only has a single cell surrounded by the housing 18 and filled with the electrolyte solution 20. According to the invention, a filterable glass is included in the cell, which can be made, for example, as at least one of the electrodes 14, 16 or as a coating on the separator 22. Mixing of particles into the electrode material and co-coating of the power outlet foil are also contemplated inclusion forms. In this case, reference numeral 24 denotes the coating of the inner surface of the housing 18 by the filterable glass according to the invention. The above embodiment provides a very large glass surface area and thus high efficiency. As indicated above, any other inclusion form is possible for the glass according to the present invention.

Various examples (EX) compared to Comparative Example (CE) are summarized in Table 1.

Example 1

As a first example, glass (EX4) with the following composition (in weight percent based on oxide base) was used:

SiO ₂ 55

B ₂ O ₃ 10

Al ₂ O ₃ 10

BaO 25.

In order to confirm the HF scavenging performance of the material in the lithium ion cell, it is possible to use an electrochemical test. Here, a current-voltage curve is recorded which represents the reactive species (eg HF) in peak form and at higher overall current values. In the field of lithium ion cells, cyclovoltammetry is commonly employed as an electrochemical method. In this method, a cycle is performed to measure the forward and reverse reactions of the species. In this case, the cycle started at 3 V, reached 0.05 volts, and returned to 3 V again. The applied voltage causes a current in the system, which is measured.

In order to be able to make cyclic current voltage measurements on materials in the environment of lithium ion cells, these materials must be in contact with the appropriate electrolyte in the appropriate form. In this example, an electrolyte based on LiPF ₆ was used.

Three electrode configurations are commonly used for electrochemical measurements. There is a need for a working electrode (including the material to be tested), a counter electrode made of lithium, and a reference electrode made of lithium. To fabricate the working electrode, a mixture of the material to be tested, conductive carbon black and a suitable binder (eg PVDF) is first introduced into a suitable solvent (eg NMP). For mixtures of materials, conductive carbon blacks and binders, it is possible to use, for example, a mixing ratio of 80: 12: 8. The ratio of mixture to solvent is 25:75. For example, the liquid mixture is applied to a suitable material (eg copper) by doctor blade coating. The electrode is then dried and placed in a suitable measuring cell together with the Li reference electrode and the Li counter electrode. Due to the use of lithium and LiPF ₆ for the construction of the measuring cell, the operation must be carried out under protective gas in the glove box. After fabrication of the measuring cell, the three electrodes are connected to the appropriate electrostatic potential and the current-voltage curve is recorded. Here, HF appears in peak form (range from 2.0 to 3.0 V) and in this range with increased current.

2 shows two examples of measurement curves showing that scavenging of HF occurs when suitable materials are used. The following figures show the current-voltage curves of two different working electrodes. When the working electrode is only coated with carbon black and a binder (no glass or alternative material) (dashed line), the maximum current and the most pronounced peak can be seen. On the other hand, if a suitable glass (EX4) is applied to the working electrode together with the carbon black and the binder (solid line), the current is much lower and the clear peaks are no longer visible. This proves successful scavenging of HF by glass.

NMR spectroscopy makes it possible to characterize the chemical environment of the nucleus due to the magnetic resonance properties of the nucleus, thus recognizing the molecular structure and identifying the compound. Moreover, the compounds can be quantified. Storage test in liquid electrolyte of lithium ion rechargeable battery with 1000 mg / kg of water (here, 1 M of LiPF ₆ at EC: DMC = 1: 1 (m / m) at 60 ° C. for 30 days). , It can be estimated that free hydrogen fluoride (HF) is formed by hydrolysis of LiPF ₆ . The formation of HF is markedly supported by the addition of water. If the material formed of the glass (EX4) is stored in a moist electrolyte for a long time in this stability test, the content of dissolved fluorine-containing compound can be measured by ¹⁹ F-NMR, and the concentration-time profile of various fluorine species Is obtained. In spite of the hydrolysis of LiPF ₆ caused by the addition of water, which resulted in significant HF formation in the absence of glass (B), no free fluorine ions (labeled HF) were found after 30 days. This demonstrates the HF scavenging properties.

This property is not common for all materials such as glass, but only glass having a specific composition and preferably containing at least boron is suitable. The results of the time dependent NMR measurement are shown in FIG. 3. The content of fluorine in the electrolyte (here relative proportion of total fluorine species dissolved) as a measure of HF formation is plotted in ordinate. It can be seen that HF is not released in the state where the glass EX4 is present.

Claims (26)

A lithium ion rechargeable battery, comprising: at least one glass-based material that has at least a positive electrode, a negative electrode, a separator, and at least one cell containing an electrolyte, and which is filterable upon contact with the electrolyte while the cell function is basically maintained Lithium ion rechargeable battery included. The lithium ion rechargeable battery according to claim 1, wherein the material has a filtering rate of at least 1 μg / h, in particular at least 10 μg / h or at least 25 μg / h upon contact with the electrolyte. The lithium ion rechargeable battery according to claim 1, wherein the material has a filtration rate of at most 3000 μg / h, in particular at most 2000 μg / h, preferably at most 1000 μg / h upon contact with the electrolyte. 4. A lithium ion rechargeable battery according to claim 2 or 3, wherein the filtration rate changes over time, in particular decreasing over time. The lithium ion rechargeable battery according to any one of claims 1 to 4, wherein the composition of the material is changed by filtration. 6. The lithium ion rechargeable battery of claim 1, wherein the material releases a getter substance to scaveng HF when in contact with an electrolyte. 7. The lithium ion rechargeable battery according to claim 1, wherein the material binds fluorine to form a species that is inert with respect to the electrolyte. The lithium ion rechargeable battery according to claim 1, wherein the material liberates the boron containing material when in contact with the electrolyte, in particular liberating oxygen bonded boron. The lithium ion rechargeable battery according to claim 1, wherein the material has a mass loss of B ₂ O ₃ of at least 3 μg / h, in particular of at least 5 μg / h when in contact with an electrolyte. 10. The lithium ion rechargeable battery according to any one of claims 1 to 9, wherein the material has a phase demixed region. The rechargeable lithium ion battery of claim 10, wherein the phase separation zone is preferably filterable. 12. The lithium ion rechargeable battery according to any one of claims 1 to 11, wherein the material is glass or glass-ceramic. 13. The lithium ion rechargeable battery of claim 12 wherein the material is glass-ceramic and the crystallites are preferably filterable. The material according to claim 1, wherein the material is included in the cell as a powder additive, in the region of the separator, as a component of the filler synthesis mixture, or as a coating of the electrode, A lithium ion rechargeable battery that is applied to a power outlet lead as a mixture with an electrode material or is included as a coating on a housing surrounding a cell. 15. The lithium ion rechargeable battery of claim 1, wherein the material is a component of a separator membrane, a nonwoven separator, or a separator composite. The lithium ion rechargeable battery according to claim 1, wherein after filtration of the material, a residual heat resistant phase, in particular a remaining glass phase, resistant to the electrolyte remains. The lithium ion rechargeable battery of claim 16, wherein the remaining filtered phase is porous and thermally stable for use as an additive to a material, wetting agent or composite for a heat resistant coating. Claim 1 to claim 17 according to any one of claims, wherein the material is a lithium-ion rechargeable battery comprises at least 1% by weight, preferably at least 3 wt%, more preferably from 4.5% by weight of B ₂ O ₃ . 19. The lithium ion rechargeable battery according to any one of claims 1 to 18, wherein the glass contains at least SiO ₂ in addition to boron. 20. The material according to any of claims 1 to 19, wherein the material is at least the following components (in weight percent units relative to the oxide base):
SiO ₂ 45 to 60
B ₂ O ₃ 5 to 30, and
Al ₂ O ₃ 5 to 30
A lithium ion rechargeable battery comprising a. The lithium ion rechargeable battery of claim 20, wherein the material further comprises 20-30 wt.% BaO. 22. The method according to any of claims 18 to 21, wherein the material comprises from 0 to 10% by weight of ZrO ₂ , in particular at least 0.1% by weight ZrO ₂ , in particular at least 1% by weight. A lithium ion rechargeable battery further comprising ZrO ₂ . 21. The method of claim 20, wherein the material is of the following composition (in weight percent units based on oxide base):
SiO ₂ 48 to 58
B ₂ O ₃ 7 to 13
Al ₂ O ₃ 7 to 13
BaO 22 to 28
ZrO ₂ 0.1 to 8
Lithium ion rechargeable battery having. 24. The lithium ion rechargeable battery according to any one of claims 1 to 23, wherein the material does not contain incidental impurities and alkali metal oxides, except Li ₂ O. The lithium ion rechargeable battery according to claim 1, wherein the material has a mass loss of Al ₂ O ₃ of at least 1 μg / h, in particular 2.5 μg / h when in contact with an electrolyte. The mass of Al ₂ O ₃ according to any one of the preceding claims, wherein the material is at most 3000 μg / h, in particular at most 2000 μg / h, preferably at most 1000 μg / h when in contact with the electrolyte. Lithium ion rechargeable battery.

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