Rechargeable non-aqueous lithium-air battery cells containing solid organic catalysts

Abstract

The invention relates to a lithium-air battery cell, wherein the positive electrode comprises a solid p-type electroactive organic catalyst lithium salt. The invention also relates to a battery pack comprising several lithium-air battery cells according to the invention. The use of the battery pack according to the invention as a rechargeable battery for vehicles, such as electric vehicles and hybrid vehicles, electronic devices and stationary power generation devices is also part of the invention. Finally, the invention relates to vehicles, electronic devices and stationary power generation devices comprising the battery pack according to the invention.

Description

Technical Field

[0001] The invention relates to a lithium-air battery cell comprising a solid p-type electroactive organic catalyst lithium salt in the positive electrode. The invention also relates to a battery pack comprising several lithium-air battery cells according to the invention. The use of the battery pack according to the invention as a rechargeable battery for vehicles, such as electric vehicles and hybrid vehicles, electronic devices and stationary power generation devices is also part of the invention. Finally, the invention relates to vehicles, electronic devices and stationary power generation devices comprising the battery pack according to the invention. Background Art

[0002] Rechargeable lithium batteries have attracted considerable attention due to their high energy density and high power. In particular, rechargeable lithium-air batteries have attracted attention for electric vehicles and hybrid vehicles that require high energy density. Lithium-air battery cells are used in a variety of devices (such as computers and phones), automobiles or stationary applications, and can be assembled in battery packs.

[0003] Rechargeable lithium-air batteries use oxygen in the air as the cathode active material. Therefore, compared with conventional lithium rechargeable batteries containing transition metal oxides (such as lithium cobalt oxide) as the cathode active material, rechargeable lithium-air batteries can have a larger capacity.

[0004] In metal-air batteries, the cathode active material oxygen is not contained within the battery. Instead, this material is provided by the ambient atmosphere. Naturally, such a system in principle allows very high specific energy (energy provided by the battery per unit weight, usually given in Wh / kg in this technical field). In such a battery, oxygen is partially reduced to peroxides, or completely reduced to hydroxides or oxides, depending on the catalyst, electrolyte, oxygen availability, etc. When the negative electrode (anode) is lithium (Li), lithium peroxide (Li2O2) or lithium oxide (Li2O) is formed.

[0005] A lithium-air battery cell typically contains the following components:

[0006] - a metal anode (e.g. containing Li),

[0007] - a non-aqueous electrolyte (e.g. containing a lithium salt), and

[0008] -Air cathode.

[0009] The battery cell device may have other components such as: a collector on the anode and / or cathode side; a separator between the cathode side electrolyte (cathode electrolyte) and the anode side electrolyte (anode electrolyte); an isolation layer between the positive electrode (cathode) and the electrolyte or between the negative electrode (anode) and the electrolyte.

[0010] Problems to be solved in developing lithium-air battery cells include:

[0011] - avoid the migration of soluble catalysts used at the positive electrode (cathode) to the anode;

[0012] - Reduce the charge voltage and / or discharge voltage of lithium-air batteries by avoiding degradation of the electrolyte, thereby reducing hysteresis effects;

[0013] -Increase the capacity of lithium-air batteries at a fixed rate.

[0014] In order to avoid the migration of soluble catalysts at the anode, special separators can be used. Lee et al. (Adv. Energy Mater., 2017, 1602417) proposed using a glass fiber separator (GF / C, Whatman) coated with a polymer mixture of PEDOT:PSS [poly (3,4-ethylenedioxythiophene) polystyrene sulfonate] to avoid the migration of soluble catalyst DMPZ (5,10-dihydro-5,10-dimethylphenazine) for oxygen evolution reaction (OER). Qiao et al. (ACS Energy Lett. 2018, 3, 463-468) suggested using a special metal-organic framework (MOF)-based separator to block soluble substances to avoid the reciprocating movement of soluble catalysts to the Li anode.

[0015] Gao et al. proposed 2,5-di-tert-butyl-1,4-benzoquinone (DBBQ) as a soluble catalyst to increase the rate performance of non-aqueous lithium-air battery cells. The air electrode uses a porous carbon electrode based on a gas diffusion layer (GDL) as an air cathode. The anode is LiFePO4 (Nature Materials, 2016, 15, 882) or Li protected by Ohara glass, which requires the use of a dual-compartment battery (Nature Energy, Vol. 2, 17118 (2017)), but Li metal cannot be used as an anode because DBBQ will migrate to the anode and cause problems at the anode.

[0016] Chen et al. (Nature Chemistry, 2013, 5, 489) reported tetrathiafulvalene (TTF) as a soluble catalyst and nanoporous gold as an air cathode. Partially charged LiFePO4 was used as an anode.

[0017] Kundu et al. (ACS Cent., Sci., 2015, 1, 510-515) used tris[4-(diethylamino)phenyl]amine (TDPA) as a soluble catalyst to promote the oxidation of LiO2 (charging process).

[0018] The main drawback of the solutions proposed by the prior art is the use of soluble catalysts, which do not allow the use of Li metal (without additional protection) as anode. Indeed, the migration of soluble catalysts at the anode deteriorates the performance and safety of lithium-air batteries, requiring the use of alternative structures, such as:

[0019] - a protective barrier layer to protect the Li metal from contamination by soluble catalysts, which would deposit at the surface of the Li metal and create nucleation sites, causing dendrite formation,

[0020] - special separators to block the solute substances, or

[0021] - Special cell designs such as dual compartment cells containing two electrolyte compartments, one for the anode side and another for the cathode side, to protect the Li anode.

[0022] Hase et al. (Chem. Commun. 2016, 52, 12151-12154) also used methoxy-2,2,6,6-tetramethylpiperidin-1-oxide (MeO-TEMPO) as a soluble catalyst to enable oxidation of Li2O2 without parasitic reactions caused by electrochemical charging. However, at the end of charging, the TEMPO molecules need to be chemically regenerated outside the battery cell, which is completely unrealistic because the battery cell must be refilled with new electrolyte after each charge.

[0023] Bergner et al. (Phys. Chem. Chem. Phys., 2015, 17, 31769-31779) involve the use of nitroxide catalysts such as 1-methyl-2-oxadamantane-N-oxyl (1-Me-AZADO). However, these nitroxides have the disadvantage of being soluble in the electrolyte, so they degrade the anode of the lithium-air battery cell.

[0024] The present invention solves all the problems of the prior art by providing a lithium-air battery cell comprising a solid organic catalyst (SOC) in the positive electrode, which:

[0025] -Increase the capacity of Li-O2 battery cells at a fixed rate,

[0026] - Increase the rechargeability of Li-O2 cells and thus increase the cyclability of the cells,

[0027] - Increase rate performance (indicates the (dis)charge speed of the battery cell) while maintaining appropriate capacity,

[0028] - Allows for simpler battery cell design, since the SOC of the present invention is insoluble, no lithium protection layer, special separators or dual compartment batteries are required,

[0029] -SOC self-regenerates within the battery cell and returns to its initial state,

[0030] - Allows to reduce the amount of carbon used at the positive electrode (air cathode), so avoiding the corrosion of the carbon (which is considered a source of poor rechargeability). Indeed, it is well known that carbon causes corrosion in lithium-air battery systems and leads to the partial formation of Li2CO3 (side reaction discharge product) instead of Li2O2 (desirable discharge product).

[0031] Additionally, the SOC of the present invention is cost-effective (compared to other catalysts used in lithium-air systems based on gold, platinum or cobalt oxides), and is an environmentally friendly organic material that can be prepared from renewable resources (biomass). Summary of the invention

[0032] One aspect of the present invention relates to a lithium-air battery cell comprising:

[0033] - a negative electrode (anode), which contains a negative electrode active material;

[0034] - a positive electrode (cathode) which uses oxygen as the positive electrode active material; and

[0035] - a non-aqueous electrolyte medium disposed between the negative electrode and the positive electrode;

[0036] The positive electrode comprises a solid p-type electroactive organic catalyst lithium salt.

[0037] In another aspect, the invention relates to a battery comprising several lithium-air battery cells according to the invention assembled together.

[0038] The invention also relates to the use of the battery pack according to the invention as a rechargeable battery for electric and hybrid vehicles, electronic devices, and stationary power generation devices.

[0039] Finally, the invention also relates to a vehicle, an electronic device and a stationary power generation device comprising a battery pack according to the invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 It shows that at 0.2 mAh cm -2 The voltage of a cycled lithium-air battery cell (V vs. Li + / Li) relative to capacity (mAh·cm -2 ), as described in Examples 1, 2 and 3 (Ex1, Ex2, Ex3) compared to Comparative Examples 1, 2 and 3 (CE1, CE2, CE3).

[0041] Figure 2 It shows that relative to Li+ / Li potential window 2.2-4.6V and 800mAh.g -1 SOC (~2.15mAh·cm -2 ) within the capacity limit, Example 1 (Li2DAnT:Carbon Super C65 (2:7)) is 0.2 mAh·cm -2 The cycling rate of lithium-air battery cells ( Figure 2 a) and capacity retention of lithium-air battery cells versus cycle number ( Figure 2 b).

[0042] Figure 3 It shows that relative to Li + / Li potential window 2.2-4.6V and 2000mAh.g -1 SOC (~6mAh·cm -2 ) within the capacity limit, Example 1 ( Figure 3 a) and Comparative Example 1 ( Figure 3 b) at 0.2 mAh cm -2 Rate of cycling of a lithium-air battery cell.

[0043] Figure 4 The results show that for an electrode containing Li2DAnT:Carbon Super C65 in a ratio of 2:7 (at 0.5 mAh cm -2 Electrostatic discharge performed), comparison of the first cycle of the lithium-air battery cell of Example 1 using Li2DAnT obtained in argon (solid line) or in oxygen (dashed line) as working electrode for SOC.

[0044] Figure 5 A metal-air battery cell with one electrochemical cell in a gas compartment ( Figure 5 a) and a metal-air battery with several cells in the gas compartment ( Figure 5 b) Schematic diagram of an electrochemical reactor, wherein: 11: gas compartment (dry air or pure oxygen), 12: metal anode, 13: cathode, 14: electrolyte / separator, 15: anode current collector, and 16: cathode current collector. DETAILED DESCRIPTION

[0045] The present invention relates to a lithium-air battery, comprising:

[0046] - a negative electrode (anode), which contains a negative electrode active material;

[0047] - a positive electrode (cathode) which uses oxygen as the positive electrode active material; and

[0048] - a non-aqueous electrolyte medium disposed between the negative electrode and the positive electrode;

[0049] The positive electrode comprises a solid p-type electroactive organic catalyst lithium salt.

[0050] The main advantage of the solid organic catalyst (SOC) of the present invention is that it is insoluble in the electrolyte, avoiding the migration of soluble species to the anode. It further improves the electrochemical performance of reactions involving oxygen such as oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), thereby improving the capacity and rechargeability of non-aqueous lithium-air battery cells.

[0051] <Anode>

[0052] In the lithium-air battery cell of the present invention, the negative electrode (which may also be referred to as "anode" hereinafter) contains at least one anode active material (which may also be referred to as "negative electrode active material" hereinafter). As the anode active material, a general anode active material for lithium batteries can be used, and there is no particular limitation on the anode active material. Generally, the anode active material is capable of storing / releasing lithium ions (Li + ).

[0053] Specific anode active materials for rechargeable lithium-air batteries are, for example, lithium metal, lithium-protected anodes, lithium alloys such as lithium-aluminum alloys, lithium-tin alloys, lithium-lead alloys and lithium-silicon alloys, metal oxides such as lithium-titanium oxides, metal nitrides such as lithium-cobalt nitrides, lithium-iron nitrides and lithium manganese nitrides. Among them, lithium metal is preferred.

[0054] "Lithium protected anode" refers here to, for example (but not limited to), a "lithium protected electrode" (LPE) as described in US8,652,692. Typically the Li metal is covered by a solid electrolyte, such as LiSiCON (lithium superionic conductor) having the formula LiM2(PO4)3. Between the LiSiCON and the Li metal, there is typically an interlayer (e.g. composed of Cu3N / Li3N). In the LPE system, the Li metal can be directly attached 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 Li ion conductivity. Such materials have been described, for example, in US7,282,295 and US7,491,458. LiSiCON materials have also been described in Nature Materials, 10, 682-686 (2011).

[0055] When a metal, alloy, or the like in the form of foil or metal is used as the anode active material, it can be used as the anode itself.

[0056] The anode needs to contain at least one anode active material; however, it may contain a binder to fix the anode active material as needed. The type and usage of the binder are the same as those of the air cathode described below.

[0057] The anode current collector may be connected to the anode, which collects current from the anode. There are no particular restrictions on the material of the anode current collector and its shape. Examples of the material of the anode current collector include stainless steel, copper and nickel. Examples of the form of the anode current collector include foil form, plate form and mesh (grid) form.

[0058] <Cathode>

[0059] In the lithium-air battery cell of the present invention, the positive electrode (which may also be referred to as “cathode” hereinafter) contains at least a cathode active material (which may also be referred to as “positive electrode active material” hereinafter).

[0060] 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.

[0061] <Catalyst>

[0062] In the lithium-air battery cell of the present invention, the catalyst present in the positive electrode is a solid p-type electroactive organic catalyst lithium salt.

[0063] In a preferred embodiment, the solid p-type electroactive organic catalyst lithium salt has the following general structure (1):

[0064]

[0065] in:

[0066] -Ar is an aromatic or heteroaromatic ring selected from the group consisting of benzene, naphthalene, perylene, anthracene, phenanthrene, tetracene, triphenylene, pyrene, pentacene, benzo[a]pyrene, corannulene, benzo[ghi]perylene, coronene, ovalene, benzo[c]fluorine, pyridine, quinolone, isoquinoline, pyrazine, quinoxaline, acridine, pyrimidine, quinazoline, pyridazine, cinnoline, phthalazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine,

[0067] -R 1 To R 4Each is independently selected from: H, aryl, alkyl, alkenyl, alkaryl, alkoxy, aryloxy, amino-alkyl, amino-aryl, thioalkyl, thioaryl, alkyl phosphonate, aryl phosphonate, cycloalkadienyl, -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 is H or C1-C 19 Alkyl, preferably R is H or C1-C6 alkyl, said R 1 To R 4 The group contains 1 to 20 carbon atoms and is optionally substituted with at least one halogen, oxygen or sulfur atom,

[0068] -R 5 and R 6 Each is independently selected from: H, aryl, alkyl, alkenyl, alkaryl, alkoxy, aryloxy, amino-alkyl, amino-aryl, thioalkyl, thioaryl, alkyl phosphonate, aryl phosphonate, cycloalkadienyl, -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 is H or C1-C 19 Alkyl, preferably R is H or C1-C6 alkyl, said R 5 and R 6 The group contains 1 to 20 carbon atoms and is optionally substituted with at least one halogen, oxygen or sulfur atom,

[0069] -Y and Y' are anionic groups, each independently selected from carboxylate, thiocarboxylate, sulfonate, thiosulfonate, phosphonate, thiophosphonate, sulfate, amidate groups.

[0070] In the meaning of the present invention, the following terms refer to:

[0071] -Alkyl: based on saturated, linear or branched C1-C 20 , preferably C1-C 12 , more preferably an aliphatic radical of a C1-C6, even more preferably a C1-C4 hydrocarbon. The term "branched" means that at least one lower alkyl group, such as a methyl or ethyl group, is carried by a linear alkyl chain. As alkyl, there may be mentioned, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl and n-pentyl;

[0072] - aryl: any functional group or substituent derived from at least one aromatic ring; the aromatic ring corresponds to any flat monocyclic or polycyclic radical containing a delocalized π system, wherein each atom of the ring contains p orbitals, which overlap one another; among such aryl radicals, mention may be made of phenyl, biphenyl, naphthalene and anthracene radicals. The aryl radicals of the invention preferably contain from 4 to 20 carbon atoms, even more preferably from 4 to 12 carbon atoms, even more preferably from 5 to 6 carbon atoms;

[0073] -Alkenyl: based on linear or branched C1-C 20 , preferably C1-C 12 , more preferably C1-C6, even more preferably C1-C4 unsaturated hydrocarbon containing at least one carbon-carbon double bond aliphatic group. The term "branched" means that at least one lower alkyl group such as methyl or ethyl is carried by a linear alkenyl chain;

[0074] - Alkaryl: any group derived from an alkyl group as defined above, in which a hydrogen atom is replaced by an aryl group as defined above. The alkaryl group preferably contains 5 to 20 carbon atoms, more preferably 5 to 12 carbon atoms;

[0075] -Alkoxy: based on saturated, linear or branched C1-C 20 , preferably C1-C 12 , more preferably C1-C6, even more preferably C1-C4 hydrocarbon containing an oxygen atom aliphatic group. As the alkyl group, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy and isobutoxy may be mentioned;

[0076] -Aryloxy: any aryl group attached to an oxygen atom, which preferably contains 4 to 20 carbon atoms, more preferably 4 to 12 carbon atoms. As aryloxy, there may be mentioned, for example, phenoxy;

[0077] -Amino-alkyl: based on saturated, linear or branched C1-C 20 , preferably C1-C 12 , more preferably C1-C6, even more preferably C1-C4 hydrocarbon, an aliphatic group with an amino group, preferably a primary amino group -NH2;

[0078] -amino-aryl: any aryl group attached to an amino group, preferably a primary amino group -NH2, preferably containing 4 to 20 carbon atoms, more preferably 4 to 12 carbon atoms;

[0079] -Thioalkyl: based on saturated, linear or branched C1-C 20 , preferably C1-C 12 , more preferably a C1-C6, even more preferably a C1-C4 hydrocarbon aliphatic group with a thiol group -SH;

[0080] -thioaryl: any aryl group attached to a thiol group -SH, preferably containing 4 to 20 carbon atoms, more preferably 4 to 12 carbon atoms;

[0081] - Alkyl phosphonate: any alkyl group attached to a phosphonic acid group -P(=O)(OR')2, wherein R' is based on a saturated, linear or branched C1-C 20 , preferably C1-C 12 , more preferably aliphatic groups of C1-C6, even more preferably C1-C4 hydrocarbons;

[0082] -Aryl phosphonate: any aromatic group attached to a phosphonate group -P(=O)(OR')2, wherein R' is based on a saturated, linear or branched C1-C 20 , preferably C1-C 12 , more preferably aliphatic groups of C1-C6, even more preferably C1-C4 hydrocarbons;

[0083] - Cycloalkadienyl: any unsaturated cyclic group containing at least two carbon-carbon double bonds, preferably comprising 5 to 20 carbon atoms, more preferably 5 to 12 carbon atoms.

[0084] The presence of anionic groups Y and Y' results in a decrease in the solubility of the solid p-type electroactive organic catalyst lithium salt in aprotic polar solvents.

[0085] In the general structure (1), the aromatic or heteroaromatic ring Ar is preferably benzene or naphthalene.

[0086] In the general structure (1), R 1 To R 4 Preferably each is independently selected from hydrogen (H) and aryl, the latter comprising from 4 to 20 carbon atoms and optionally substituted with at least one halogen, oxygen or sulfur atom. 1 To R 4 Even more preferably each is independently selected from H and phenyl (-C6H5).

[0087] In the general structure (1), R 5 and R 6 Preferred is H, -CH3 or -C2H5, more preferred is H.

[0088] In the general structure (1), Y and Y' are preferably carboxylate groups.

[0089] In a more preferred embodiment, the solid p-type electroactive organic catalyst lithium salt exhibits the following general structure (2):

[0090]

[0091] in:

[0092] -R1 and R 3 Each is independently selected from: H, aryl, alkyl, alkenyl, alkaryl, alkoxy, aryloxy, amino-alkyl, amino-aryl, thioalkyl, thioaryl, alkyl phosphonate, aryl phosphonate, cycloalkadienyl, -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 is H or C1-C 19 Alkyl, preferably R is H or C1-C6 alkyl, said R 1 and R 3 The group contains 1 to 20 carbon atoms and is optionally substituted with at least one halogen, oxygen or sulfur atom,

[0093] -R 5 and R 6 Each is independently selected from: H, aryl, alkyl, alkenyl, alkaryl, alkoxy, aryloxy, amino-alkyl, amino-aryl, thioalkyl, thioaryl, alkyl phosphonate, aryl phosphonate, cycloalkadienyl, -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 is H or C1-C 19 Alkyl, preferably R is H or C1-C6 alkyl, said R 5 and R 6 The group contains 1 to 20 carbon atoms and is optionally substituted with at least one halogen, oxygen or sulfur atom.

[0094] In the general structure (2), R 1 and R 3 Preferably each is independently selected from H and aryl, the latter comprising from 4 to 20 carbon atoms and optionally substituted with at least one halogen, oxygen or sulfur atom. 1 and R 3 Even more preferred is phenyl (-C6H5).

[0095] In the general structure (2), R 5 and R 6 Preferred is H, -CH3 or -C2H5, more preferred is H.

[0096] The presence of carboxylic acid esters in the solid p-type electroactive organic catalyst lithium salt of the present invention further reduces the solubility of the SOC in aprotic polar solvents, which are typically used in electrolytes for non-aqueous lithium-air batteries.

[0097] In a particularly preferred embodiment, the solid p-type electroactive organic catalyst lithium salt of the present invention is dilithium 2,5-(diphenylamino)terephthalate (Li2DAnT).

[0098] Li2DAnT is already known for its use as an organic Li-ion battery material, but not as a lithium-air battery material (Deunf et al., Journal of Materials Chemistry A, 2016, 4, 6131-6139). In this organic lithium-ion battery material, the electrolyte is based on carbonates, which are not recommended for lithium-air batteries due to their decomposition.

[0099] The solid p-type electroactive organic catalyst lithium salt of the present invention advantageously exhibits a carbonylation rate of less than 0.148 g·L when in 1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in tetraethylene glycol dimethyl ether (TEGDME). -1 Solubility.

[0100] The positive electrode of the lithium-air battery cell of the present invention may further comprise a solid n-type electroactive organic catalyst lithium salt.

[0101] In a preferred embodiment, the solid n-type electroactive organic catalyst lithium salt exhibits the following general structure (3):

[0102]

[0103] Where R 7 and R 8 Each is independently selected from: H, aryl, alkyl, alkenyl, alkaryl, alkoxy, aryloxy, amino-alkyl, amino-aryl, thioalkyl, thioaryl, alkyl phosphonate, aryl phosphonate, cycloalkadienyl, -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 is H or C1-C 19 Alkyl, preferably R is H or C1-C6 alkyl, said R 7 and R 8 The group contains 1 to 20 carbon atoms and is optionally substituted with at least one halogen, oxygen or sulfur atom.

[0104] R 7 and R 8 Preferably each is independently selected from H and aryl, the latter comprising from 4 to 20 carbon atoms and optionally substituted with at least one halogen, oxygen or sulfur atom. 7 and R 8More preferred is H, -CH3 or -C2H5, and more preferred is H.

[0105] In a particularly preferred embodiment, the solid n-type electroactive organic catalyst lithium salt of the present invention is (2,5-dilithio)-p-dilithium terephthalate (Li4-p-DHT).

[0106] Li4-p-DHT is known as a positive active material in Li-ion battery systems (Renault et al., Energy & Environmental Science, 2013, 6, 2124-2133). The electrolyte used in these systems is 1M LiPF6 in EC:DMC (1:1), and the battery is therefore operated in an oxygen-free inert atmosphere, since EC:DMC decomposes in the presence of oxygen.

[0107] The weight ratio of the solid p-type electroactive organic catalyst lithium salt to the solid n-type electroactive organic catalyst lithium salt may be 0.1 / 99.9 to 100 / 0, preferably 60 / 40 to 40 / 60, more preferably 50 / 50.

[0108] In the lithium-air battery cell of the present invention, the positive electrode may be a component in which a redox catalyst is supported on a carrier. An example of a carrier is carbon. Therefore, in the lithium-air battery cell of the present invention, the positive electrode advantageously further comprises carbon. Examples of carbon include carbon black, such as Ketjen black, acetylene black, channel black, furnace black, lamp black, and thermal black; graphite, such as natural graphite, such as flake graphite, artificial graphite, and expanded graphite; activated carbon 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. Modified carbon such as N-doped carbon may also be used.

[0109] Positive electrode materials for the lithium-air battery cells of the present invention based on materials other than carbon can also be used. For example, positive electrode materials based on metal foams, stable and conductive metal oxides, or steel can be used.

[0110] In the present invention, in the case of using carbon, it is preferably a porous material in the form of a powder, and preferably has a carbon content of 20 to 2000 m 2 ·g -1 , more preferably 60 to 2000 m 2 ·g -1 , even more preferably 60 to 1500 m 2 ·g -1For example, carbon can be used on which a conventional treatment is performed to increase porosity or surface area, followed by another treatment to increase wettability. Different forms of carbon can be used in the present invention, including SUPER Li (from TIMCAL), which exhibits a particle size of 40 nm and 62 m 2 ·g -1 Specific surface area (determined by the Brunauer-Emmett-Teller method); BLACK 2000 (from Cabot Corporation), which exhibited a particle size of 12 nm and a 2 ·g -1 Specific surface area (determined by the Brunauer-Emmett-Teller method); EC-600JD powder (from AzkoNobel) shows 1400m 2 ·g -1 The specific surface area of ​​​​the present invention is determined by the Brunauer-Emmett-Teller method. Examples of commercially available carbon products that can be used in the present invention include Carbon Super C65 (from Imerys), KS series, SFG series and Super S series (from TIMCAL), activated carbon products obtained from Norit and AB-Vulcan 72 (from 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).

[0111] Examples of methods for increasing the porosity, surface area, and wettability of carbon include physical activation or chemical activation. Chemical activation methods include, for example, immersing the carbon material in a strong aqueous base solution (e.g., potassium hydroxide solution), an acid solution (e.g., nitric acid or phosphoric acid), or a salt (e.g., zinc chloride). This treatment may be followed (but not necessarily) by a calcination step at a relatively low temperature (e.g., 450 to 900° C.).

[0112] In addition, carbon preferably has a pore size of 5nm or larger, preferably 20nm or larger holes. The specific surface area and pore size of carbon can be measured, for example, by BET method or BJH method. In addition, usually, the preferred average particle size (primary particle size) of carbon is 8 to 350nm, more preferably 30 to 50nm. The average primary particle size of carbon can be measured by TEM.

[0113] In the lithium-air battery cell of the present invention, the weight ratio of carbon to (solid p-type electroactive organic catalyst lithium salt+solid n-type electroactive organic catalyst lithium salt+carbon) is advantageously greater than or equal to 77%.

[0114] 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 powder, nickel powder, aluminum powder; and organic conductive materials such as polyphenylene derivatives. They may be used separately or in combination as a mixture.

[0115] In the lithium-air battery cell of the present invention, the positive electrode may include a polymer binder. There is no particular limitation on the polymer binder. The polymer binder may include a thermoplastic resin or a thermosetting resin. Examples include polyethylene, polypropylene, polytetrafluoroethylene (PTFE), styrene-butadiene rubber, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer (ETFE resin), polychlorotrifluoroethylene (PCTFE), vinylidene fluoride-pentafluoropropylene copolymer, propylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer (ECTFE), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene copolymer, ethylene-acrylic acid copolymer. Copolymers having perfluorovinyl ether groups terminated by sulfonate / ester groups attached to the polytetrafluoroethylene backbone are generally referred to as Those of can also be used as the polymer binder of the present invention. These polymer binders can be used separately or in combination as a mixture. Polytetrafluoroethylene (PTFE) is a particularly preferred polymer binder.

[0116] In the lithium-air battery cell of the present invention, the weight ratio between the polymer binder and (solid p-type electroactive organic catalyst lithium salt+solid n-type electroactive organic catalyst lithium salt+carbon+polymer binder) is less than or equal to 20%.

[0117] Typically, in a favorable embodiment of the present invention, an air cathode current collector is connected to the air cathode, which collects current from the air cathode. There is no particular limitation on the material of the air cathode current collector and its shape. Examples of materials for the air cathode current collector include stainless steel, aluminum, iron, nickel, titanium and carbon. Examples of the form of the air cathode current collector include foil form, plate form, mesh (grid) form and fiber form. Preferably, the air cathode current collector has a porous structure such as a mesh form, because the current collector having a porous structure has excellent efficiency in supplying oxygen to the air cathode.

[0118] In some embodiments, the air electrode (air cathode) further comprises hydrophobic hollow fibers. Hydrophobic fibers tend to create spaces between itself and the electrolyte. These spaces are conducive to oxygen diffusion in the air electrode, which enables the use of thicker electrodes. Typically, the thickness of the carbon-based air electrode is 0.5 to 0.7 mm. Adding hydrophobic fibers allows the use of electrodes with a thickness of at least 1 mm. Suitable fibers include DuPont (100% polyester fiber with multiple holes in the core), goose down (very small, extremely light fluff close to goose skin), PTFE fiber, and woven hollow fiber cloth, etc. Carbon can also be coated on these fibers.

[0119] <Electrolytes>

[0120] In the lithium-air battery cell of the present invention, the non-aqueous ion-conductive (electrolyte) medium arranged between the negative electrode and the positive electrode is a non-aqueous electrolytic solution containing one or more organic solvents and usually containing salts. Non-limiting examples of salts that can be used include known supporting electrolytes such as LiPF6, LiClO4, LiAsF6, LiBF4, Li(CF3SO2)2N(LiTFSI), LiFSI, Li(CF3SO3) (lithium trifluoromethanesulfonate), LiN(C2F5SO2)2, LiBOB, LiFAP, LiDMSI, LiHPSI, LiBETI, LiDFOB, LiBFMB, LiBison, LiDCTA, LiTDI, LiPDI. These salts can be used separately or in combination. The concentration of the salt is preferably 0.1 to 2.0M, more preferably 0.8 to 1.2M.

[0121] Lithium salts are suitable for use in electrolyte media in combination with aprotic organic solvents known for 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 ethyl methyl 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, triethylene glycol dimethyl ether, with a weight average molecular weight Mw of 90 to 225 g·mol -1 Polyethylene glycol dimethyl ether. Nitrile solvents such as acetonitrile, propionitrile and 3-methoxypropionitrile can also be used. These aprotic organic solvents can be used separately or in combination as a mixture. Glycol ethers are preferred aprotic organic solvents, particularly tetraethylene glycol dimethyl ether (TEGDME).

[0122] In the framework of the present invention, gel polymer electrolytes may also be used. A gelled electrolyte having lithium ion conductivity may be obtained, for example, by adding a polymer to a non-aqueous electrolytic solution for gelation. Specifically, gelation may be induced by adding polymers such as polyethylene oxide (PEO), polyvinylidene fluoride (PVDF, commercially available as Kynar, etc.), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA) and polyvinyl chloride (PVC). A review of the use of gel-type polymer electrolytes for lithium ion batteries is provided by Song et al., Journal of Power Sources, 77 (1999), 183-197.

[0123] Crosslinkable and / or thermosetting components may also be added to the gel electrolyte formulation to improve its mechanical properties.

[0124] Likewise, large amounts of plasticizers (PEG, crown ethers, etc.) can be introduced to improve the ionic conductivity of polymer electrolytes.

[0125] In addition, nanoparticles / ceramics (Al2O3, SiO2, ZrO2, MgO, CeO2, etc.) can be added to such gel polymer electrolytes to increase their conductivity. In this regard, reference can be made to EP1096591A1 or Croce et al., Electrochimica Acta 46 (2001), 2457-2461.

[0126] The nanoparticle / ceramic filler content is typically less than 10 wt % of the film. For example, Al2O3 nanoparticles can be obtained from Aldrich Research Grade and have a 5.8 nm particle size (Swierczynski et al., Chem. Mater., 2001, 13, 1560-1564). SiO2 fumed silica can be obtained from Aldrich Reagents Grade and has a 7 nm particle size. Typically, the nanoparticle size is preferably about 15 nm or less.

[0127] It is further contemplated that an oxygen solubility enhancer is added to the electrolyte medium within the framework of the present invention. Such an oxygen solubility enhancer may be a fluorinated polymer, a fluorinated ether, a fluorinated ester, a fluorinated carbonate, a fluorinated carbon material, a fluorinated blood substitute, or even a metalloprotein. Such oxygen solubility enhancers are described in US2010 / 0266907.

[0128] <Partition>

[0129] In the rechargeable lithium-air battery cell of the present invention, a separator may be advantageously provided between the air cathode and the anode to complete electrical insulation between these electrodes. There is no particular limitation on the separator as long as it can electrically insulate the air cathode and the anode from each other and has a structure that allows an electrolyte to be present between the air cathode and the anode.

[0130] Examples of the separator include porous films and nonwoven fabrics comprising polyethylene, polypropylene, cellulose, polyvinylidene fluoride, glass ceramics, etc. Among them, a glass ceramic separator is preferred.

[0131] <Battery cell case>

[0132] As a cell shell for accommodating a rechargeable lithium-air battery cell, a general battery shell for a rechargeable lithium battery cell can be used. There is no particular limitation on the shape of the cell shell as long as it can hold the above-mentioned air cathode, anode and electrolyte. Specific examples of the shape of the cell shell include coin-shaped, flat-plate-shaped, cylindrical and laminated body-shaped. The battery of the present invention can be completely enclosed in an oxygen-permeable membrane, advantageously a membrane that exhibits selectivity for oxygen diffusion relative to water.

[0133] <Application of the battery cell of the present invention>

[0134] When the active material oxygen is supplied to the air cathode, the rechargeable lithium-air battery cell of the present invention is discharged. Examples of oxygen supply sources include air and oxygen, preferably oxygen. There is no particular limitation on the pressure of the supplied air or oxygen, and it can be appropriately determined.

[0135] The lithium-air battery cell of the present invention can be used as a primary battery cell or a rechargeable secondary battery cell.

[0136] The lithium-air battery cell of the present invention may, for example, be used in practice in a method in which the battery is cycled between certain limits defined by initial and final voltages, or initial and final capacities or specific capacities. For example, a method of using a lithium-air battery cell of the present invention may consist of a method in which:

[0137] (a) providing a lithium-air battery cell in a fully charged state;

[0138] (b) subjecting the lithium-air battery cell to discharge until the specific capacity reaches a value X;

[0139] (c) recharging the lithium-air battery cell;

[0140] (d) Repeat steps (b) and (c).

[0141] The selected specific capacity value X may vary widely, for example, suitably between 200 and 10000 mAh·g -1 The specific capacity of the lithium-air battery cell can be determined by discharging until 2V. It would be appropriate to cycle the battery cell within the limits of not reaching full discharge or charge during operation of the battery cell. Advantageously, the battery cell can be cycled at 10 to 90%, preferably 20 to 80%, more preferably 20 to 70% of its specific capacity (determined in step (b)). Cycling can also be performed between certain limits of the initial or maximum theoretical discharge capacity. Capacity-limited cycling will result in a longer battery life, so it would be appropriate to limit the cycle capacity to about 30% of the full discharge capacity.

[0142] A battery cell product may be provided whose air cathode contains added Li2O2. Such a battery cell will typically be charged before use.

[0143] The lithium-air battery cells of the present invention can be used as rechargeable lithium batteries for electric and hybrid vehicles, electronic devices (such as computers and phones), and stationary power generation devices, and can be assembled in battery packs. The number of battery cells can vary depending on the final use of the lithium-air battery, preferably ranging from 2 to 250 battery cells. Depending on the final goal, there are two possible ways to assemble the battery cells: in parallel or in series. When in parallel, the capacity of each battery is added while maintaining the same voltage. When in series, the voltage of each battery is added while the capacity is one of the smallest batteries.

[0144] The present invention includes any combination of the above-mentioned elements in all possible variations thereof, unless otherwise indicated herein or clearly contradictory to the context. Therefore, all features and embodiments specifically described herein as applicable, advantageous or preferred in the context of the present invention are interpreted as being used in combination with each other in preferred embodiments of the present invention.

[0145] Example

[0146] Preparation of SOC according to the present invention: Li2DAnT

[0147] Lithiation of 2,5-(dianilino)terephthalic acid (H2DAnT), also known as 2,5-bis(phenylamino)terephthalic acid (1.0 g, 2.9 mmol) was carried out in anhydrous tetrahydrofuran (30 mL) with a stoichiometric amount of lithium hydride (45.6 mg, 5.8 mmol). The solution was stirred at room temperature for 20 hours under an inert atmosphere. After filtering the precipitate, washing it thoroughly with diethyl ether and drying it under vacuum at 60 ° C overnight, the final Li2DAnT was obtained. 1.95 THF compound (1.2 g, 86%) . Li2DAnT 1.95THF: pale yellow powder; IR: vmax(KBr) / cm -1 3360, 2980-2880 (THF), 1600, 1570, 1530, 1500, 1440, 1420, 1370, 1285, 1050 (THF)cm -1 ; 1 H NMR: δ H (400 MHz, (CD3)2SO) 11.22 (2H, s, H unstable), 7.92 (2H, s), 7.20-7.16 (4H, t, J = 6.8 Hz, H-meta), 7.06-7.03 (4H, d, J = 8.0 Hz, H-ortho), 6.74-6.70 (2H, t, J = 6.8 Hz, H-para), 3.62-3.59 (t, H-THF), 1.78-1.75 (t, H-THF); 13 CNMR: δ C : (400 MHz, (CD3)2SO) 170.4 (C, C=O), 144.7 (C, C-NH), 135.4 (C, C-NHPh), 128.9 (CH, C-meta), 127.0 (C, C-COOLi), 118.8 (CH), 118.1 (CH, C-para), 116.1 (CH, C-ortho), 67.0 (CH2, THF), 25.1 (CH2, THF); ESI-HRMS m / z 353.1104 [M-Li] - (C 20 H 14 LiN2O4 calculated value, 353.1114); elemental analysis; found: C, 64.86%; H, 5.83%; N, 5.18% (C 20 H 14 Li2N2O4.1.95THF·0.75H2O Calculated: C, 64.92%; H, 6.09%; N, 5.45%), since traces of water cannot be avoided due to the high hygroscopicity of the compound; ICP-OES for Li quantification; found: Li, 2.73% (C 20 H 14 Li·N2O4·1.95THF Calculated value: Li, 2.77%) For Li2DAnT 1.95 For the desolvation of THF, a small amount (100 mg scale) of the previously ground powder was heated in a Büchner glass oven (B-585 Kugelrohr) at a real internal temperature of 250° C. for 18 hours. The final Li2DAnT compound (100 mg scale, quantitative yield) was obtained. The effectiveness of the desolvation process was checked by thermal analysis, and the absence of traces of THF was confirmed by NMR and IR spectroscopy.

[0148] Li2DAnT: bright yellow powder; IR: vmax(KBr) / cm -1 3370, 1600, 1570, 1530, 1500, 1440, 1420, 1280cm -1 ; 1 H NMR: δ H (400 MHz, (CD3)2SO) 11.26 (2H, s), 7.98 (2H, s), 7.25-7.22 (4H, t, J = 8.0 Hz, H-meta), 7.12-7.10 (4H, d, J = 8.0 Hz, H-ortho), 6.79-6.76 (2H, t, J = 7.2 Hz, H-para); 13 C NMR: δ C : (100 MHz, (CD3)2SO) 170.4 (C, C=O), 144.7 (C, C-NH), 135.5 (C, C-NHPh), 128.9 (CH, C-meta), 127.0 (C, C-COOLi), 118.8 (CH), 118.1 (CH, C-para) 116.1 (CH, C-ortho); ESI-HRMS m / z 353.1104 [M-Li] + (C 20 H 14 LiN2O4 calculated, 353.1114); ICP-OES for Li quantification; found: Li, 4.02% (C 20 H 14 LiN2O4 calculated value: Li, 3.85%).

[0149] The characteristics of the obtained Li2DAnT are as follows:

[0150] -Specific surface area: 316m 2 ·g -1 ,

[0151] -Density: 1.375 g cm -3 ,and

[0152] -Morphology: small plate.

[0153] Preparation of SOC according to the present invention: Li4-p-DHT

[0154] Lithiation of commercially available 2,5-dihydroxyterephthalic acid (H4-p-DHT) (Aldrich, 198.1 mg, 1 mmol) was carried out in anhydrous methanol (15 mL Aldrich) with a stoichiometric amount of lithium methoxide (MeOLi) (Aldrich, 2.2 M methanol solution, 1.82 mL, 4 mmol). A yellow precipitate was formed rapidly. After 14 h of reaction, methanol was removed (by filtering the precipitate or evaporating at room temperature under vacuum in a Büchner glass oven B-585 Kugelrohr), and the yellow solid was dried overnight at 100 ° C in a Büchner glass oven B-585 Kugelrohr under vacuum, and then at 200 ° C for 12 hours.

[0155] Yield = 98%. IR: vmax (KBr) / cm -1 1582(C=O), 1472-1432(C=C), 1372(OC-O), 1237(CO), 1115, 887, 823cm -1 ; 1 H NMR: δ H (300MHz, (CD3)2SO)+H2SO4 11.20 (s, H acid), 7.21ppm (s, 2H, H aromatics); 13 C NMR: δ C (75MHz, (CD3)2SO) 170.74(COOH), 152.42(C-OH), 119.88(C-COOH), 117.87ppm(CH).

[0156] The specific surface area of ​​Li4-p-DHT obtained is 35 m 2 ·g -1 .

[0157] Prepare electrolyte:

[0158] Prepare three electrolyte solutions by dissolving the following components:

[0159] a) 1.0 M bis(trifluoromethane)sulfonyl imide lithium salt (LiTFSI, BASF) in TEGDME (Sigma Aldrich, humidity controlled grade),

[0160] b) 1.0 M LiTFSI and 10 -2 M (10 mM) DBBQ (Sigma Aldrich),

[0161] c) 1.0 M LiTFSI and 10 -2 M (10 mM) TTF (Sigma Aldrich).

[0162] LiTFSI, DBBQ and TTF were dried under vacuum at 100 °C overnight in a glove box. TEGDME solvent was used after drying / storage on 100 μM molecular sieves (Sigma Aldrich) for at least 15 days. The water content of solvent and electrolyte was determined by means of 831 KF Karl Fischer coulometer (Metrohm) technique and was measured to be less than 4 ppm.

[0163] Preparation of LiFePO4 (LFP) anode:

[0164] wt% composition: LFP / carbon black / binder (PVdF): 88 / 4.5 / 7.5

[0165] Expected loading capacity: 1.3 mAh cm -2

[0166] Expected loading amount: 9.89 mg tot cm -2

[0167] Coating thickness (without aluminum foil): 47μm

[0168] Aluminum foil thickness: 15μm (ρ Al =2.7 g cm -3 )

[0169] Coating porosity: 35%

[0170] Expected features:

[0171] Q 可逆 (@C / 5, potential window: 2.1-4.3V)~152mAh·g LFP -1

[0172] The LFP electrodes used in the following tests were perforated 11 mm diameter disks (area: 0.9503 cm 2 ).

[0173] A partially oxidized LFP electrode was used as the counter electrode for all tests for standardization purposes.

[0174] Also for normalization purposes, all data are plotted in voltage using a 3.4 volt calibration, plotted in volts vs. Li + / Li expression.

[0175] Battery assembly:

[0176] In order to compare the SOC of the present invention with soluble catalysts (DBBQ and TTF) under the same experimental conditions, the test was performed in a configuration of partially oxidized LFP / electrolyte / O2 electrode with LFP anode.

[0177] Modified Swagelok cells with openings to the atmosphere were assembled using pure lithium metal discs (diameter = 11 mm and thickness = 0.7 mm) or LFP discs (provided by IMN) (diameter = 11 mm, thickness = 0.045 mm, and active material weight was 9.4 mg) as anodes. Two glass fiber separators (Whatman, diameter = 13 mm) 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 removed from the glove box, they were placed in a specially designed airtight container with inlet and outlet valves. Some of the Swagelok cells in the containers were kept under argon, while other containers were filled with a continuous, relatively high flow rate of dry oxygen (5.0 purity, overflowed from a high-pressure cylinder through a stainless steel gas line) for 30 minutes. Similar to the cathode, the LFP and separator were dried at 120°C under vacuum overnight, and all cell components (modified Swagelok and designed airtight container) were dried in a 70°C oven for 12 hours before use.

[0178] Comparative Example 1: Air electrode containing only carbon (reference)

[0179] Carbon Super C65 (Imerys) and polytetrafluoroethylene (PTFE, 60 wt% aqueous dispersion, Sigma Aldrich) were mixed in an agate mortar at a weight ratio of 4:1 w / w (carbon:PTFE) for 20 minutes. The resulting black paste was diluted with 2-propanol (VWR International, 1.4 mL 2-丙醇 / g 糊剂 ) to improve mixing and ductility. Once the rubbery composite material is obtained, about 160 mg is placed in a 4×4 cm 2 Then use Teflon TM The cylinder compresses the rubbery composite material until the net is evenly covered with black paste. The net is then placed between two aluminum foils and, relying on a hydraulic press, a pressure of 35 MPa is applied for 30 seconds three times. Thereafter, it is dried in a ventilated oven at 100 ° C for 1 hour and then cut into discs of 4 mm in diameter. Before using the electrodes prepared above, they are dried overnight at 150 ° C under vacuum. After deducting the net weight, the final weight of the electrode is 0.8 ± 0.1 mg, and the thickness is 0.32 ± 0.04 mm.

[0180] This air electrode containing only carbon and PTFE was assembled in a cell with an electrolyte without any soluble catalyst (electrolyte a)).

[0181] Comparative Example 2: Air electrode containing carbon + 10 mM DBBQ added to the electrolyte

[0182] An air electrode containing carbon and PTFE was prepared according to the same protocol as Comparative Example 1 and assembled in a cell with an electrolyte containing 10 mM DBBQ (electrolyte b)).

[0183] Comparative Example 3: Air electrode containing carbon + 10 mM TTF added to the electrolyte

[0184] An air electrode containing carbon and PTFE was prepared according to the same protocol as Comparative Example 1 and assembled in a cell with an electrolyte containing 10 mM TTF (electrolyte c)).

[0185] Example 1: Air electrode containing carbon + Li2DAnT (7:2 weight ratio) in electrolyte a)

[0186] Carbon Super C65 and PTFE (dry powder, Oxford University) were first dried at 120°C under vacuum overnight, while Li2DAnT obtained from University of Nantes was used directly without further drying or purification.

[0187] Carbon Super C65 and Li2DAnT were mixed in a mortar at a weight ratio of 7:2 (carbon: Li2DAnT) for 20 minutes. Thereafter, PTFE was blended with the paste at a weight ratio of (carbon + Li2DAnT): PTFE of 4:1, and about 2 mL of 2-propanol was added. All components were mixed in an agate mortar for another 20 minutes until the two obtained rubbery composites were uniformly black (weight ratio carbon: Li2DAnT = 7:2) (total weight ratio: Carbon Super C65: Li2DAnT: PTFE = 28:8:9). Then, a small amount of the formed composite material was spread onto a pre-punched stainless steel mesh disc with a diameter of 4 mm. The disc was then placed between two aluminum foils, and a pressure of 35 MPa was finally applied for 30 seconds three times. The electrode prepared above was dried again at 120 ° C under vacuum overnight to remove any traces of 2-propanol. After subtracting the mesh weight, the final weight was 1.2 ± 0.2 mg.

[0188] Example 2: Air electrode containing carbon + Li2DAnT (2:7 weight ratio) in electrolyte a)

[0189] The procedure was the same as in Example 1, except that the weight ratio of carbon:Li2DAnT was 2:7 (total weight ratio: Carbon SuperC65:Li2DAnT:PTFE=8:28:9).

[0190] Example 3: Air electrode containing carbon + Li2DAnT + Li4-p-DHT (50:50) (carbon: (Li2DAnT + Li4-p-DHT) 7:2 weight ratio) in electrolyte a)

[0191] Carbon Super C65 and PTFE (dry powder, Oxford University) were dried overnight under vacuum at 120 ° C, while Li2DAnT and yellow Li4-p-DHT purchased from University of Nantes were used directly without further drying or purification. Li2DAnT and Li4-p-DHT were mixed in a mortar at a weight ratio of 1: 1 for 20 minutes. Then, Carbon SuperC65 and the mixture Li2DAnT / Li4-p-DHT were mixed in a mortar at a weight ratio of 7: 2 (total weight ratio Carbon Super C65: Li2DAnT: Li4-p-DHT = 7: 1: 1) for 20 minutes. Then, PTFE was blended with the paste at a weight ratio of 4: 1 ((carbon + Li2DAnT + Li4-p-DHT): PTFE), and about 2 mL of 2-propanol had been added. All components were mixed in an agate mortar for another 20 minutes until the two obtained rubbery composites were uniformly black. The final mixture Carbon Super C65:Li2DAnT:Li4-p-DHT:PTFE weight ratio is 28:4:4:9. Then, a small amount of the formed composite material is spread on a pre-punched stainless steel mesh disc with a diameter = 4mm. The disc is placed between two aluminum foils and a pressure of 35MPa is finally applied for 30 seconds three times. The electrode prepared above is dried again at 120°C under vacuum overnight to remove any traces of 2-propanol. After subtracting the mesh weight, the final weight is 1.2±0.2mg.

[0192] Figure 1 The electrodes containing Li2DAnT as the sole SOC or containing Li2DAnT in combination with Li4-p-DHT showed an increase in discharge capacity (mAh cm -2 ) and recharge the lithium-air battery at 100% efficiency, which is not the case for CE1, CE2 and CE3.

[0193] Figure 2 It shows that relative to Li / Li + The potential window is 2.2 to 4.6 V and the capacity limit is 800 mAh g-1 SOC (~2.15mAh·cm -2 ), Example 1 (Li2DAnT:Carbon Super C65 (2:7) at 0.2 mAh·cm -2 Rate of lithium-air battery cell cycling ( Figure 2 a) and capacity retention of lithium-air battery cells versus cycle number ( Figure 2 b) Using 2.15 mAh cm -2 When the capacity limit is reached, the cycling capability of the lithium-air battery cell of Example 1 is very high during the first 20 cycles.

[0194] Figure 3 It shows that relative to Li / Li + The potential window is 2.2 to 4.6 V and the capacity limit is 2000 mAh g -1 SOC (~6mAh·cm -2 ), Example 1 (Li2DAnT:Carbon Super C65 (2:7) ( Figure 3 a) and Comparative Example 1 ( Figure 3 b) at 0.2 mAh cm -2 The lithium-air battery cell cycle rate is 6 mAh cm -2 When the capacity limit is reached, the cycling capacity of the lithium-air battery cell of Example 1 is very high during the first 5 cycles compared with the lithium-air battery cell of Comparative Example 1.

[0195] Figure 4 The results show that for an electrode containing a 7:2 ratio of Carbon Super C65:Li2DAnT (at 0.5 mAh cm -2 Electrostatic discharge performed), comparison of the first cycle of the lithium-air battery cell of Example 1 using a working electrode containing SOC Li2DAnT obtained in argon (solid line) or in oxygen (dashed line). Figure 4 It was confirmed that SOC alone does not have high capacity, but the effect on capacity can be clearly seen under oxygen conditions.

[0196] Comparison with prior art catalysts:

[0197] The following table (Table 1) summarizes the performance of the SOC used in the lithium-air battery cell described in the present invention compared with the batteries disclosed in the following above-mentioned prior art references:

[0198] - Prior art 1: Renault et al., Energy & Environmental Science, 2013, 6, 2124-2133,

[0199] - Prior art 2: Gao et al., Nature Materials, 2016, 15, 882,

[0200] - Prior art 3: Chen et al., Nature Chemistry, 2013, 5, 489,

[0201] - Prior art 4: Gao et al., Nature Energy, Vol. 2, 17118 (2017),

[0202] - Prior art 5: Hase et al., Chem. Commun. 2016, 52, 12151-12154,

[0203] - Prior art 6: Bergner et al., Phys. Chem. Chem. Phys., 2015, 17, 31769-31779, and

[0204] - Prior art 7: Kundu et al., ACS Cent., Sci., 2015, 1, 510-515.

[0205] Table 1

[0206]

[0207]

[0208] NA = Not applicable

Claims

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 disposed between the negative electrode and the positive electrode; The positive electrode comprises a solid p-type electroactive organic catalyst lithium salt, and the solid p-type electroactive organic catalyst lithium salt exhibits the following general structure (1): in: -Ar is an aromatic or heteroaromatic ring selected from the group consisting of benzene, naphthalene, perylene, anthracene, phenanthrene, tetracene, triphenylene, pyrene, pentacene, benzo[a]pyrene, coronene, benzo[ghi]perylene, coronene, ovalene, benzo[c]fluorine, pyridine, quinolone, isoquinoline, pyrazine, quinoxaline, acridine, pyrimidine, quinazoline, pyridazine, cinnoline, phthalazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, -R 1 To R 4 Each is independently selected from: H, aryl, alkyl, alkenyl, alkaryl, alkoxy, aryloxy, amino-alkyl, amino-aryl, thioalkyl, thioaryl, alkyl phosphonate, aryl phosphonate, cycloalkadienyl, -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 is H or C1-C 19 Alkyl, the R 1 To R 4 The group contains 1 to 20 carbon atoms and is optionally substituted with at least one halogen, oxygen or sulfur atom, -R 5 and R 6 Each is independently selected from: H, aryl, alkyl, alkenyl, alkaryl, alkoxy, aryloxy, amino-alkyl, amino-aryl, thioalkyl, thioaryl, alkyl phosphonate, aryl phosphonate, cycloalkadienyl, -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 is H or C1-C 19 Alkyl, the R 5 and R 6 The group contains 1 to 20 carbon atoms and is optionally substituted with at least one halogen, oxygen or sulfur atom, -Y and Y' are anionic groups, each independently selected from carboxylate, thiocarboxylate, sulfonate, thiosulfonate, phosphonate, thiophosphonate, sulfate, amidate groups.

2. The lithium-air battery cell according to claim 1, wherein: -Ar is benzene or naphthalene, -R 1 To R 4 is selected from H or aryl, the latter containing 4 to 20 carbon atoms and optionally substituted with at least one halogen, oxygen or sulfur atom, and -R 5 and R 6 It's H.

3. The lithium-air battery cell according to claim 1 or 2, wherein the solid p-type electroactive organic catalyst lithium salt exhibits a conductivity of less than 0.148 g·L in 1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in tetraethylene glycol dimethyl ether (TEGDME). -1 solubility.

4. The lithium-air battery cell according to claim 1 or 2, wherein the solid p-type electroactive organic catalyst lithium salt exhibits the following general structure (2): in: -R 1 and R 3 Each is independently selected from: H, aryl, alkyl, alkenyl, alkaryl, alkoxy, aryloxy, amino-alkyl, amino-aryl, thioalkyl, thioaryl, alkyl phosphonate, aryl phosphonate, cycloalkadienyl, -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 is H or C1-C 19 Alkyl, the R 1 and R 3 The group contains 1 to 20 carbon atoms and is optionally substituted with at least one halogen, oxygen or sulfur atom, -R 5 and R 6 Each is independently selected from: H, aryl, alkyl, alkenyl, alkaryl, alkoxy, aryloxy, amino-alkyl, amino-aryl, thioalkyl, thioaryl, alkyl phosphonate, aryl phosphonate, cycloalkadienyl, -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 is H or C1-C 19 Alkyl, the R 5 and R 6 The group contains 1 to 20 carbon atoms and is optionally substituted with at least one halogen, oxygen or sulfur atom.

5. The lithium-air battery cell according to claim 4, wherein: -R 1 and R 3 is selected from H or aryl, the latter containing 4 to 20 carbon atoms and optionally substituted with at least one halogen, oxygen or sulfur atom, and -R 5 and R 6 It's H.

6. The lithium-air battery cell according to claim 5, wherein R 1 and R 3 It is phenyl (-C6H5).

7. The lithium-air battery cell according to claim 1 or 2, wherein the positive electrode further comprises a solid n-type electroactive organic catalyst lithium salt.

8. The lithium-air battery cell according to claim 7, wherein the solid n-type electroactive organic catalyst lithium salt exhibits the following general structure (3): Where R 7 and R 8 Each is independently selected from: H, aryl, alkyl, alkenyl, alkaryl, alkoxy, aryloxy, amino-alkyl, amino-aryl, thioalkyl, thioaryl, alkyl phosphonate, aryl phosphonate, cycloalkadienyl, -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 is H or C1-C 19 Alkyl, the R 7 and R 8 The group contains 1 to 20 carbon atoms and is optionally substituted with at least one halogen, oxygen or sulfur atom.

9. The lithium-air battery cell according to claim 8, wherein R 7 and R 8 is selected from H or aryl, the latter comprising 4 to 20 carbon atoms and optionally substituted with at least one halogen, oxygen or sulfur atom.

10. The lithium-air battery cell according to claim 9, wherein R 7 and R 8 It's H.

11. The lithium-air battery cell of claim 7, wherein the weight ratio of the solid p-type electroactive organic catalyst lithium salt to the solid n-type electroactive organic catalyst lithium salt is 0.1 / 99.9 to 100 / 0.

12. The lithium-air battery cell of claim 11, wherein the weight ratio of the solid p-type electroactive organic catalyst lithium salt to the solid n-type electroactive organic catalyst lithium salt is 60 / 40 to 40 / 60.

13. The lithium-air battery cell of claim 1 or 2, wherein the positive electrode further comprises carbon.

14. The lithium-air battery cell of claim 13, wherein the weight ratio of carbon to the total weight of solid p-type electroactive organic catalyst lithium salt + solid n-type electroactive organic catalyst lithium salt + carbon is greater than or equal to 77%.

15. The lithium-air battery cell of claim 1 or 2, wherein the positive electrode further comprises a polymer binder selected from the group consisting of polyethylene, polypropylene, polytetrafluoroethylene (PTFE), styrene-butadiene rubber, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer (ETFE resin), polychlorotrifluoroethylene (PCTFE), vinylidene fluoride-pentafluoropropylene copolymer, propylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer (ECTFE), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene copolymer, ethylene-acrylic acid copolymer, or a copolymer having perfluorovinyl ether groups terminated by sulfonate groups attached to a polytetrafluoroethylene backbone.

16. The lithium-air battery cell of claim 15, wherein the polymer binder is polytetrafluoroethylene (PTFE).

17. The lithium-air battery cell of claim 15, wherein the weight ratio of the polymer binder to the total weight of solid p-type electroactive organic catalyst lithium salt + solid n-type electroactive organic catalyst lithium salt + carbon + polymer binder is less than or equal to 20%.

18. The lithium-air battery cell according to claim 1 or 2, 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 or nitrile solvents.

19. A battery pack comprising at least two assembled lithium-air battery cells according to any one of claims 1 to 18.

20. The battery pack according to claim 19 is used as a rechargeable battery for electric and hybrid vehicles, electronic devices and stationary power generation devices.

21. A vehicle comprising the battery pack according to claim 19.

22. An electronic device comprising the battery pack according to claim 19.

23. A stationary power generation device comprising the battery pack according to claim 19.

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