WO2021148836A1 - Composés de lithium à base de naphtalène, procédé pour leur préparation, leur utilisation en tant que catalyseur organique solide, et leur utilisation dans des cellules de batterie lithium-air non aqueuses rechargeables - Google Patents

Composés de lithium à base de naphtalène, procédé pour leur préparation, leur utilisation en tant que catalyseur organique solide, et leur utilisation dans des cellules de batterie lithium-air non aqueuses rechargeables Download PDF

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WO2021148836A1
WO2021148836A1 PCT/IB2020/000090 IB2020000090W WO2021148836A1 WO 2021148836 A1 WO2021148836 A1 WO 2021148836A1 IB 2020000090 W IB2020000090 W IB 2020000090W WO 2021148836 A1 WO2021148836 A1 WO 2021148836A1
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lithium
air battery
group
battery cell
copolymers
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PCT/IB2020/000090
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English (en)
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Steven Renault
Marco Carboni
Fanny Jeanne Julie Barde
Laurent CASTRO
Philippe Poizot
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Toyota Motor Europe
Centre National De La Recherche Scientifique
Universite De Nantes
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Priority to PCT/IB2020/000090 priority Critical patent/WO2021148836A1/fr
Priority to DE112020006564.2T priority patent/DE112020006564T5/de
Publication of WO2021148836A1 publication Critical patent/WO2021148836A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/41—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
    • C07C309/43—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton having at least one of the sulfo groups bound to a carbon atom of a six-membered aromatic ring being part of a condensed ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
    • C07C65/105—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups polycyclic
    • C07C65/11—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups polycyclic with carboxyl groups on a condensed ring system containing two rings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • NAPHTHALENE BASED LITHIUM COMPOUNDS A PROCESS FOR THEIR PREPARATION, THEIR USE AS SOLID ORGANIC CATALYST, AND THEIR USE IN RECHARGEABLE NON-AQUEOUS LITHIUM-AIR BATTERY CELLS
  • the present invention relates to novel naphthalene-based compounds, to their process of preparation, and to their use as Solid Organic Catalysts (SOC) in lithium-air battery cells to promote oxygen reactions.
  • the invention also concerns a lithium-air battery cell wherein the positive electrode comprises a SOC according to the invention, as well as a battery pack comprising several lithium-air battery cells according to the invention.
  • the use of a lithium-air battery cell according to the invention as a rechargeable battery for vehicles, such as electric vehicles and hybrid vehicles, electronic devices, and stationary power generating devices, is also part of the invention.
  • the invention is directed at a vehicle, an electronic device, and a stationary power generating device, comprising a battery pack according to the invention.
  • Rechargeable lithium batteries are of considerable interest due to their high energy density and high power. Especially, rechargeable lithium-air batteries have attracted attention for electric vehicles and hybrid vehicles, where high energy density is required. Lithium-air battery cells are used In various devices (such as computers and telephones), in automotive or stationary applications, and can be assembled in battery packs.
  • Rechargeable lithium-air batteries use oxygen in the air as a cathode active material. Therefore, compared to conventional lithium rechargeable batteries containing a transition metal oxide (e.g. lithium cobaltate), as a cathode active material, rechargeable lithium-air batteries are able to have larger capacity.
  • a transition metal oxide e.g. lithium cobaltate
  • the cathode active material oxygen
  • the cathode active material is not contained within the battery. Instead, this material is provided by the surrounding atmosphere.
  • oxygen may be partially reduced to peroxide, or fully reduced to hydroxide or oxide depending on the catalyst, electrolyte, availability of oxygen, etc.
  • the negative electrode (anode) is lithium (Li)
  • lithium peroxide (Li 2 O 2 ) or lithium oxide (Li 2 O) may be formed.
  • a lithium-air battery cell comprises in general the following parts:
  • - metal anode e.g. containing Li
  • non-aqueous electrolyte e.g. containing a lithium salt
  • Other parts of the battery cell device may be present 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 electrolyte, or between a negative electrode (anode) and electrolyte.
  • Gao et al. propose 2,5-Di-tert-Butyl-l,4-BenzoQuinone (DBBQ) as a soluble catalyst to increase the rate performances of a non-aqueous lithium-air battery cell.
  • the air electrode is a Gas Diffusion Layer (GDL) based porous carbon electrode as air cathode.
  • GDL Gas Diffusion Layer
  • the anode is LiFePO 4 (Nature Materials, 2016, 15, 882) or Li protected by a Ohara glass necessitating the use of a two- compartment cell (Nature Energy, Vol. 2, 17118 (2017)), but Li metal cannot be used as anode because DBBQ would migrate to it and causes problem at the anode.
  • TTF TetraThiaFulvalene
  • TDPA tris[4- (diethylamino)phenyl]amine
  • the major drawback of the solutions proposed by the prior art is the use of a soluble catalyst which does not permit the use of Li metal (without extra protection) as anode. Indeed, the migration of soluble catalysts at the anode deteriorates the lithium-air battery cell performances and safety, needing the use of additional features such as: a protection barrier to protect the Li metal from soluble catalysts contamination which can deposit at the surface of the Li metal and create nucleation site causing the formation of dendrites, special separators blocking the solute species, or specific cell design such as a two-compartment cell composed of two electrolyte compartments, i.e. one for the anode side and the other for the cathode side, to protect the Li anode.
  • a protection barrier to protect the Li metal from soluble catalysts contamination which can deposit at the surface of the Li metal and create nucleation site causing the formation of dendrites
  • special separators blocking the solute species or specific cell design such as a two-compartment cell composed of two
  • nitroxides catalysts such as l-methyl-2-azaadamantane-N-oxyl (1- Me-AZADO).
  • these nitroxides have the disadvantage of being soluble in the electrolyte, thus deteriorating the anode of lithium-air battery cells.
  • the present invention remedies to all the problems of the prior art by providing a novel naphthalene-based compound used as SOC in lithium-air battery cells, and which:
  • the SOC is self-regenerated inside the battery cell and returns to ib initial state
  • the SOC of the 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 may be prepared from renewable resources (biomass).
  • the present invention in one aspect, relates to a novel naphthalene- based compound of specific formula (1) as defined hereinafter.
  • the invention also concerns a process of preparation of such specific compound of formula (1).
  • the invention also concerns a lithium-air battery cell comprising:
  • the positive electrode comprises the compound of formula (1) as
  • the invention in another aspect, relates to a battery pack comprising several lithium-air battery cells according to the invention assembled together.
  • the invention also relates to the use of a battery pack according to the invention as a rechargeable battery for electric vehicles and hybrid vehicles, electronic devices, and stationary power generating devices.
  • the invention also relates to a vehicle, an electronic device, and a stationary power generating device, comprising a battery pack according to the invention.
  • Figure 1 shows the ThermoGravimetric Analysis (TGA) of tetra lithium salt of 1,5-dihydroxy-2,6-naphthalenedicarboxylic acid (Li 4 DHNDC) obtained with (Fig. la) or without (Fig. lb) excess of lithium methoxide (MeOLi).
  • TGA ThermoGravimetric Analysis
  • Figure 2 shows Fourier Transform Infrared Spectroscopy (FT-IR) spectra of precursor 1,5-dihydroxy-2,6-naphthalenedicarboxylic acid (H 4 DHNDC) (Fig. 2a) and Li 4 DHNDC (Fig. 2b).
  • FT-IR Fourier Transform Infrared Spectroscopy
  • Figure 3 represents the Scanning Electron Microscopy (SEM) pictures of Li 4 DHNDC.
  • Figure 4 shows the voltage (V versus Li + /Li) versus the capacity (mAh.cm -2 ) for a lithium-air battery cell cycled at 0.2 mAh.cm -2 as described in Example 1 (Exl) compared to Comparative Examples 1, 2 and 3 (CE1, CE2, CE3).
  • Figure 5 shows the cycling of the lithium-air battery cell (Fig. 5a) of Example 1 at 0.2 mAh.cm -2 rate, 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 capacity retention versus the cycle number (Fig. 5b) of Example 1.
  • Figure 6 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 (plain 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 ),
  • Figure 7 Is a schematic view of a metal-air battery cell with one electrochemical cell inside a gas compartment (Fig. 7a) and a metal-air battery pack with several cells inside a gas compartment (Fig. 7b), with: 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.
  • 11 gas compartment (dry air or pure oxygen)
  • 12 metal anode
  • 13 cathode
  • 14 electrolyte/separator
  • 15 anode current collector
  • 16 cathode current collector
  • the present invention relates to a novel naphthalene-based compound of formula (1) below: wherein:
  • 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 (-C(-O)-N--) groups,
  • 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,
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , or R 8 comprises at least one lithium ion, the number of lithium ions being the same as the number of groups A comprising a permanent negative charge in order to render the compound of formula (I) globally neutral.
  • 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.
  • branched means that at least one lower alkyl group such as methyl or ethyl is carried by a linear alkyl chain.
  • alkyl group there may be mentioned, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyi, 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 ⁇ -system in which each atom of the cycle comprises a p-orbital, said p-orbital overlapping each other; among such aryl groups there may be mentioned phenyl, biphenyl, naphthalene and anthracene groups.
  • the aryl groups of the invention preferably comprise from 4 to 20 carbon atoms, even 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 that contains at least one carbon-carbon double bond.
  • 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 from 5 to 20 carbon atoms, and more preferably from 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.
  • alkyl group there may be mentioned, for example, methyloxy, ethyloxy, n-propyloxy, iso-propyloxy, n- butyloxy, sec-butyloxy, tert-butyloxy and isobutyloxy radicals;
  • Aryloxy any ary] radical linked to an oxygen atom, preferably comprising from 4 to 20 carbon atoms, and more preferably from 4 to 12 carbon atoms.
  • the aryloxy group it may be mentioned, for example, phenoxy radical;
  • Amino-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 bearing an amino group, and preferably 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;
  • Thio-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 bearing a thiol group -SH;
  • Thio-aryl any aryl radical linked to a thiol group -SH, preferably comprising from 4 to 20 carbon atoms, and more preferably from 4 to 12 carbon atoms;
  • Thio-ether 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 functional group with the structure C-S-C;
  • 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 bearing a functional group with the structure C-S-S-C;
  • R' is 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;
  • 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 bearing an nitroxide radical -N(O . )-.
  • 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)carboxylates, (thio)sulfonates, (thio)phosphonates, sulfates, and amidates, and more preferably carboxylate groups.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , or R 8 are groups B selected from the group consisting of -OLi, nitroxide, alkyl nitroxide, thioether, disulfide, alkylamine, and arylamine, and more preferably -OLi.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , or R 8 groups, others than groups A and B, are H.
  • R 1 , R 2 , R 5 , and R 6 are H.
  • the compound of formula (1) of the invention is selected from the group consisting of:
  • the compound of formula (1) Is tetra lithium salt of 1,5-dihydroxy-2,6-naphthalenedicarboxylic acid (Li 4 DHNDC) of formula:
  • the present invention also relates to a process for the preparation of a compound Of formula (1) according to the invention, comprising the step of reacting a naphthoi with MeOLi in MeOH or LiH in DMF (lithiation step), and preferably MeOLi in MeOH, in stoichiometric amount, and under inert atmosphere (in a giovebox).
  • the stoichiometric conditions are important to avoid having unreacted MeOLi mixed with the final compound of formula (1), the only remaining by-product when a complete conversion occurred being the solvent which is easily removed in vacuo.
  • the invention aims at a process for the preparation of Li 4 DHNDC according to the following reaction scheme:
  • H 4 DHNDC is lithiated by MeOLi or LiH which is added under inert atmosphere and in stoichiometric amount in order 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 also concerns the use of a compound of formula (1) of the invention as SQC in a lithium-air battery cell.
  • the compound of formula (1) is a solid n-type electroactive organic catalyst lithium salt which may be used in lithium-air battery cells to promote oxygen reactions.
  • the invention also relates to a SOC comprising, and preferably consisting of, a compound of formula (1) according to the invention.
  • the SOC of the invention has the main advantage of not being soluble in electrolyte, avoiding the migration of soluble species to the anode. It further enhances the electrochemical performances of the reactions involving oxygen such as Oxygen Evolution Reaction (OER) and Oxygen Reduction Reaction (ORR), thus improving the capacity and re-chargeability of non-aqueous lithium-air battery cells.
  • OER Oxygen Evolution Reaction
  • ORR Oxygen Reduction Reaction
  • the SOC of the invention is advantageously in the form of lamellar particles.
  • the SOC of the invention has advantageously a specific surface area greater than or equal to 5 m 2 .g -1 .
  • Another subject-matter of the present invention is a lithium-air battery cell comprising: a negative eiectrode (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 formula (1) according to the invention as SOC.
  • Prior art 1 already discloses the synthesis of IMNQ and DANQ, those materials being used as active cathode materials in lithium-ion battery cells, which are closed battery systems, not In lithium-air battery cells.
  • the main drawback of closed battery systems is their low capacity.
  • the negative electrode (which may also be referred to as “anode” hereinafter) comprises at least an anode active material (which may also be referred to as “negative electrode active material” hereinafter).
  • anode active material general anode active materials for lithium batteries can be used and the anode active material is not particularly limited. In general, the anode active material is able to store/release a litiiium ion (Li + ).
  • Specific anode active materials for rechargeable lithium-air batteries are, for example, a lithium metal, lithium protected anodes, lithium alloys such as a lithium-aluminum alloy, a lithium-tin alloy, a lithium-lead alloy and a lithium- silicon alloy, metal oxides such as a a 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.
  • lithium-protected anode reference Is made here for example (but is not limited to) to a “Lithium Protected Electrode” (LPE) as described in US 8,652,692.
  • LiSiCON lithium superionic conductor
  • Li ⁇ 2 ( ⁇ O 4 ) 3 a solid electrolyte
  • Interlayer for example consisting of Cu 3 N/Li 3 N.
  • Li metal can be attached directly to one side of LiSiCON material, or alternatively a small amount of solvent containing a Li salt electrolyte may be added between the LiSiCON material and the Li metal to ensure U ionic conductivity.
  • solvent containing a Li salt electrolyte may be added between the LiSiCON material and the Li metal to ensure U ionic conductivity.
  • anode active material 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.
  • the anode is required to contain at least an anode active material; however, as needed, it can contain a binder for fixing the anode active material.
  • the type and usage of the binder are the same as those of the air cathode described hereinafter.
  • An anode collector may be connected to the anode, which collects current from the anode.
  • the material for the anode collector and the shape of the same are not particularly limited. Examples of the material for the anode collector include stainless steel, copper and nickel. Examples of the form of the anode collector include a foil form, a plate form and a mesh (grid) form. ⁇ Cathode>
  • the positive electrode (which may also be referred to as "cathode” hereinafter) comprises at least a cathode active material (which may also be referred to as “positive electrode active material” hereinafter).
  • the positive electrode uses oxygen as a positive-electrode active material.
  • Oxygen serving as the positive-electrode active material may be contained in air or oxygen gas.
  • the catalyst present in the positive electrode is a SOC of formula (1)
  • the SOC of formula (1) of the invention advantageously shows less than 150 g.L -1 solubility In lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) 1M in tetraethylene glycol dimethyl ether (TEGDME).
  • LiTFSI lithium bis(trifluoromethanesulfonyl)imide
  • TEGDME tetraethylene glycol dimethyl ether
  • the positive electrode of the lithium-air battery cell of the invention may further comprise another SOC.
  • the weight ratio between the SOC of formula (1) of the invention and the other SOC may range from 0.1/99.9 to 100/0, preferably from 60/40 to 40/60, and more preferably is of 50/50.
  • the positive electrode may be a component in which the redox catalyst is supported on a carrier.
  • An example of the carrier is carbon. Therefore, in the lithium-air battery cell of the invention, the positive electrode advantageously further comprises carbon.
  • carbon blacks such as Ketjen Black, acetylene black, channel black, furnace black, lamp black, and thermal black
  • graphite such as natural graphite, e.g., scaly 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 obtained by carbonizing synthetic Fibers and petroleum pitch- based materials
  • molecular carbon such as fullerenes
  • tubular carbon such as carbon nanotubes.
  • Modified carbons such as N-doped carbon may also be used.
  • Positive electrode materials can also be used in a lithium-air battery cell of the present invention based on materials other than carbon.
  • positive electrode materials based on metal foam, stable and conductive metal oxides, or steel, can be used.
  • carbon is preferably a porous material in the form of a powder and preferably has a high specific surface area of 20 to 2000 m 2 .g -1 , more preferably of 60 to 2000 m 2 .g -1 , and even more preferably of 60 to 1500 m 2 .g -1
  • carbon may be used upon which a treatment is performed by a general method to increase porosity or surface area, followed by another treatment to increase the wettability.
  • Different forms of carbon can be used in the present invention including SUPER P ® Li (from TIMCAL) showing a particle size of 40 nm and a specific surface area (determined by the Brunauer-Emmett-Teller method) of 62 m 2 .g -1 ; BLACK PEARLS® 2000 (from Cabot Corporation) showing a particle size of 12 nm and a specific surface area (determined by the Brunauer-Emmett-Teller method) of 1487 m 2 .g -1 ; Ketjen black® EC-600JD powder (from AzkoNobel) showing a specific surface area (determined by the Brunauer-Emmett-Teller method) of 1400 m 2 .g -1 .
  • Examples of the commercial carbon products which 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 available from Norit and AB-Vulcan 72 (from Cabot).
  • Other examples of commercially available carbon include the WAC powder series (from Xiamen All Carbon Corporation), PW15-type, 3-type, and S-type Activated Carbons (from Kureha), and Maxsorb MSP-15 (from Kansai Netsu Kagaku).
  • Examples of the method for increasing 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 (potassium hydroxide solution for example), in an acid solution (nitric acid or phosphoric acid for example) or in a salt (zinc chloride for example). This treatment can be followed (but not necessarily) by a calcination step at relatively low temperature (450 to 900°C for example).
  • the carbon preferably has pores having a pore diameter of 5 nm or more, preferably of 20 nm or more.
  • the specific surface area of the carbon and the pores size can be measured by the BET method or the BJH method, for example.
  • the carbon preferably has an average particle diameter (primary particle diameter) of 8 to 350 nm, more preferably of 30 to 50 nm.
  • the average primary particle diameter of the carbon can be measured by TEM.
  • the weight ratio between carbon and the SOC of formula (1) of the invention is advantageously 7:2.
  • the weight ratio between carbon : SOC of formula (1) of the invention is advantageously 7:1:1.
  • the positive electrode may contain a conductive material, in addition to the carbon and non- carbon materials discussed above.
  • further conductive materials include conductive fibers such as metal fibers; metal powders, such as silver, nickel, aluminium powders; and organic conductive materials such as polyphenylene derivatives. These may be used separately or in combination as a mixture.
  • 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 thereof include polyethylene, polypropylene, polytetrafluoroethylene (FIFE), styrene-butadiene rubber, tetrafluoroethylene- hexafluoropropylene copolymers, tetrafiuoroethylene-hexafluoropropylene copolymers (FEP), tetrafluoroethylene-perfiuoroalkyl vinyl ether copolymers (PFA), vinylidene fluoride-hexafluoropropylene copolymers, vinylidene fluoride- chlorotrifluoroethylene copolymers, ethylene-tetrafluoroethylene copolymers
  • EFE 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.
  • PCTFE polychlorotrifluoroethylene
  • ECTFE ethylene-chlorotrifluoroethylene copolymers
  • vinylidene fluoride- hexafluoropropylene-tetrafluoroethylene copolymers vinylidene fluoride- perfluoromethyl vinyl ether-tetrafluoroethylene copolymers
  • ethylene-acrylic acid copolymers ethylene
  • Copolymers having sulfonate group-terminated perfluorovlnyl ether groups attached to a poly(tetrafluoroethylene) backbone may also be envisaged as polymer binders in the present invention. These polymer binders may be used separately or in combination as a mixture.
  • Polytetrafluoroethylene (PTFE) is a particularly preferred polymer binder.
  • the weight ratio between the polymer binder and (SOC of formula (1) + carbon + polymer binder) is lower than or equal to 20%.
  • 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 lower than or equal to 20%.
  • an air cathode collector is connected to the air cathode, which collects current from the air cathode.
  • the material for the air cathode collector and the shape of the same are not particularly limited.
  • Examples of the material for the air cathode collector include stainless steel, aluminium, iron, nickel, dtanium and carbon.
  • Examples of the form of the air cathode collector include a foil form, a plate form, a mesh (grid) form and a fibrous form.
  • the air cathode collector has a porous structure such as a mesh form since the collector having a porous structure has excellent efficiency of oxygen supply to the air cathode.
  • the air electrode (air cathode) further comprises hydrophobic hollow fibers.
  • a hydrophobic fiber tends to generate a space between itself and the electrolyte. These spaces facilitate oxygen diffusion in the air electrode, enabling a thicker electrode to be used.
  • carbon- based air electrodes are 0.5 to 0.7 mm thick. Addition of hydrophobic fibers allows use of electrodes that are at least 1 mm thick. Suitable fibers include DuPont HOLLOFIL ® (100% polyester fiber with one more holes in the core), goose down (very small, extremely light down found next to the skin of geese), PTFE fiber, and woven hollow fiber doth, among others. KETJENBLACK® carbon can also be coated on these fibers.
  • the non-aqueous Ion-conducting (electrolyte) medium arranged between the negative electrode and the positive electrode is a non-aqueous 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 , LiCIO 4 , LIAsF 6 , LiBF 4 , Li(CF 3 SO 2 ) 2 N (LiTFSI), LIFSI, LKCF 3 SO 3 ) (LiTriflate), LiN(C 2 F 5 SO 2 ) 2 , LiBOB, LIFAP, LIDMSI, LIHPSI, LIBETI, LiDFOB, LIBFMB, LiBison, LiDCTA, LiTDI, LiPDL
  • the concentration of the salt Is preferably in the range of 0.1 to 2.0 M, and more preferably of 0.8 to 1.2 M.
  • the lithium salts are appropriately used in the electrolyte medium in combination with aprotic organic solvents known for use in lithium-air batteries.
  • aprotic organic solvents include chain carbonates, cyclic ester carbonates, chain ethers, cyclic ethers, glycol ethers, and nitrile solvents.
  • chain carbonates include dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate.
  • cyclic ester carbonates include ⁇ - butyrolactone and ⁇ -valerolactone.
  • chain ethers include dimethoxyethane and ethylene glycol dimethyl ether.
  • cyclic ethers include tetrahydrofuran and 2-methyltetrahydrofuran.
  • glycol ethers examples include tetraethylene glycol dimethyl ether (TEGDME), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), polyethylene glycol) dimethyl ether with a weight average molecular weight Mw from 90 to 225 g.mol -1 .
  • Nitrile solvents can also be used, such as acetonitrile, propionltrile, and 3-methoxypropionitrile. These aprotic organic solvents may be used separately 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.
  • the gelled electrolyte having lithium ion conductivity can be obtained by, for example, adding a polymer to the non-aqueous electrolytic solution for gelation.
  • gelation can be caused by adding a polymer such as polyethylene oxide (PEG), polyvinylidene fluoride (PVDF, commercially available as Kynar, etc,), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), and poly(vinyl) chloride (PVC).
  • PEG polyethylene oxide
  • PVDF polyvinylidene fluoride
  • PAN polyacrylonitrile
  • PMMA polymethyl methacrylate
  • PVC poly(vinyl) chloride
  • Components which can be cross-linked and/or thermoset may also be added to the gel electrolyte formulation to improve its mechanical properties.
  • plasticizers PEG, crown ethers, etc.
  • incorporation of substantial amount of plasticizers may be carried out to improve the ionic conductivity of the polymer electrolytes.
  • nanopart!cles/ceramics may be added to such gel polymer electrolytes to increase their conductivities.
  • Reference in this regard may be made to EP 1 096 591 A1 or Croce et a!., Electrochimica Acta 46 (2001), 2457-2461.
  • the nanoparticle/ceramic filler content is usually less than 10 wt% of the membrane.
  • AI 2 O 3 nanoparticles may be obtained from Aldrich Research Grade and have 5.8 nm particle size (Swierczynski et al., Chem. Mater., 2001, 13, 1560-1564).
  • SiO 2 fumed silica may be obtained from Aldrich Reagents Grade, with a 7 nm particle size.
  • the nanopartide size is preferentially around 15 nm or below.
  • This oxygen dissolution enhancer may be a fluorinated polymer, a fluorinated ether, a fluorinated ester, a fluorinated carbonate, a fluorinated carbon material, a fluorinated blood substitute, or indeed a metalloprotein.
  • oxygen dissolution enhancers are described in US 2010/0266907.
  • 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 able to electrically insulate the air cathode and the anode from each other and has a structure that allows the electrolyte to be present between the air cathode and the anode.
  • separator examples include porous films and nonwoven fabrics comprising polyethylene, polypropylene, cellulose, polyvinylidene fluoride, glass ceramics, etc. Of these, a separator of glass ceramics is preferred.
  • the battery cell case for housing the rechargeable lithium-air battery cell general battery cases for rechargeable lithium battery cell can be used.
  • the shape of the battery cell case is not particularly limited as long as it can hold 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 which shows selectivity for oxygen diffusion over that of water.
  • the rechargeable lithium-air battery cell of the invention can discharge when an active material, which is oxygen, is supplied to the air cathode.
  • oxygen supply source include the air and oxygen gas, and preferred is oxygen gas.
  • 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 may be used as a primary battery cell or a rechargeable secondary battery cell.
  • the specific capacity value X selected may vary widely and, for example, be situated in the range of 200 to 10000 mAh.g -1 .
  • the specific capacity of a lithium-air battery cell may be determined by discharging up until 2 V. It may be appropriate during operation of the battery cell to cycle the battery cell within limits that do not go to full discharge or charge. It may be advantageous to cycle the battery cell from 10 to 90% of its specific capacity (determined in step (b)), preferably from 20 to 80%, and more preferably from 20 to 70%. Cycling may also be carried out between certain limits of initial or maximum theoretical discharge capacity. Capacity-limited cycling may enable the cell to survive longer, and it may thus be appropriate to limit the cycling capacity to around 30% of the full discharge capacity.
  • the lithium-air battery cell of the present invention can be used as a rechargeable lithium battery for electric vehicles and hybrid vehicles, electronic devices (such as computers and telephones), and stationary power generating devices, and can be assembled in battery packs.
  • the number of battery cells may vary depending on the final use of the lithium-air battery, and preferably may vary from 2 to 250 battery cells.
  • ATR-IR v max/cm -1 3210, 2975, 2844, 2596, 2532, 1650, 1598, 1490, 1438, 1415, 1296, 1237, 1209, 1189, 1167, 1013, 881, 826, 766, 743, 677 cm "
  • ATR-IR v max/cm -1 2942, 2846, 2791, 1567, 1531, 1482, 1426, 1385, 1268, 1230, 1187, 1164, 1078, 1025, 912, 833, 801, 767, 705, 658 cm 1 ;
  • Lamellar particles Lamellar particles.
  • Figure 1 shows the TGA of Li 4 DHNDC obtained with (Fig. la) or without (Fig. lb) excess of MeOLi
  • Figure 2 the FT-IR spectra of precursor H4DHNDC (Fig. 2a) and Li 4 DHNDC (Fig. 2b)
  • Figure 3 the SME pictures of Li 4 DHNDC.
  • Three electrolyte solutions were prepared by dissolving: a) 1.0 M bis(trifluoromethane)sulfonimide lithium salt (LiTFSI, BASF) in TEGDME (Sigma Aldrich, moisture controlled grade), b) 1.0 M LiTFSI and 10 '2 M (10 mM) DBBQ (Sigma Aldrich) in TEGDME, c) 1.0 M LiTFSI and 10 '2 M (10 mM) TTF (Sigma Aldrich) in TEGDME.
  • LiTFSI bis(trifluoromethane)sulfonimide lithium salt
  • LiTFSI, DBBQ and TTF were dried at 1Q0°C overnight under vacuum while TEGDME solvent was used after drying/storage on regenerated 3 A molecular sieves (Sigma Aldrich) for at least 15 days in a glovebox.
  • the water content in the solvent and in the electrolytes was determined by means 831KF Karl Fischer coulometer (Metrohm) technique and was measured to be lower than 4 ppm.
  • Expected loading 1.3 mAh.cnrV 2
  • Expected loading 9.89 mg tot .cm -2
  • the LFP electrodes used for the following tests are punched 11 mm diameter discs (area: 0.9503 cm 2 ).
  • the LFP electrodes were used as a counter electrode for all tests for standardization purposes.
  • Vvs LFP 3.4V - Vvs LFP.
  • the above prepared carbon- based electrodes were used as working electrodes.
  • They were placed inside a special designed airtight container with inlet and outlet valves.
  • 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, spilled from a high-pressure cylinder through a stainless steel gas lines) for 30 minutes.
  • dry oxygen 5.0 purity, spilled from a high-pressure cylinder through a stainless steel gas lines
  • LFP and separators were dried at 120°C overnight under vacuum and all the cell components (modified Swagelok and designed airtight containers) were dried in an oven at 70°C for 12 h before usage.
  • Carbon Super C65 (Imerys) and polytetrafluoroethylene (PTFE, 60 wt% dispersion in H 2 O, Sigma Aldrich) were mixed with a weight ratio of 4:1 w/w (carbon: PTFE) in a agate mortar for 20 minutes.
  • the resulting black paste was wetted with 2-propanol (VWR International, 1.4 mL 2-propanol/gpaste ) in order to improve the mixing and malleability.
  • VWR International 2-propanol
  • 2-propanol/gpaste 2-propanol
  • the mesh was then placed between two aluminum foils and, by means a hydraulic press, a pressure of 35 MPa was applied for 30 seconds three times. Afterwards, it was dried in a ventilating oven for 1 h at 100°C and then cut into discs of diameter 4 mm. Before using the above prepared electrodes, they were dried at 150°C overnight under vacuum. The final weight of electrodes was 0.8 ⁇ 0.1 mg after mesh weight subtraction and with a thickness of 0.32 ⁇ 0 .04 mm.
  • This air electrode containing only carbon and PTFE was assembled in a battery with an electrolyte free of any soluble catalyst (electrolyte a)).
  • the air electrode containing carbon and PTFE was prepared according to the same protocol as in Comparative Example 1 and was assembled in a battery with electrolyte containing 10 mM DBBQ (electrolyte b)).
  • Comparative example 3 Air electrode containing carbon + 10 mM TTF added in the electrolyte
  • the air electrode containing carbon and PTFE was prepared according to the same protocol as in Comparative Example 1 and was assembled in battery with electrolyte containing 10 m M TTF (electrolyte c)).
  • Example 1 Air electrode containing carbon + Li 4 DHNDC (7:2 weight ratio) in electrolyte a) Li 4 DHNDC, Carton Super C65 and PTFE (dry powder, Oxford University) were first dried overnight at 120°C under vacuum.
  • the discs were then placed between two aluminum foils and, finally, a pressure of 35 MPa was applied for 30 seconds three times.
  • the above prepared electrodes were dried again at 120°C overnight under vacuum to remove any trace of 2- propanol.
  • the final weight was 1.2 ⁇ 0.2 mg after mesh weight subtraction.
  • Figure 4 shows the voltage (V versus Li + /Li) versus the capacity (mAh.cm -2 ) for a lithium-air battery cell cycled at 0.2 mAh.cm -2 as described in Example 1 (Exl) compared to Comparative Examples 1, 2 and 3 (CE1, CE2, CE3).
  • Figure 4 demonstrates that the electrode containing Li 4 DHNDC (Exl) allows increasing the discharge capacity (mAh.cm -2 ) and to recharge the lithium-air battery cell with 100% efficiency thanks to a lower hysteresis, which is not the case for CE1, CE2, CE3.
  • Figure 5 shows the cycling of the lithium-air battery cell (Fig. 5a) of Example 1 (Exl) at 0.2 mAh.cm -2 rate, 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 capacity retention versus the cycle number (Fig. 5b) of Example 1.
  • Figure 6 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 (plain 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 theoretical capacity expected.
  • Figure 6 demonstrates that the SOC alone does not have a high capacity, while under oxygen an effect on the capacity is dearly seen.
  • Table 1 summarizes properties of SOC used in lithium-air battery cells described in the present invention as compared to the ones disclosed in the following prior art references discussed above:

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Abstract

La présente invention concerne de nouveaux composés à base de naphtalène, leur procédé de préparation et leur utilisation en tant que catalyseurs organiques solides (SOC) dans des cellules de batterie lithium-air pour favoriser des réactions d'oxygène. L'invention concerne également une cellule de batterie lithium-air dans laquelle l'électrode positive comprend un SOC selon l'invention, ainsi qu'un bloc-batterie comprenant plusieurs cellules de batterie lithium-air selon l'invention. L'invention concerne en outre l'utilisation d'un bloc-batterie selon l'invention en tant que batterie rechargeable pour véhicules, tels que des véhicules électriques et des véhicules hybrides, des dispositifs électroniques et des dispositifs de production d'énergie stationnaire. Enfin, l'invention concerne un véhicule, un dispositif électronique et un dispositif de génération d'énergie stationnaire, comprenant un bloc-batterie selon l'invention.
PCT/IB2020/000090 2020-01-20 2020-01-20 Composés de lithium à base de naphtalène, procédé pour leur préparation, leur utilisation en tant que catalyseur organique solide, et leur utilisation dans des cellules de batterie lithium-air non aqueuses rechargeables WO2021148836A1 (fr)

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DE112020006564.2T DE112020006564T5 (de) 2020-01-20 2020-01-20 Lithiumverbindungen auf naphthalin-basis, verfahren für deren herstellung, verwendung davon als fester organischer katalysator, und verwendung davon in wiederaufladbaren nichtwässrigen lithium-luft- batteriezellen

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