DE112020006564T5 - NAPHTHALINE-BASED LITHIUM COMPOUNDS, PROCESS FOR THEIR MANUFACTURE, USE THEREOF AS A SOLID ORGANIC CATALYST, AND USE THEREOF IN RECHARGEABLE NON-AQUEOUS LITHIUM AIR BATTERY CELLS - Google Patents

Abstract

The present invention relates to novel naphthalene-based compounds, processes for their preparation and their use as solid organic catalysts (SOC) in lithium-air battery cells to promote oxygen reactions. The invention also relates to a lithium-air battery cell, in which the positive electrode comprises an SOC according to the invention, and a battery pack with a plurality of lithium-air battery cells according to the invention. The use of a battery pack according to the invention as a rechargeable battery for vehicles such as electric and hybrid vehicles, electronic devices and stationary power generation devices is also part of the invention. Finally, the invention is directed to a vehicle, an electronic device and a stationary power generation device, which comprise a battery pack according to the invention.

Description

field of invention

The present invention relates to novel naphthalene-based compounds, processes for their preparation and their use as solid organic catalysts (SOC) in lithium-air battery cells to promote oxygen reactions. The invention also relates to a lithium-air battery cell in which the positive electrode contains an SOC according to the invention, and a battery pack having a plurality of lithium-air battery cells according to the invention. Furthermore, the use of a lithium-air battery cell according to the invention as a rechargeable battery for vehicles such as electric and hybrid vehicles, electronic devices and stationary power generation devices is part of the invention. Finally, the invention is directed to a vehicle, an electronic device and a stationary power generation device with a battery pack according to the invention.

Technological background

Rechargeable lithium batteries are of great interest due to their high energy density and high performance. In particular, rechargeable lithium-air batteries have attracted attention for electric and hybrid vehicles where high energy density is required. Lithium-air battery cells are used in various devices (such as computers and phones), in automobiles or stationary applications, and can be assembled into battery packs.

Rechargeable lithium-air batteries use the oxygen in the air as a cathode active material. Therefore, rechargeable lithium-air batteries can have a larger capacity compared to conventional lithium batteries containing a transition metal oxide (e.g., lithium cobaltate) as a cathode active material.

In metal-air batteries, the cathode active material, oxygen, is not contained within the battery. Instead, this material is provided by the surrounding atmosphere. Of course, such a system allows in principle a very high specific energy (energy provided by the battery per unit weight, usually given in Wh/kg in this technical field). In such batteries, depending on the catalyst, electrolyte, availability of oxygen, etc., the oxygen may be partially reduced to peroxide or fully reduced to hydroxide or oxide. When the negative electrode (anode) is lithium (Li), lithium peroxide (Li ₂ O ₂ ) or lithium oxide (Li ₂ O) can be formed.

• - Metallanode (beispielsweise Li enthaltend),
• - nichtwässriger Elektrolyt (beispielsweise ein Lithiumsalz enthaltend), und
• - Luftkathode.

A lithium-air battery cell generally consists of the following parts:

• - metal anode (e.g. containing Li),
• - non-aqueous electrolyte (for example containing a lithium salt), and
• - air cathode.

Other parts of the battery cell device such as current collectors on the anode and/or cathode side, a separator between the cathode-side electrolyte (catholyte) and anode-side electrolyte (anolyte), a barrier layer between a positive electrode (cathode) and an electrolyte, or between a negative electrode (anode) and an electrolyte may be present.

• - Vermeidung der Migration von löslichen Katalysatoren, die an der positiven Elektrode (Kathode) verwendet werden, zur Anode;
• - Absenkung der Hysterese durch Verringerung der Ladespannung und/oder Erhöhung der Entladespannung der Lithium-Luft-Batteriezelle durch Vermeidung der Degradation bzw. Verschlechterung des Elektrolyten;
• - Erhöhung der Kapazität der Lithium-Luft-Batteriezelle bei einer festen Rate.

The development of lithium-air battery cells has the following problems, among others:

• - avoidance of migration of soluble catalysts used on the positive electrode (cathode) to the anode;
• - Reduction of the hysteresis by reducing the charging voltage and/or increasing the discharging voltage of the lithium-air battery cell by avoiding the degradation or deterioration of the electrolyte;
• - Increasing the capacity of the lithium-air battery cell at a fixed rate.

Special separators can be used to avoid the migration of soluble catalysts at the anode. Lee et al. (Adv. Energy Mater., 2017, 1602417) propose the use of glass fiber separators (GF/C, Whatman) coated with a polymer blend of PEDOT:PSS [poly(3,4-ethylenedio xythiophene) polystyrene sulfonate] to avoid the migration of the soluble catalyst DMPZ (5,10-dihydro-5,10-dimethylphenazine) used for the Oxygen Evolution Reaction (OER). Qiao et al. (ACS Energy Lett. 2018, 3, 463-468) propose to avoid the shuttling of soluble catalysts to the Li anode by using a special separator based on a metal-organic framework framework, MOF) that blocks the soluble species is used.

Gao et al. propose 2,5-di-tert-butyl-1,4-benzoquinone (DBBQ) as a soluble catalyst to increase the performance rate of a non-aqueous lithium-air battery cell. The air electrode is a porous carbon electrode based on a gas diffusion layer (GDL) as the air cathode. The anode is LiFePO ₄ (Nature Materials, 2016, 15, 882) or Li protected by Ohara glass, which necessitates the use of a two-chamber cell (Nature Energy, Vol. 2, 17118 (2017)), but Li-metal cannot be used as anode because DBBQ would migrate there and cause problems at the anode.

Chen et al. report in Nature Chemistry, 2013, 5, 489 on tetrathiafulvalene (TTF) as a soluble catalyst and nano-porous gold as the air cathode. Partially charged LiFePO ₄ is used as an anode.

Kundu et al. (ACS Cent., Sci., 2015, 1, 510-515) use tris[4-(diethylamino)phenyl]amine (TDPA) as a soluble catalyst to promote the oxidation of LiO ₂ (loading process).

• - eine Schutzbarriere, um das Li-Metall vor Verunreinigungen durch lösliche Katalysatoren zu schützen, die sich an der Oberfläche des Li-Metalls ablagern und Keimbildungsstellen bilden können, die zur Bildung von Dendriten führen,
• - spezielle Separatoren, die die gelösten Species blockieren, oder
• - spezifisches Zellendesign, wie beispielsweise eine Zwei-Kammer-Zelle, die aus zwei Elektrolytkammern zusammengebaut ist, d. h. eine für die Anodenseite und die andere für die Kathodenseite, um die Li-Anode zu schützen.

The main disadvantage of the solutions proposed by the prior art is the use of a soluble catalyst, which does not allow the use of Li metal (without additional protection) as an anode. In fact, the migration of soluble catalysts at the anode degrades the performance and safety of lithium-air battery cells, necessitating the use of additional features such as

• - a protective barrier to protect the Li-metal from contamination by soluble catalysts that can deposit on the surface of the Li-metal and form nucleation sites leading to the formation of dendrites,
• - special separators that block the dissolved species, or
• - specific cell design, such as a two-chamber cell assembled from two electrolyte chambers, i.e. one for the anode side and the other for the cathode side to protect the Li anode.

Hase et al., Chem. Commun. 2016, 52, 12151-12154 further use methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MeO-TEMPO) as a soluble catalyst to promote the oxidation of Li ₂ O ₂ without parasitic reactions occurring on the electrochemical Loading are due to allow. However, the TEMPO molecule has to be chemically regenerated outside the battery cell at the end of the charging process, which is impractical since the battery cell has to be topped up with new electrolyte after each charging process.

Bergner et al., Phys. Chem. Chem. Phys., 2015, 17, 31769-31779 report the use of nitroxide catalysts such as 1-methyl-2-azaadamantane-N-oxyl (1-Me-AZADO). However, these nitroxides have the disadvantage that they are soluble in the electrolyte and thus degrade the anode of lithium-air battery cells.

• - die Kapazität der Li-O₂ Batteriezelle bei einer festen Rate erhöht,
• - die Wiederaufladbarkeit der Li-O₂ Batteriezelle und damit die Zyklisierbarkeit (engl. cyclability) der Batteriezelle erhöht,
• - die Ladeleistung, d. h. die Geschwindigkeit der (Ent-)Ladung der Batteriezelle, bei gleichzeitiger Beibehaltung einer angemessenen Kapazität erhöht,
• - ein einfacheres Batteriezellendesign ermöglicht, da der erfindungsgemäße SOC nicht löslich ist und daher keine Lithium-Schutzschicht, keinen speziellen Separator und keine Zwei-Kammer-Zelle benötigt,
• - der SOC wird innerhalb der Batteriezelle selbst regeneriert und kehrt in seinen Ausgangszustand zurück,
• - ermöglicht es, die Menge des an der positiven Elektrode (Luftkathode) verwendeten Kohlenstoffs zu verringern und somit die Korrosion des Kohlenstoffs zu vermeiden, die als Ursache für eine schlechte Wiederaufladbarkeit bekannt ist. Es ist bekannt, dass Kohlenstoff in Lithium-Luft-Batteriesystemen korrodiert und zur teilweisen Bildung von U₂CO₃ (Nebenreaktions-Entladeprodukt) anstelle von Li₂O₂ (ideales Entladeprodukt) führt.

The present invention solves all the problems of the prior art by providing a novel naphthalene-based compound used as a SOC in lithium-air battery cells that:

• - increases the capacity of the Li-O ₂ battery cell at a fixed rate,
• - increases the rechargeability of the Li-O ₂ battery cell and thus the cyclability of the battery cell,
• - increases the charging power, ie the speed of (dis)charging the battery cell, while maintaining an adequate capacity,
• - enables a simpler battery cell design, since the SOC according to the invention is not soluble and therefore does not require a lithium protective layer, no special separator and no two-chamber cell,
• - the SOC is regenerated within the battery cell itself and returns to its initial state,
• - makes it possible to reduce the amount of carbon used on the positive electrode (air cathode), thus avoiding carbon corrosion, known to be the cause of poor rechargeability. It is known that carbon in lithium-air battery systems corrodes and leads to the partial formation of U ₂ CO ₃ (side reaction discharge product) instead of Li ₂ O ₂ (ideal discharge product).

In addition, the SOC of the invention is inexpensive (compared to other catalysts based on gold, platinum or cobalt oxides used in lithium-air systems) and an environmentally friendly organic material that can be produced from renewable resources (biomass).

Summary of the Invention

The present invention relates in one aspect to a novel naphthalene-based compound represented by the specific formula (1) as defined below.

The invention further relates to a process for preparing such a specific compound of formula (1).

The use of such a specific compound of formula (1) as SOC in lithium-air battery cells is also part of the invention.

• - eine negative Elektrode (Anode), die ein Negativelektrodenaktivmaterial enthält;
• - eine positive Elektrode (Kathode), die Sauerstoff als ein Positivelektrodenaktivmaterial verwendet, und
• - ein nichtwässriges Elektrolytmedium, das zwischen der negativen Elektrode und der positiven Elektrode angeordnet ist;

wobei die positive Elektrode die Verbindung der Formel (1) als SOC umfasst.The invention also relates to a lithium-air battery cell comprising:

• - a negative electrode (anode) containing a negative electrode active material;
• - a positive electrode (cathode) using oxygen as a positive electrode active material, and
• - a non-aqueous electrolytic medium disposed between the negative electrode and the positive electrode;

wherein the positive electrode comprises the compound of formula (1) as SOC.

In another aspect, the invention relates to a battery pack containing a plurality of assembled lithium-air battery cells according to the invention.

The invention further relates to the use of a battery pack according to the invention as a rechargeable battery for electric and hybrid vehicles, electronic devices and stationary power generation devices.

Finally, the invention also relates to a vehicle, an electronic device and a stationary power generation device, which include a battery pack according to the invention.

character list

• shows the thermogravimetric analysis (TGA) of the tetra-lithium salt of 1,5-dihydroxy-2,6-naphthalenedicarboxylic acid (Li ₄ DHNDC) obtained with ( ) or without ( ) excess lithium methoxide (MeOLi).
• shows Fourier transform infrared spectroscopy (FT-IR) spectra of the precursor 1,5-dihydroxy-2,6-naphthalenedicarboxylic acid (H ₄ DHNDC) ( ) and Li ₄ DHNDC ( ).
• shows the scanning electron microscopy (SEM) images of Li ₄ DHNDC.
• shows the voltage (V versus Li ⁺ /Li) versus capacity (mAh.cm ^-2 ) for a lithium-air battery cell cycled at 0.2 mAh.cm ^-2 as described in Example 1 (Ex1). . cycled) compared to comparative examples 1, 2 and 3 (comparative example 1, comparative example 2, comparative example 3).
• shows the cycling of the lithium-air battery cell ( ) of Example 1 at a rate of 0.2 mAh.cm ^-2 , within the potential window 2.2 - 4.6 V versus Li ⁺ /Li and with a capacity limitation of 800 mAh.g ^-1 _SOC (~2.15 mAh.cm ^-2 ), and the retention of capacity versus the number of cycles ( ) from example 1.
• shows a comparison of the 1 ^st cycle of the lithium-air battery cell of Example 1 using a working electrode containing Li ₄ DHNDC as SOC obtained in argon (dotted line) or in oxygen (solid line) for electrodes containing a weight ratio of Carbon Super C65 : Li ₄ DHNDC of 7:2 included (galvanostatic discharge performed at 0.5 mAh.cm ^-2 ).
• is a schematic representation of a metal-air battery cell with an electrochemical cell within a headspace ( ) and a multi-cell metal-air battery pack within a gas compartment ( ), with: 11: gas space (dry air or pure oxygen), 12: metal anode, 13: cathode, 14: electrolyte/separator, 15: anode current collector and 16: cathode current collector.

Detailed description of the invention

wobei:

• - mindestens eines von R¹, R², R³, R⁴, R⁵, R⁶, R⁷ oder R⁸ eine Gruppe A, die eine permanente negative Ladung umfasst, ausgewählt aus der Gruppe bestehend aus (Thio)carboxylat-, (Thio)sulfonat-, (Thio)phosphonat-, Sulfat- und Amidatgruppen (-C(=O)-N^--), ist,
• - mindestens eines von R¹, R², R³, R⁴, R⁵, R⁶, R⁷ oder R⁸ eine Gruppe B, ausgewählt aus der Gruppe bestehend aus -OLi, Nitroxid (-N(O^•)-), C₁-C₂₀-Alkylnitroxid, Thio-C₁-C₂₀-Ether, C₁-C₂₀-Alkyldisulfid, C₃-C₂₀-Aryldisulfid, C₁-C₂₀-Alkylamin und C₃-C₂₀-Arylamin-Gruppen, ist,
• - die anderen R¹, R², R³, R⁴, R⁵, R⁶, R⁷ oder R⁸ ausgewählt sind aus der Gruppe bestehend aus: Wasserstoff (H), Aryl, Alkyl, Alkenyl, Alkaryl, Alkyloxy, Aryloxy, Aminoalkyl, Aminoaryl, Thioalkyl, Thioaryl, Alkylphosphonat, Arylphosphonat, Cyclodienyl, -OCR, -(O=)CHNR, -HN(O =)CR, -(O=)COR, -HN(O=)CHNR, -HN(O=)COR, -(HN=)CHNR, -HN(HN= )CHNR, -(S=)CHNR, -HN(S=)CHNR, wobei R H oder eine C₁-C₁₉-Alkylgruppe ist, und vorzugsweise wobei R H oder eine C₁-C₆-Alkylgruppe ist, wobei besagte Gruppen R¹, R², R³, R⁴, R⁵, R⁶, R⁷ oder R⁸ 1 bis 20 Kohlenstoffatome umfassen und gegebenenfalls mit mindestens einem Halogen-, Sauerstoff- oder Schwefelatom substituiert sind,
• - mindestens eines von R¹, R², R³, R⁴, R⁵, R⁶, R⁷ oder R⁸ mindestens ein Lithium-Ion enthält, wobei die Anzahl der Lithium-Ionen gleich der Anzahl der Gruppen A, die eine permanente negative Ladung umfassen, ist, um die Verbindung der Formel (1) insgesamt neutral zu machen.

The present invention relates to a novel naphthalene-based compound represented by the following formula (1):

whereby:

• - at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ is a group A comprising a permanent negative charge selected from the group consisting of (thio)carboxylate-, (Thio)sulfonate, (thio)phosphonate, sulfate and amidate groups (-C(=O)-N ^- -), is,
• - at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ is a group B selected from the group consisting of -OLi, nitroxide (-N(O ^• )-) , C ₁ -C ₂₀ alkyl nitroxide, thio C ₁ -C ₂₀ ether, C ₁ -C ₂₀ alkyl disulfide, C ₃ -C ₂₀ aryl disulfide, C ₁ -C ₂₀ alkylamine and C ₃ -C ₂₀ arylamine -groups, is,
• - the other R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ are selected from the group consisting of: hydrogen (H), aryl, alkyl, alkenyl, alkaryl, alkyloxy, aryloxy , aminoalkyl, aminoaryl, thioalkyl, thioaryl, alkylphosphonate, arylphosphonate, cyclodienyl, -OCR, -(O=)CHNR, -HN(O=)CR, -(O=)COR, -HN(O=)CHNR, -HN (O=)COR, -(HN=)CHNR, -HN(HN= )CHNR, -(S=)CHNR, -HN(S=)CHNR, where R is H or a C ₁ -C ₁₉ alkyl group, and preferably wherein R is H or a C ₁ -C ₆ alkyl group, said groups R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ comprising 1 to 20 carbon atoms and optionally containing at least one Halogen, oxygen or sulfur atom are substituted,
• - At least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ contains at least one lithium ion, wherein the number of lithium ions equal to the number of groups A, the one comprise a permanent negative charge is to make the compound of formula (1) neutral overall.

• - Alkyl: eine gesättigte, lineare oder verzweigte, C₁-C₂₀, vorzugsweise C₁-C₁₂, noch bevorzugter C₁-C₆ und noch mehr bevorzugt C₁-C₄, Kohlenwasserstoffbasierte aliphatische Gruppe. Der Begriff „verzweigt“ bedeutet, dass mindestens eine niedere Alkylgruppe wie Methyl oder Ethyl von einer linearen Alkylkette getragen wird. Als die Alkylgruppe können beispielsweise Methyl, Ethyl, n-Propyl, i-Propyl, n-Butyl, t-Butyl, i-Butyl, s-Butyl und n-Pentyl genannt werden;
• - Aryl: irgendeine funktionelle Gruppe oder Substituent abgeleitet von mindestens einem aromatischen Ring; ein aromatischer Ring entspricht irgendeiner planaren mono- oder polyzyklischen Gruppe, die ein delokalisiertes π-System umfasst, in dem jedes Atom des Zyklus ein p-Orbital aufweist, wobei besagte p-Orbitale einander überlappen; unter diesen Arylgruppen können Phenyl-, Biphenyl-, Naphthalin- und Anthracengruppen genannt werden. Die Arylgruppen der Erfindung umfassen vorzugsweise 4 bis 20 Kohlenstoffatome, noch bevorzugter 4 bis 12 Kohlenstoffatome und noch mehr bevorzugt 5 bis 6 Kohlenstoffatome;
• - Alkenyl: eine lineare oder verzweigte C₁-C₂₀, vorzugsweise C₁-C₁₂, noch bevorzugter C₁-C₆ und noch mehr bevorzugt C₁-C₄, ungesättigte Kohlenwasserstoffbasierte aliphatische Gruppe, die mindestens eine Kohlenstoff-Kohlenstoff-Doppelbindung enthält. Der Begriff „verzweigt“ bedeutet, dass mindestens eine niedere Alkylgruppe wie Methyl oder Ethyl von einer linearen Alkenylkette getragen wird;
• - Alkaryl: irgendeine Gruppe abgeleitet von einer wie oben definierten Alkylgruppe, wobei ein Wasserstoffatom durch ein wie oben definiertes Aryl ersetzt ist. Das Alkaryl umfasst vorzugsweise 5 bis 20 Kohlenstoffatome, und noch bevorzugter 5 bis 12 Kohlenstoffatome;
• - Alkyloxy: eine gesättigte, lineare oder verzweigte, C₁-C₂₀, vorzugsweise C₁-C₁₂, noch bevorzugter C₁-C₆ und noch mehr bevorzugt C₁-C₄, Kohlenwasserstoffbasierte aliphatische Gruppe, die ein Sauerstoffatom enthält. Als die Alkylgruppe können beispielsweise Methyloxy-, Ethyloxy-, n-Propyloxy-, iso-Propyloxy-, n-Butyloxy-, sec-Butyloxy-, tert-Butyloxy- und iso-Butyloxy-Radikale genannt werden;
• - Aryloxy: irgendein an ein Sauerstoffatom gebundenes Arylradikal, das vorzugsweise 4 bis 20 Kohlenstoffatome und noch bevorzugter 4 bis 12 Kohlenstoffatome umfasst. Als die Aryloxygruppe kann beispielsweise ein Phenoxyradikal genannt werden;
• - Aminoalkyl: eine gesättigte, lineare oder verzweigte, C₁-C₂₀, vorzugsweise C₁-C₁₂, noch bevorzugter C₁-C₆ und noch mehr bevorzugt C₁-C₄, Kohlenwasserstoffbasierte aliphatische Gruppe, die eine Aminogruppe, und vorzugsweise eine primäre Aminogruppe -NH₂, trägt;
• - Amino-Aryl: irgendein Arylradikal, das an eine Aminogruppe, und vorzugsweise eine primäre Aminogruppe -NH₂, gebunden ist, das vorzugsweise 4 bis 20 Kohlenstoffatome und noch bevorzugter 4 bis 12 Kohlenstoffatome umfasst;
• - Thioalkyl: eine gesättigte, lineare oder verzweigte, C₁-C₂₀, vorzugsweise C₁-C₁₂, noch bevorzugter C₁-C₆ und noch mehr bevorzugt C₁-C₄, Kohlenwasserstoffbasierte aliphatische Gruppe, die eine Thiolgruppe -SH trägt;
• - Thioaryl: irgendein Arylradikal, das an eine Thiolgruppe -SH gebunden ist, vorzugsweise 4 bis 20 Kohlenstoffatome und noch bevorzugter 4 bis 12 Kohlenstoffatome umfasst;
• - Thioether: eine gesättigte, lineare oder verzweigte, C₁-C₂₀, vorzugsweise C₁-C₁₂, noch bevorzugter C₁-C₆, und noch mehr bevorzugt C₁-C₄, Kohlenwasserstoffbasierte aliphatische Gruppe, die eine funktionelle Gruppe mit der Struktur C-S-C trägt;
• - Alkyldisulfid: eine gesättigte, lineare oder verzweigte, C₁-C₂₀, vorzugsweise C₁-C₁₂, noch bevorzugter C₁-C₆ und noch mehr bevorzugt C₁-C₄, Kohlenwasserstoffbasierte aliphatische Gruppe, die eine funktionelle Gruppe mit der Struktur C-S-S-C trägt;
• - Alkylphosphonat: irgendein Alkylradikal, das an eine Phosphon-Gruppe -P(=O)(OR')₂ gebunden ist, wobei R' eine gesättigte, lineare oder verzweigte, C₁-C₂₀, vorzugsweise C₁-C₁₂, noch bevorzugter C₁-C₆, und noch mehr bevorzugt C₁-C₄, Kohlenwasserstoffbasierte aliphatische Gruppe ist;
• - Arylphosphonat: irgendein Arylradikal, das an eine PhosphonatGruppe -P(=O)(OR')₂ gebunden ist, wobei R' eine gesättigte, lineare oder verzweigte, C₁-C₂₀, vorzugsweise C₁-C₁₂, noch bevorzugter C₁-C₆ und noch mehr bevorzugt C₁-C₄, Kohlenwasserstoffbasierte aliphatische Gruppe ist;
• - Cyclodienyl: irgendein ungesättigtes cyclisches Radikal, das mindestens zwei Kohlenstoff-Kohlenstoff-Doppelbindungen enthält, und vorzugsweise 5 bis 20 Kohlenstoffatome und noch bevorzugter 5 bis 12 Kohlenstoffatome umfasst;
• - Alkylnitroxid: eine gesättigte, lineare oder verzweigte, C₁-C₂₀, vorzugsweise C₁-C₁₂, noch bevorzugter C₁-C₆ und noch mehr bevorzugt C₁-C₄, Kohlenwasserstoffbasierte aliphatische Gruppe, die ein Nitroxidradikal -N(O^•)-trägt.

For the purposes of the invention, the following terms mean:

• - Alkyl: a saturated, linear or branched, C ₁ -C ₂₀ , preferably C ₁ -C ₁₂ , more preferably C ₁ -C ₆ and even more preferably C ₁ -C ₄ , hydrocarbon-based aliphatic group. The term "branched" means at least one lower alkyl group such as methyl or ethyl is carried by a linear alkyl chain. As the alkyl group, there can be mentioned, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, s-butyl and n-pentyl;
• - aryl: any functional group or substituent derived from at least one aromatic ring; an aromatic ring corresponds to any planar mono- or polycyclic group comprising a delocalized π-system in which each atom of the cycle has a p-orbital, said p-orbitals overlapping one another; among these aryl groups there can be mentioned phenyl, biphenyl, naphthalene and anthracene groups. The aryl groups of the invention preferably contain from 4 to 20 carbon atoms, more preferably from 4 to 12 carbon atoms, and even more preferably from 5 to 6 carbon atoms;
• - alkenyl: a linear or branched C ₁ -C ₂₀ , preferably C ₁ -C ₁₂ , more preferably C ₁ -C ₆ and even more preferably C ₁ -C ₄ unsaturated hydrocarbon-based aliphatic group containing at least one carbon-carbon double bond contains. The term "branched" means that at least one lower alkyl group such as methyl or ethyl is carried by a linear alkenyl chain;
• - alkaryl: any group derived from an alkyl group as defined above, wherein a hydrogen atom is replaced by an aryl as defined above. The alkaryl preferably comprises 5 to 20 carbon atoms, and more preferably 5 to 12 carbon atoms;
• - Alkyloxy: a saturated, linear or branched, C ₁ -C ₂₀ , preferably C ₁ -C ₁₂ , more preferably C ₁ -C ₆ and even more preferably C ₁ -C ₄ , hydrocarbon-based aliphatic group containing an oxygen atom. As the alkyl group, there can be mentioned, for example, methyloxy, ethyloxy, n-propyloxy, iso-propyloxy, n-butyloxy, sec-butyloxy, tert-butyloxy and iso-butyloxy radicals;
• - aryloxy: any aryl radical linked to an oxygen atom, preferably containing from 4 to 20 carbon atoms and more preferably from 4 to 12 carbon atoms. As the aryloxy group, there can be mentioned, for example, a phenoxy radical;
• - Aminoalkyl: a saturated, linear or branched, C ₁ -C ₂₀ , preferably C ₁ -C ₁₂ , more preferably C ₁ -C ₆ and even more preferably C ₁ -C ₄ , hydrocarbon-based aliphatic group containing an amino group, and preferably carries a primary amino group -NH ₂ ;
• - amino-aryl: any aryl radical linked to an amino group, and preferably a primary amino group -NH ₂ , preferably comprising from 4 to 20 carbon atoms and more preferably from 4 to 12 carbon atoms;
• - Thioalkyl: a saturated, linear or branched, C ₁ -C ₂₀ , preferably C ₁ -C ₁₂ , more preferably C ₁ -C ₆ and even more preferably C ₁ -C ₄ hydrocarbon-based aliphatic group bearing a thiol group -SH ;
• - thioaryl: any aryl radical linked to a thiol group -SH, preferably containing from 4 to 20 carbon atoms and more preferably from 4 to 12 carbon atoms;
• - thioether: a saturated, linear or branched, C ₁ -C ₂₀ , preferably C ₁ -C ₁₂ , more preferably C ₁ -C ₆ , and even more preferably C ₁ -C ₄ , hydrocarbon-based aliphatic group containing a functional group having the structure bears CSC;
• - Alkyl disulfide: a saturated, linear or branched, C ₁ -C ₂₀ , preferably C ₁ -C ₁₂ , more preferably C ₁ -C ₆ and even more preferably C ₁ -C ₄ , hydrocarbon-based aliphatic group having a functional group with the Structure CSSC bears;
• - alkylphosphonate: any alkyl radical attached to a phosphonic group -P(=O)(OR') ₂ , where R' is a saturated, linear or branched, C ₁ -C ₂₀ , preferably C ₁ -C ₁₂ , nor more preferably C ₁ -C ₆ , and even more preferably C ₁ -C ₄ , hydrocarbon-based aliphatic group;
• - Arylphosphonate: any aryl radical attached to a phosphonate group -P(=O)(OR') ₂ , where R' is a saturated, linear or branched, C ₁ -C ₂₀ , preferably C ₁ -C ₁₂ , more preferably C C ₁ -C ₆ and more preferably C ₁ -C ₄ hydrocarbon based aliphatic group;
• - cyclodienyl: any unsaturated cyclic radical containing at least two carbon-carbon double bonds and preferably comprising from 5 to 20 carbon atoms and more preferably from 5 to 12 carbon atoms;
• - Alkyl nitroxide: a saturated, linear or branched, C ₁ -C ₂₀ , preferably C ₁ -C ₁₂ , more preferably C ₁ -C ₆ , and even more preferably C ₁ -C ₄ , hydrocarbon-based aliphatic group containing a nitroxide radical -N( O ^• )-carries.

The presence of a group A comprising a permanent negative charge results in lower solubility of the compound of formula (1) in aprotic polar solvents.

In a preferred embodiment, in the compound of formula (1) at least two R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ groups A comprising a permanent negative charge are selected from the group consisting of (thio)carboxylates, (thio)sulfonates, (thio)phosphonates, sulfates and amidates, and more preferably carboxylate groups.

In a preferred embodiment, in the compound of formula (1) at least two R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ groups B are selected from the group consisting of - OLi, nitroxide, alkyl nitroxide, thioether, disulfide, alkylamine and arylamine, and more preferably -OLi.

In a preferred embodiment, the groups R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ that are not groups A and B are H. In a more preferred embodiment, R ¹ is , R ² , R ⁵ and R ⁶ H.

According to a preferred embodiment, the compound of the formula (1) according to the invention is selected from the group consisting of:

In a particularly preferred embodiment, the compound of formula (1) is a tetra-lithium salt of 1,5-dihydroxy-2,6-naphthalenedicarboxylic acid (Li ₄ DHNDC) of the formula:

The present invention further relates to a process for preparing a compound of formula (1) according to the invention, which comprises the step of reacting a naphthol with MeOLi in MeOH or LiH in DMF (lithiation step), and preferably MeOLi in MeOH, in a stoichiometric amount and under an inert atmosphere (in a glove box). The stoichiometric conditions are important in order to avoid unreacted MeOLi mixing with the final compound of formula (1), the only remaining by-product when the reaction is complete is the solvent, which is simply removed in vacuo.

In particular, the invention aims at a process for the production of Li ₄ DHNDC according to the following reaction scheme:

The synthesis of H ₄ DHNDC of the first step has already been described in Journal of Material Chemistry A 2015, 3, 19177-19185.

In a second step, H ₄ DHNDC is lithiated by MeOLi or LiH added under an inert atmosphere and in stoichiometric amount to obtain Li ₄ DHNDC. The second step is advantageously carried out in a protic solvent such as methanol, ethanol, isopropanol, n-propanol, n-butanol, ethylene glycol and more advantageously methanol (MeOH).

The present invention further relates to the use of a compound of the formula (1) according to the invention as an SOC in a lithium-air battery cell. The compound of formula (1) is a solid n-type electroactive organic catalyst lithium salt that can be used in lithium-air battery cells to promote oxygen reactions.

The invention further relates to an SOC which contains and preferably consists of a compound of the formula (1) according to the invention.

The SOC according to the invention has the main advantage that it is not soluble in the electrolyte, thus avoiding the migration of soluble species to the anode. It also increases the electrochemical performance of reactions involving oxygen, such as the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), thereby improving the capacity and rechargeability of nonaqueous lithium-air battery cells.

The SOC according to the invention is advantageously in the form of lamellar particles.

The SOC according to the invention advantageously has a specific surface area greater than or equal to 5 m ² ·g ^-1 .

• - eine negative Elektrode (Anode), die ein Negativelektrodenaktivmaterial enthält,
• - eine positive Elektrode (Kathode), die Sauerstoff als ein Positivelektrodenaktivmaterial verwendet, und
• - ein nichtwässriges Elektrolytmedium, das zwischen der negativen Elektrode und der positiven Elektrode angeordnet ist,

wobei die positive Elektrode eine erfindungsgemäße Verbindung der Formel (1) als SOC umfasst.Another subject of the present invention is a lithium-air battery cell, which comprises:

• - a negative electrode (anode) containing a negative electrode active material,
• - a positive electrode (cathode) using oxygen as a positive electrode active material, and
• - a non-aqueous electrolyte medium arranged between the negative electrode and the positive electrode,

wherein the positive electrode comprises a compound of the formula (1) according to the invention as SOC.

The prior art 1 already discloses the synthesis of IMNQ and DANQ, which are used as cathode active materials in lithium-ion battery cells, which are sealed battery systems, and not in lithium-air battery cells. The main disadvantage of sealed battery systems is their low capacity.

<anode>

In the lithium-air battery cell of the present invention, the negative electrode (which may also be referred to as “anode” hereinafter) includes at least an anode active material (which may also be referred to as “negative-electrode active material” hereinafter). As the anode active material, general anode active materials for lithium batteries can be used, and the anode active material is not particularly limited. The anode active material is generally capable of storing/releasing a lithium ion (Li ⁺ ).

Specific anode active materials for rechargeable lithium-air batteries are, for example, a lithium metal, lithium-protected anodes, lithium alloys such as lithium-aluminum alloy, lithium-tin alloy, lithium-lead alloy and lithium-silicon alloy, metal oxides such as lithium -Titanium oxide, metal nitrides such as a lithium cobalt nitride, a lithium iron nitride and a lithium manganese nitride. Of these, lithium metal is preferred.

The term "lithium-protected anode" refers here, for example (but not exclusively) to a "Lithium Protected Electrode" (LPE) as described in U.S. 8,652,692 is described. As a rule, the Li metal is covered by a solid electrolyte (for example LiSiCON (Lithium Superionic Conductor) with the formula LiM ₂ (PO ₄ ) ₃ ). There is usually an intermediate layer (consisting of Cu ₃ N/Li ₃ N, for example) between the LiSiCON and the Li metal. In LPE systems, the Li metal can be attached directly to one side of the LiSiCON material, or alternatively, a small amount of a solvent containing a Li salt electrolyte can be added between the LiSiCON material and the Li metal to ensure the ionic conductivity of Li. Such materials were used, for example, in U.S. 7,282,295 and U.S. 7,491,458 described. LiSiCON materials have also been described in Nature Materials, 10, 682-686 (2011).

When a metal, an alloy or the like in the form of a foil or a metal is used as the anode active material, it itself can be used as the anode.

The anode must contain at least one anode active material; however, if required, it can contain a binder for fixing the anode active material. The type and use of the binder are the same as for the air cathode described below.

An anode collector can be connected to the anode, which collects the current from the anode. The material for the anode collector and its shape are not particularly limited. Examples of the material of the anode collector include stainless steel, copper and nickel. Examples of the shape of the anode collector include a foil shape, a plate shape, and a mesh (lattice) shape.

<cathode>

In the lithium-air battery cell of the present invention, the positive electrode (which may also be referred to as “cathode” hereinafter) includes at least one cathode active material (which may also be referred to as “positive electrode active material” hereinafter).

In the lithium-air battery cell of the present invention, the positive electrode uses oxygen as a positive electrode active material. The oxygen serving as the positive electrode active material may be contained in air or oxygen gas.

<Catalyst>

In the lithium-air battery cell of the present invention, the catalyst present in the positive electrode is an SOC represented by formula (1).

The SOC of formula (1) of the invention advantageously exhibits a solubility of less than 150 gL ^-1 in lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) 1M in tetraethylene glycol dimethyl ether (TEGDME).

In addition to the compound of the formula (1), the positive electrode of the lithium-air battery cell according to the invention can also comprise another SOC.

When additional SOC are present, the weight ratio between the SOC of formula (1) of the invention and the other SOC can range from 0.1/99.9 to 100/0, preferably from 60/40 to 40/60 and more preferably of 50/50.

In the lithium-air battery cell of the present invention, the positive electrode may be a member in which the redox catalyst is carried on a carrier. An example of such a support is carbon. Therefore, in the lithium-air battery cell according to the invention, the positive electrode advantageously also comprises carbon. Examples of carbon include carbon blacks such as ketjen black, acetylene black, channel black, furnace black, lamp black and thermal black; graphite such as natural graphite such as flaky graphite, artificial graphite and expanded graphite; activated charcoal made from charcoal and coal; carbon foam; carbon fibers obtained by carbonizing synthetic fibers and petroleum pitch-based materials; carbon nanofibers; molecular carbon such as fullerenes; and tubular carbon such as carbon nanotubes. Furthermore, modified carbons such as N-doped carbon can be used.

Positive electrode materials may also be used in a lithium-air battery cell of the present invention based on materials other than carbon. For example, positive electrode materials based on metal foam, stable and conductive metal oxides or steel can be used.

In the present invention, where carbon is used, it is preferably a porous material in the form of powder and preferably has a high specific surface area of 20 to 2000 m ² .g ^-1 , more preferably 60 to 2000 m ² .g ^-1 and even more preferably from 60 to 1500 m ² .g ^-1 . For example, carbon can be used which has been treated by a general method to increase porosity or surface area, followed by a further treatment to increase wettability. Various forms of carbon can be used in the present invention, including SUPER P ^® Li (from TIMCAL) which has a particle size of 40 nm and a specific surface area (determined by the Brunauer-Emmett-Teller method) of 62 m ² .g ^-1 has; BLACK PEARLS ^® 2000 (from Cabot Corporation), which has a particle size of 12 nm and a specific surface area (determined by the Brunauer-Emmett-Teller method) of 1487 m ² .g ^-1 ; Ketjenblack ^® EC-600JD powder (from AzkoNobel) which has a specific surface area (determined by the Brunauer-Emmett-Teller method) of 1400 m ² .g ^-1 . Examples of commercial carbon products that can be used in the present invention include Carbon Super C65 (from Imerys), the KS series, SFG series and Super S series (from TIMCAL), activated carbon products from Norit and AB-Vulcan 72 ( by Cabot). Other examples of commercially available carbon include WAC powder series (from Xiamen All Carbon Corporation), PW15-type, J-type and S-type activated carbon (from Kureha), and Maxsorb MSP-15 (from Kansai Netsu Kagaku) .

Examples of methods to increase the porosity, surface area and wettability of the carbon include physical activation or chemical activation. The chemical activation method includes, for example, immersing the carbon material in a strong alkaline aqueous solution (e.g. potassium hydroxide solution), in an acid solution (e.g. nitric acid or phosphoric acid) or in a salt (e.g. zinc chloride). This treatment may (but need not) be followed by a relatively low temperature (e.g. 450-900°C) calcination step.

In addition, the carbon preferably has pores with a pore diameter of 5 nm or more, preferably 20 nm or more. The specific surface area of carbon and the pore size can be measured by, for example, the BET method or the BJH method. Also, in general, the carbon preferably has an average particle diameter (primary particle diameter) from 8 to 350 nm, preferably from 30 to 50 nm. The average primary particle diameter of carbon can be measured by TEM.

In the lithium-air battery cell according to the invention, the weight ratio between carbon and the SOC of the formula (1) of the invention is advantageously 7:2. When another SOC is present, the weight ratio between carbon:SOC of formula (1) of the invention:additional SOC (carbon:SOC1:SOC2) is advantageously 7:1:1.

In the lithium-air battery cell of the present invention, the positive electrode may contain a conductive material in addition to the carbon and non-carbon materials described above. Examples of such additional conductive materials include conductive fibers such as metal fibers, metal powders such as silver, nickel or aluminum powder, and organic conductive materials such as polyphenylene derivatives. These can be used singly or in combination as a mixture.

In the lithium-air battery cell of the present invention, the positive electrode may contain a polymer binder. The polymer binder is not particularly limited. The polymer binder may be composed of a thermoplastic resin or a thermosetting resin. Examples include polyethylene, polypropylene, polytetrafluoroethylene (PTFE), styrene-butadiene rubber, tetrafluoroethylene-hexafluoropropylene copolymers, tetrafluoroethylene-hexafluoropropylene copolymers (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers (PFA), vinylidene fluoride-hexafluoropropylene copolymers, vinylidene fluoride Chlorotrifluoroethylene copolymers, ethylene tetrafluoroethylene copolymers (ETFE resins), polychlorotrifluoroethylene (PCTFE), vinylidene fluoride pentafluoropropylene copolymers, propylene tetrafluoroethylene copolymers, ethylene chlorotrifluoroethylene copolymers (ECTFE), vinylidene fluoride hexafluoropropylene tetrafluoroethylene copolymers, vinylidene fluoride - Perfluoromethyl vinyl ether-tetrafluoroethylene copolymers, ethylene-acrylic acid copolymers. Copolymers having sulfonate-terminated perfluorovinyl ether groups (or sulfonate-terminated perfluorovinyl ether groups) attached to a poly(tetrafluoroethylene) backbone, such as those commonly referred to as ^Nafion® , are also contemplated as polymeric binders in the present invention to be pulled. These polymer binders can be used singly or in combination as a mixture. Polytetrafluoroethylene (PTFE) is a particularly preferred polymer binder.

In the lithium-air battery cell of the present invention, the weight ratio between the polymer binder and (SOC of the formula (1) + carbon + polymer binder) is less than or equal to 20%. When another SOC is present, the proportion of binder remains constant and the weight ratio between the polymer binder and (SOC of formula (1) + additional SOC + carbon + polymer binder) remains less than or equal to 20%.

In general, in advantageous embodiments of the present invention, an air cathode collector is connected to the air cathode and collects the current from the air cathode. The material for the air cathode collector and the shape thereof are not particularly limited. Examples of the material of the air cathode collector include stainless steel, aluminum, iron, nickel, titanium and carbon. The shape of the air cathode collector may include, for example, a foil shape, a plate shape, a mesh shape (lattice shape), or a fiber shape. Preferably, the air cathode collector has a porous structure such as a mesh shape, because the collector having a porous structure is excellent in efficiency in supplying oxygen to the air cathode.

In some embodiments, the air electrode (air cathode) also includes hydrophobic hollow fibers. A hydrophobic fiber tends to create a space between itself and the electrolyte. These spaces facilitate oxygen diffusion in the air electrode, so a thicker electrode can be used. Typically, carbon-based air electrodes are 0.5-0.7mm thick. The addition of hydrophobic fibers allows the use of electrodes with a thickness of at least 1 mm. Suitable fibers include DuPont HOLLOFIL ^® (100% polyester fiber with another hole in the core), goose down (very small, extremely light down found close to the skin of gooses), PTFE fibers and woven hollow fiber cloth. Furthermore, these fibers can be coated with KETJENBLACK ^® .

<electrolyte>

In the lithium-air battery cell of the present invention, the nonaqueous ion conductive (electrolyte) medium interposed between the negative electrode and the positive electrode is a nonaqueous one electrolytic solution containing one or more organic solvents and typically containing a salt. Non-limiting examples of the salt that can be used include known supporting electrolytes such as LiPF ₆ , LiClO ₄ , LiAsF ₆ , LiBF ₄ , Li(CF ₃ SO ₂ ) ₂ N (LiTFSI), LiFSI, Li(CF ₃ SO ₃ ) (LiTriflate), LiN(C ₂ F ₅ SO ₂ ) ₂ , LiBOB, LiFAP, LiDMSI, LiHPSI, LiBETI, LiDFOB, LiBFMB, LiBison, LiDCTA, LiTDI, LiPDI. These salts can be used individually or in combination. The concentration of the salt preferably ranges from 0.1 to 2.0M, and more preferably from 0.8 to 1.2M.

The lithium salts are suitably used in the electrolyte medium in combination with aprotic organic solvents known for use in lithium-air batteries. Examples of such aprotic organic solvents include chain carbonates, cyclic ester carbonates, chain ethers, cyclic ethers, glycol ethers and nitrile solvents. Examples of chain carbonates include dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate. Examples of cyclic ester carbonates include γ-butyrolactone and γ-valerolactone. Examples of chain ethers include dimethoxyethane and ethylene glycol dimethyl ether. Examples of cyclic ethers include tetrahydrofuran and 2-methyltetrahydrofuran. Examples of glycol ethers include tetraethylene glycol dimethyl ether (TEGDME), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), poly(ethylene glycol) dimethyl ether with a weight-average molecular weight Mw of 90 to 225 g.mol ^-1 . Also, nitrile solvents such as acetonitrile, propionitrile and 3-methoxypropionitrile can be used. These aprotic organic solvents can be used singly or in combination as a mixture. Glycol ethers are the preferred aprotic organic solvents, and in particular tetraethylene glycol dimethyl ether (TEGDME).

Gel polymer electrolytes can also be used in the present invention. The gelled electrolyte having lithium ion conductivity can be obtained, for example, by adding a polymer to the nonaqueous electrolytic solution for gelation. Specifically, gelation can be accomplished by adding a polymer such as polyethylene oxide (PEO), polyvinylidene fluoride (PVDF, commercially available as Kynar, etc.), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), and poly(vinyl) chloride (PVC). An overview of the use of gel-type polymer electrolytes for lithium-ion batteries is given by Song et al. in Journal of Power Sources, 77 (1999), 183-197.

Furthermore, components that can be crosslinked and/or thermoset can be added to the gel electrolyte formulation to improve its mechanical properties.

Furthermore, a substantial amount of plasticizers (PEG, crown ether, etc.) can be added to improve the ionic conductivity of the polymer electrolytes.

Furthermore, nanoparticles/ceramics (Al ₂ O ₃ , SiO ₂ , ZrO ₂ , MgO, CeO ₂ , etc.) can be added to such gel polymer electrolytes in order to increase their conductivity. In this context, on EP 1 096 591 A1 or Croce et al. in Electrochimica Acta 46 (2001), 2457-2461.

The nanoparticle/ceramic filler content is typically less than 10% by weight of the membrane. For example, Al ₂ O ₃ nanoparticles can be obtained from Aldrich Research Grade and have a particle size of 5.8 nm (Swierczynski et al., Chem. Mater., 2001, 13, 1560-1564). SiO ₂ can be obtained from Aldrich Reagents Grade with a particle size of 7 nm. In general, the size of the nanoparticles is preferably 15 nm or below.

It is also within the scope of the present invention to envisage adding an oxygen dissolution enhancer to the electrolyte medium. This oxygen dissolution enhancer can be a fluorinated polymer, fluorinated ether, fluorinated ester, fluorinated carbonate, fluorinated carbon material, fluorinated blood substitute, or even a metalloprotein. Such oxygen dissolution enhancers are in US2010/0266907 described.

<separator>

In the lithium-air rechargeable battery cell of the present invention, a separator may advantageously be provided between the air cathode and the anode for complete electrical insulation between these electrodes. The separator is not particularly limited as long as it is capable of electrically insulating the air cathode and the anode from each other and has a structure that allows the electrolyte to exist between the air cathode and the anode.

Examples of separators include porous films and non-woven fabrics comprising polyethylene, polypropylene, cellulose, polyvinylidene fluoride, glass-ceramic, and so on. Among these, a glass-ceramic separator is preferable.

<Battery Cell Case>

As the battery cell case for accommodating the rechargeable lithium-air battery cell, general battery cases for rechargeable lithium battery cells can be used. The shape of the battery case is not particularly limited as long as it can accommodate the above-mentioned air cathode, anode, and electrolyte. Specific examples of the shape of the battery cell case include a coin shape, a flat plate shape, a cylindrical shape, and a laminate shape. It is possible for the battery of the present invention to be completely encased in an oxygen permeable membrane, advantageously one that exhibits selectivity for oxygen diffusion over that of water.

<Use of the Battery Cell of the Invention>

The lithium-air rechargeable battery cell of the invention can discharge when an active material, namely oxygen, is supplied to the air cathode. Examples of oxygen supply sources include air and oxygen gas, and oxygen gas is preferred. The pressure of the supplied air or oxygen gas is not particularly limited and can be appropriately determined.

The lithium-air battery cell of the present invention can be used as a primary battery cell or as a rechargeable secondary battery cell.

1. (a) die Lithium-Luft-Batteriezelle in einem vollständig geladenen Zustand bereitgestellt wird;
2. (b) die Lithium-Luft-Batteriezelle entladen wird, bis die spezifische Kapazität einen Wert X erreicht;
3. (c) die Lithium-Luft-Batteriezelle wieder aufgeladen wird;
4. (d) die Schritte (b) und (c) wiederholt werden.

For example, the lithium-air battery cell of the present invention can be practically used in a process in which the battery is cycled between certain limits defined by initial and final voltage or initial and final capacity or specific capacity. For example, a method of using the lithium-air battery cell of the present invention may consist of a method in which:

1. (a) the lithium-air battery cell is provided in a fully charged state;
2. (b) the lithium-air battery cell is discharged until the specific capacity reaches a value X;
3. (c) the lithium-air battery cell is recharged;
4. (d) steps (b) and (c) are repeated.

The selected value X for the specific capacity can vary very widely and can be, for example, in the range from 200 to 10000 mAh.g ^-1 . The specific capacity of a lithium-air battery cell can be determined by discharging to 2V. During operation of the battery cell, it may be appropriate for the battery cell to cycle within limits that do not go through to full discharge or full charge. It may be advantageous to cycle the battery cell between 10 and 90% of its specific capacity (determined in step (b)), preferably between 20 and 80%, and more preferably between 20 and 70%. The cycling can also be performed between certain limits of the initial or maximum theoretical discharge capacity. capacity-limited cycling can allow the cell to live longer, and it may therefore make sense to limit cycling capacity to around 30% of full discharge capacity.

It is possible to provide, as a product, a battery cell whose air cathode contains addition of Li ₂ O ₂ . Such a battery cell is usually charged before use.

The lithium-air battery cell of the present invention can be used as a rechargeable lithium battery for electric and hybrid vehicles, electronic devices (such as computers and telephones), and stationary power generation devices, and can be assembled into battery packs. The number of battery cells can vary depending on the end use of the lithium-air battery and is preferably between 2 and 250 battery cells. There are two ways to assemble the battery cells depending on the objective: parallel or in series. When connected in parallel, the capacity of each cell is added while the voltage remains the same. When connected in series, the voltage of each cell is added while the capacitance is that of the smallest cell.

Any combination of the elements described above, in all possible variations thereof, is included in the invention unless otherwise indicated herein or unless the context clearly dictates otherwise. Thus, all features and embodiments that are described herein in particular as being applicable, advantageous or preferred in connection with the invention are to be interpreted in such a way that they can be used in combination with one another in preferred embodiments of the invention.

examples

Preparation of a SOC according to the invention: Li ₄ DHNDC

a) First step: Preparation of H ₄ DHNDC

2.24 g (14 mmol) of 1,5-dihydronaphthalene and 4.2 g (42 mmol) of KHCO ₃ were ground together and placed in a 45 mL Parr reactor along with 8 mL of 1,2,4-trichlorobenzene and 9 g of dry ice given. The Parr reactor was sealed and heated to 250°C for 17 hours. The resulting paste was washed with 80 mL diethyl ether (Et ₂ O) at room temperature (25° C.) and then dissolved in 1.5 L ultrapure water. The solution was filtered and then acidified with a 12N HCl solution, precipitating a light green solid. The solid was filtered, washed liberally with ultrapure water and dried.

2.81 g of a green powder was obtained (yield = 81%).
ATR-IR: νmax/cm ^-1 3210, 2975, 2844, 2596, 2532, 1650, 1598, 1490, 1438, 1415, 1296, 1237, 1209, 1189, 1167, 1013, 881, 826, 736, 67,366, 67,366 cm-1;
¹ H NMR: δ _H (400 MHz, (CD ₃ ) ₂ SO) 7.77 (2H, d, J=8.9 Hz), 7.69 (2H, d, J=8.8 Hz), 4 .06 (4H, wide);
¹³ C NMR: δc: (400 MHz, (CD ₃ ) ₂ SO) 173.1, 159.9, 128.2, 125.5, 113.7, 109.5.

b) Second step: Preparation of Li ₄ DHNDC

In a flat-bottomed flask, 248.2 mg (1 mmol) of the previously prepared H ₄ DHNDC was dissolved in 8 mL of dry MeOH under an inert atmosphere (in a glove box). 1.82 mL (4 mmol) of a 2.2 M solution of MeOLi in MeOH (Aldrich) was added at room temperature (25°C). The mixture, which was initially a green solution, became a light brown/orange solution that slowly turned to a dark brown/black solution. The mixture was stirred at room temperature (25°C) for 2 days until a suspension of light brown powder was obtained. Excess MeOH was removed in vacuo (in vacuo) and the resulting light brown powder was dried in a Buchi oven in vacuo at 100°C for 15 hours and then at 150°C for 4 hours. 271.7 mg of a light brown powder were obtained (quantitative yield).

ATR-IR: νmax/cm ^-1 2942, 2846, 2791, 1567, 1531, 1482, 1426, 1385, 1268, 1230, 1187, 1164, 1078, 1025, 912, 833, 801, 767, 705 cm -, 658 cm ^{- 1} ;

¹ H NMR: δ _H (400 MHz, (CD ₃ ) ₂ SO) 7.23 (2H, dd, J=5.7, 3.4 Hz), 7.01 (2H, dd, J=5.7, 3.4 Hz).

• - Spezifische Oberfläche: 5,7 m²·g^-1, und
• - Morphologie: Lamellare Partikel.

The properties of the obtained Li ₄ DHNDC were as follows:

• - Specific surface area: 5.7 m ² g ^-1 , and
• - Morphology: Lamellar particles.

shows the TGA of Li ₄ DHNDC obtained with ( ) or without ( ) excess of MeOLi, shows the FT-IR spectra of the precursor H ₄ DHNDC ( ) and Li ₄ DHNDC ( ), and shows the SEM images of Li ₄ DHNDC.

• Drei Elektrolytlösungen wurden durch Lösen hergestellt:
  1. a) 1,0 M Bis(trifluormethan)sulfonimid-Lithiumsalz (LiTFSI, BASF) in TEGDME (Sigma Aldrich, feuchtigkeitskontrollierte Qualität),
  2. b) 1,0 M LiTFSI und 10^-2 M (10 mM) DBBQ (Sigma Aldrich) in TEGDME,
  3. c) 1,0 M LiTFSI und 10^-2 M (10 mM) TTF (Sigma Aldrich) in TEGDME. LiTFSI, DBBQ und TTF wurden bei 100°C über Nacht unter Vakuum
  getrocknet, während das Lösungsmittel TEGDME nach dem Trocknen/Lagern auf regenerierten 3 Ä-Molekularsieben (Sigma Aldrich) für mindestens 15 Tage in einer Glovebox verwendet wurde. Der Wassergehalt im Lösungsmittel und in den Elektrolyten wurde mit dem Karl-Fischer-Coulometer 831KF (Metrohm) bestimmt und lag bei durchschnittlich weniger als 4 ppm.

Production of the electrolytes:

• Three electrolyte solutions were prepared by dissolving:
  1. a) 1.0 M bis(trifluoromethane)sulfonimide lithium salt (LiTFSI, BASF) in TEGDME (Sigma Aldrich, moisture-controlled grade),
  2. b) 1.0 M LiTFSI and 10 ^-2 M (10 mM) DBBQ (Sigma Aldrich) in TEGDME,
  3. c) 1.0 M LiTFSI and 10 ^-2 M (10 mM) TTF (Sigma Aldrich) in TEGDME. LiTFSI, DBBQ and TTF were dried at 100°C under vacuum overnight
  dried while using TEGDME solvent after drying/storing on regenerated 3 Å molecular sieves (Sigma Aldrich) for at least 15 days in a glove box. The water content in the solvent and in the electrolyte was determined using the Karl Fischer coulometer 831KF (Metrohm) and was less than 4 ppm on average.

• Gew.-% Zusammensetzung: LFP/Industrieruß/Bindemittel (PVdF): 88/4.5/7.5 Erwartete Belastung: 1,3 mAh.cm^-2
• Erwartete Belastung: 9,89 mg_tot.cm^-2
• Beschichtungsdicke (ohne Aluminiumfolie): 47 µm
• Dicke der Aluminiumfolie: 15 µm (ρ_Al =2,7 g.cm^-3)
• Porosität der Beschichtung: 35%
• Erwartete Eigenschaften:
  • Q_reversibel (@ C/5, Potenzialfenster: 2,1 - 4,3 V) ~ 152 mAh.g_LFP ^-1

Manufacturing a LiFePO ₄ (LFP) anode:

• Wt% composition: LFP/carbon black/binder (PVdF): 88/4.5/7.5 Expected load: 1.3 mAh.cm ^-2
• Expected load: 9.89 mg _tot .cm ^-2
• Coating thickness (without aluminum foil): 47 µm
• Aluminum foil thickness: 15 µm (ρ _Al =2.7 g.cm ^-3 )
• Coating porosity: 35%
• Expected properties:
  • Q _reversible (@ C/5, potential window: 2.1 - 4.3 V) ~ 152 mAh.g _LFP ^-1

The LFP electrodes used for the following tests are 11 mm diameter die-cut discs (area: 0.9503 cm ² ).

The LFP electrodes were used as a counter electrode for standardization in all tests.

The recorded voltages (V _{vs LFP} ) were plotted against Li ⁺ /Li (V _{vs Li} ) according to the following equation: V _{vs Li} = 3.4 V - V _{vs LFP} .

• Galvanostatische Vorladeversuche der SOC-Elektrode wurden unter Argon unter Verwendung von Metall Li als Anode und einem Arbin-Batteriezyklisierer durchgeführt. Ein konstanter Strom von 25 mA g^-1Li_4DHNDC wurde bis zu einer Abschaltspannung von 4,0 V gegen Li⁺/Li angelegt.

Manufacturing the SOC electrode:

• Galvanostatic precharge experiments of the SOC electrode were performed under argon using metal Li as the anode and an Arbin battery cycler. A constant current of 25 mA g ^-1 Li _4DHNDC was applied up to a cut-off voltage of 4.0 V versus Li ⁺ /Li.

• Um den SOC der Erfindung mit löslichen Katalysatoren (DBBQ und TTF) unter den gleichen Versuchsbedingungen zu vergleichen, wurden die Versuche in einer Konfiguration LFP/Elektrolyt/O₂ Elektroden mit einer LFP-Anode durchgeführt.

Assembling the battery:

• In order to compare the SOC of the invention with soluble catalysts (DBBQ and TTF) under the same experimental conditions, the experiments were carried out in an LFP/electrolyte/O ₂ electrodes configuration with an LFP anode.

Modified Swagelok cells with an opening to the atmosphere were assembled using as the anode a pure lithium metal disc (diameter = 11 mm and thickness = 0.7 mm) or a disc of LFP (from IMN) (diameter = 11 mm, thickness = 0.045 mm and 9.4 mg in weight of active material) was used. Two pieces of glass fiber separators (Whatman, diameter=13 mm) which were impregnated with 210 μL of electrolyte were used as separators. The carbon-based electrodes prepared above were used as working electrodes. Before the assembled Swagelok cells were shipped out of the glove box, they were placed in a specially designed airtight container with inlet and outlet valves. Some Swagelok cells in the containers were kept under argon while the other containers were filled with a continuous, relatively high flow of dry oxygen (5.0 purity, flowing from a high-pressure cylinder through a stainless steel gas line) for 30 minutes. Similar to the cathodes, the LFP and separators were dried overnight at 120°C under vacuum and all cell components (modified Swagelok and engineered airtight containers) were oven dried at 70°C for 12 hours before use.

Comparative Example 1: Air Electrode Containing Only Carbon (Reference)

Carbon Super C65 (Imerys) and polytetrafluoroethylene (PTFE, 60% by weight dispersion in H ₂ O, Sigma Aldrich) in a weight ratio of 4:1 w/w (carbon:PTFE) were mixed in an agate mortar for 20 minutes. The resulting black paste was wetted with 2-propanol (VWR International, 1.4 mL ₂ -propanol/g _paste ) to improve mixing and moldability. Once a rubbery composite was obtained, about 160 mg was placed on a stainless steel mesh with an area of 4×4 cm ² . The rubbery composite was then pressed using a Teflon™ cylinder until the web was evenly dislodged was covered with the black paste. The mesh was then placed between two aluminum foils and pressurized to 35 MPa three times for 30 seconds using a hydraulic press. It was then dried in a circulating air oven at 100°C for 1 hour and then cut into discs with a diameter of 4 mm. Before using the electrodes thus prepared, they were dried overnight at 150°C under vacuum. The final weight of the electrodes was 0.8 ± 0.1 mg after net weight subtraction and with a thickness of 0.32 ± 0.04 mm.

This air electrode containing only carbon and PTFE was installed in a battery with an electrolyte without a soluble catalyst (electrolyte a).

Comparative example 2: Air electrode with carbon + 10 mM DBBQ added in the electrolyte

The air electrode containing carbon and PTFE was manufactured according to the same protocol as in Comparative Example 1 and incorporated into a battery with an electrolyte containing 10 mM DBBQ (electrolyte b).

Comparative example 3 Air electrode with carbon + 10 mM TTF added in the electrolyte

The air electrode containing carbon and PTFE was manufactured according to the same protocol as in Comparative Example 1 and incorporated into a battery with an electrolyte containing 10 mM TTF (electrolyte c).

Example 1: Air electrode with carbon + Li ₄ DHNDC (weight ratio 7:2) in electrolyte a)

Li ₄ DHNDC, Carbon Super C65 and PTFE (dry powder, University of Oxford) were first dried in vacuo at 120 °C overnight.

Carbon Super C65 and Li ₄ DHNDC (carbon:Li ₄ DHNDC weight ratio=7:2) were mixed in a mortar for 20 minutes. Thereafter, PTFE was mixed with the pastes in a weight ratio (carbon + Li4DHNDC):PTFE of 4:1 and about 2 ml of 2-propanol was added. All components were mixed for a further 20 minutes in an agate mortar until the two rubbery composites obtained appeared homogeneously black (weight ratio carbon: Li ₄ DHNDC = 7:2) (total weight ratio: Carbon Super C65: Li ₄ DHNDC: PTFE = 28:8:9 ). A small amount of the resulting composites was then applied to pre-cut discs of 4 mm diameter stainless steel mesh. The disks were then placed between two aluminum foils and finally a pressure of 35 MPa was applied three times for 30 seconds. The electrodes so prepared were vacuum dried at 120°C overnight to remove any trace of 2-propanol. The final weight was 1.2 ± 0.2 mg after subtracting the net weight.

shows the voltage (V versus Li ⁺ /Li) versus capacity (mAh.cm ^-2 ) for a lithium-air battery cell that was cycled at 0.2 mAh.cm ^-2 as described in Example 1 (Ex1). compared to Comparative Examples 1, 2 and 3 (Comparative Ex1, Comparative Ex2, Comparative Ex3). shows that the electrode containing Li ₄ DHNDC (Bsp1) allows an increase in the discharge capacity (mAh.cm ^-2 ) and a recharging of the lithium-air battery cell with 100% efficiency thanks to a lower hysteresis, which is the case with ComparativeBsp1, ComparativeBsp2 , Comparative Example 3 is not the case.

shows the cycling of the lithium-air battery cell ( ) of Example 1 (Ex1) at a rate of 0.2 mAh.cm ^-2 , within the potential window 2.2 - 4.6 V versus Li ⁺ /Li and with a capacity limitation of 800 mAh.g ^-1 _SOC (~ 2.15 mAh.cm ^-2 ), and the retention of capacity versus the number of cycles ( ) from example 1.

shows a comparison of the 1 ^st (first) cycle of the lithium-air battery cell of Example 1 using a working electrode containing Li ₄ DHNDC as SOC obtained in argon (dotted line) or in oxygen (solid line) for electrodes containing a weight ratio of Carbon Super C65:Li ₄ DHNDC of 7:2 (galvanostatic discharge performed at 0.5 mAh.cm ^-2 ). The vertical line indicates the theoretically expected capacity. shows that the SOC alone does not have a high capacity, while under oxygen there is a clear effect on the capacity.

Comparison with state-of-the-art catalysts:

• - Stand der Technik 1: Renault et al., Energy & Environmental Science, 2013, 6, 2124-2133,
• - Stand der Technik 2: Gao et al., Nature Materials, 2016, 15, 882,
• - Stand der Technik 3: Chen et al., Nature Chemistry, 2013, 5, 489,
• - Stand der Technik 4: Gao et al, Nature Energy, Vol. 2, 17118 (2017),
• - Stand der Technik 5: Hase et al., Chem. Commun. 2016, 52, 12151-12154,
• - Stand der Technik 6: Bergner et al., Phys. Chem. Chem. Phys., 2015, 17, 31769-31779, und
• - Stand der Technik 7: Kundu et al., ACS Cent. Sci., 2015, 1, 510-515.

Tabelle 1: Organischer Katalysator Formel Elektrolyt Rate max (mAh. cm^-2) Aktivität p/n-Typ SOC der vorliegenden Erfindung Li₄DHNDC

1M LiTFSI in TEGDME 0.2 ORR + OER n-Typ Stand der Technik 1 Li₄-p-DHT

1M LiPF₆ in EC: PC NA ORR n-Typ Stand der Technik 2 DBBQ

1M LiTFSI in DME oder TEDME NA ORR n-Typ Stand der Technik 3 TTF

1M LiClO₄ in DMSO NA OER p-Typ Stand der Technik 4 DBBQ + TEMPO

0,3M LiClO₄ in DME NA ORR + OER p + n-Typ Stand der Technik 5 MeO-TEMPO

- - OER p-Typ Stand der Technik 6 1-Me-AZADO

1M LiTFSI in Diglyme 0.1 OER P-Typ Stand der Technik 7 TDPA

0,5 M LiTSFI in TEGDME 0.1 OER P-Typ
NA = nicht anwendbarThe following table (Table 1) summarizes the characteristics of the SOC used in the lithium-air battery cells described in the present invention compared to those disclosed in the prior art references described above:

• - Prior art 1: Renault et al., Energy & Environmental Science, 2013, 6, 2124-2133,
• - Prior art 2: Gao et al., Nature Materials, 2016, 15, 882,
• - Prior Art 3: Chen et al., Nature Chemistry, 2013, 5, 489,
• - Prior Art 4: Gao et al, Nature Energy, Vol. 2, 17118 (2017),
• - Prior art 5: Hase et al., Chem. Commun. 2016, 52, 12151-12154,
• - Prior art 6: Bergner et al., Phys. Chem. Chem. Phys., 2015, 17, 31769-31779, and
• - Prior Art 7: Kundu et al., ACS Cent. Sci., 2015, 1, 510-515.

Table 1: Organic Catalyst formula electrolyte Rate max (mAh. cm ^-2 ) activity p/n type SOC of the present invention _Li4DHNDC

1M LiTFSI in TEGDME 0.2 ORR + OER n-type State of the art 1 Li ₄ -p-DHT

1M LiPF ₆ in EC:PC N / A ORR n-type state of the art 2 DBBQ

1M LiTFSI in DME or TEDME N / A ORR n-type state of the art 3 TTF

1M _LiClO4 in DMSO N / A OER p-type state of the art 4 DBBQ + PACE

0.3M _LiClO4 in DME N / A ORR + OER p + n type State of the art 5 MeO TEMPO

- - OER p-type state of the art 6 1-Me-AZADO

1M LiTFSI in diglyme 0.1 OER P type State of the art 7 TDPA

0.5M LiTSFI in TEGDME 0.1 OER P type
NA = not applicable

QUOTES INCLUDED IN DESCRIPTION

This list of documents cited by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent Literature Cited

• US8652692 [0045]
• US7282295 [0045]
• US7491458 [0045]
• EP 1096591 A1 [0071]
• US20100266907 [0073]

Claims (21)

Compound represented by formula (1) below:

wherein: - at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ is a group A comprising a permanent negative charge selected from the group consisting of (thio)carboxylate -, (thio)sulfonate, (thio)phosphonate, sulfate and amidate groups, - at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ is a group B selected from the group consisting of -OLi, nitroxide, C ₁ -C ₂₀ alkyl nitroxide, thio C ₁ -C ₂₀ ether, C ₁ -C ₂₀ alkyl disulfide, C ₃ -C ₂₀ aryl disulfide, C ₁ - C ₂₀ alkylamine and C ₃ -C ₂₀ arylamine groups, - the other R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ are selected from the group consisting of : H, aryl, alkyl, alkenyl, alkaryl, alkyloxy, aryloxy, aminoalkyl, aminoaryl, thioalkyl, thioaryl, alkylphosphonate, arylphosphonate, cyclodienyl, -OCR, -(O=)CHNR, -HN(O=)CR, -(O =)COR, -HN(O=)CHNR, -HN(O=)COR, -(HN=)CHNR, -HN(HN= )CHNR, -(S=)CHNR, -HN(S=)CHNR, wherein R H or a C ₁ -C ₁₉ alkyl group, and preferably wherein R H or a C ₁ -C ₆ alkyl group, wherein said R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ groups comprise 1 to 20 carbon atoms and optionally with at least one halogen -, oxygen or sulfur atom are substituted, - at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ contains at least one lithium ion, the number of lithium ions is equal to the number of groups A comprising a permanent negative charge to make the compound of formula (1) neutral overall. connection after claim 1 , wherein at least two R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ are groups A comprising a permanent negative charge selected from the group consisting of (thio)carboxylate, (Thio)sulfonate, (thio)phosphonate, sulfate and amidate groups. connection after claim 1 or claim 2 , wherein at least two R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ are B groups selected from the group consisting of -OLi, nitroxide, alkyl nitroxide, thioether, disulfide, alkylamine and arylamine. Connection after one of Claims 1 until 3 , where R ¹ , R ² , R ⁵ and R ⁶ are hydrogen atoms. Connection after one of Claims 1 until 4 , wherein said compound is selected from the group consisting of:

connection after claim 5 , wherein said compound is a tetra-lithium salt of 1,5-dihydroxy-2,6-naphthalenedicarboxylic acid (Li ₄ DHNDC) of the formula:

A process for preparing a compound of formula (1) according to any one of Claims 1 until 6 comprising the step of reacting a naphthol with MeOLi or LiH (lithiation step) in stoichiometric amount and under an inert atmosphere. procedure after claim 7 for the preparation of the tetra-lithium salt of 1,5-dihydroxy-2,6-naphthalenedicarboxylic acid (Li ₄ DHNDC). claim 5 , according to the following reaction scheme:

Use of a compound of formula (1) according to any one of Claims 1 until 6 as a solid organic catalyst (SOC) in a lithium-air battery cell. A solid organic catalyst (SOC) comprising a compound of formula (1) according to any one of Claims 1 until 6 . Solid Organic Catalyst (SOC) after claim 10 in the form of lamellar particles. Solid Organic Catalyst (SOC) after claim 10 or claim 11 with a specific surface area greater than or equal to 5 m ² .g ^-1 . A lithium-air battery cell comprising: - a negative electrode containing a negative electrode active material, - a positive electrode using oxygen as a positive electrode active material, and - a non-aqueous electrolyte medium interposed between the negative electrode and the positive electrode, wherein the positive electrode a solid organic catalyst (SOC) of formula (1) according to claims 10 until 12 includes. Lithium-air battery cell after Claim 13 , wherein the positive electrode further comprises carbon. Lithium-air battery cell after Claim 13 or Claim 14 , wherein the weight ratio between carbon and the solid organic catalyst (SOC) is 7:2. Lithium-air battery cell according to one of Claims 13 until 15 wherein the positive electrode further comprises a polymer binder selected from the group consisting of: polyethylene, polypropylene, polytetrafluoroethylene (PTFE), styrene-butadiene rubber, tetrafluoroethylene-hexafluoropropylene copolymers, tetrafluoroethylene-hexafluoropropylene copolymers (FEP), tetrafluoroethylene -Perfluoroalkyl vinyl ether copolymers (PFA), vinylidene fluoride-hexafluoropropylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers, ethylene-tetrafluoroethylene copolymers (ETFE resins), polychlorotrifluoroethylene (PCTFE), vinylidene fluoride-pentafluoropropylene copolymers, propylene-tetrafluoroethylene copolymers, ethylene- Chlorotrifluoroethylene copolymers (ECTFE), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymers, vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene copolymers, ethylene-acrylic acid copolymers and copolymers with sulfonate-terminated perfluorovinyl ether groups attached to a poly(tetrafluoroethylene) backbone, and preferably ice polytetrafluoroethylene (PTFE). Lithium-air battery cell after Claim 16 , wherein the weight ratio between the polymer binder and (solid organic catalyst (SOC) + carbon + polymer binder) is less than or equal to 20%. Lithium-air battery cell according to one of Claims 14 until 17 wherein the non-aqueous electrolyte medium comprises one or more aprotic organic solvents selected from the group consisting of: chain carbonates, cyclic ester carbonates, chain ethers, cyclic ethers, glycol ethers and nitrile solvents, and preferably glycol ethers such as tetraethylene glycol dimethyl ether (TEGDME). Battery pack with at least two assembled lithium-air battery cells according to any one of Claims 14 until 18 . using a battery pack claim 19 as a rechargeable battery for electric and hybrid vehicles, electronic devices, and stationary power generation devices. Vehicle, electronic device, and stationary power generating device that uses a battery pack claim 19 includes.

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