EP3997748A1 - Élimination des retards de tension et stabilisation de l'impédance au moyen d'additifs électrolytiques dans des cellules électrochimiques de métal alcalin - Google Patents

Élimination des retards de tension et stabilisation de l'impédance au moyen d'additifs électrolytiques dans des cellules électrochimiques de métal alcalin

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Publication number
EP3997748A1
EP3997748A1 EP20734772.5A EP20734772A EP3997748A1 EP 3997748 A1 EP3997748 A1 EP 3997748A1 EP 20734772 A EP20734772 A EP 20734772A EP 3997748 A1 EP3997748 A1 EP 3997748A1
Authority
EP
European Patent Office
Prior art keywords
tetramethyl
dioxaborolane
alkyl
dioxaborinane
dimethyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20734772.5A
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German (de)
English (en)
Inventor
Sofiane Bouazza
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Litronik Batterietechnologie GmbH
Original Assignee
Litronik Batterietechnologie GmbH
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Filing date
Publication date
Application filed by Litronik Batterietechnologie GmbH filed Critical Litronik Batterietechnologie GmbH
Publication of EP3997748A1 publication Critical patent/EP3997748A1/fr
Pending legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/5835—Comprising fluorine or fluoride salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
    • 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
    • H01M2300/0037—Mixture of solvents
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • 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
    • 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
    • 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
    • H01M4/626—Metals
    • 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

  • the present invention relates to boron-based electrolyte additives for a primary alkali metal electrochemical cell and a corresponding primary alkali metal electrochemical cell.
  • a monotonous pulse course is desirable.
  • the voltage curve of this pulse series is usually rectangular (Fig. 1).
  • a voltage delay also called voltage delay, is an undesirable characteristic in the discharge process of implantable alkali metal cells under current pulse discharge conditions.
  • a voltage delay is caused by the formation of relatively high-resistance cover layers on the anode surface, which leads to an increase in the battery internal resistance. This effect can only be seen when the batteries are loaded with high pulse current densities and the battery voltage drops disproportionately.
  • H. the voltage at the beginning of the first pulse is lower than at the end of the pulse or when the first pulse is lower than the minimum voltage of the last pulse
  • a voltage delay is usually evident in alkali metal / metal oxide and alkali metal / mixed metal oxide cells at over 40% DoD (depth of discharge) of their capacity discharge or below their capacity for the first time after longer storage Pulse load.
  • DoD depth of discharge
  • a high-resistance cover layer forms on the anode surface, for example due to the dissolution of cathode active material or due to discharge products in the battery electrolyte, which under certain pulse discharge conditions can lead to a voltage delay or non-monotonous behavior.
  • Electrolyte additives such as phosphates, dicarbonates, nitrites, alkyl phosphates and organic additives with hydroxyl groups (-OH) and carboxy groups to suppress or reduce the voltage delays for alkali metal / transition metal oxide (e.g. Li / SVO) and alkali metal / mixed oxides x and / or transition metal oxide or for Li / SVO cells are known in the art.
  • alkali metal / transition metal oxide e.g. Li / SVO
  • alkali metal / mixed oxides x and / or transition metal oxide or for Li / SVO cells are known in the art.
  • the aforementioned additives are typically used for alkali metal / transition metal oxide systems, in particular for lithium / silver vanadium oxide (Li / SVO) and lithium / silver vanadium oxide mixed cathodes (Li / SVO mixed cathodes), in which there is an increase in impedance and, as a consequence, a voltage delay due to high-resistance cover layers comes from metal deposits such as vanadium, silver and / or metal alloys on the electrode surface.
  • the aforementioned additives are not suitable for alkali metal / carbon monofluoride (Li / CFx) systems in which the voltage delay occurs due to fluoride-lithium deposits on the anode surface.
  • Organoborate salts are also known from the prior art as electrolyte conducting salt or electrolyte additive to reduce self-discharge and to reduce / eliminate the voltage delay after storage at room temperature and at elevated temperature of the Li / CFx cells (for example from US Pat. No. 7740986 B2).
  • the electrolytes based on organoborates show an increased battery resistance compared to the standard electrolyte (see Example 01).
  • an object of the present invention is to provide an electrolyte additive for primary cells, especially with lithium as the active electrode material, which reduces, preferably eliminates, the voltage delay and reduces the battery impedance.
  • the object is achieved by a primary cell with the features of claim 1 and by using a boron compound with the features of claim 9. Suitable embodiments are given in the corresponding dependent claims and in the following description.
  • a primary cell which comprises alkali metal as active electrode material, in particular as active anode material, and an electrolyte with a boron compound, in particular an organic boron compound.
  • primary cell is used in the context of the present description in its generally known, technical meaning. In particular, it refers to a galvanic cell that can no longer be electrically charged after discharging. Primary cells are sometimes referred to as primary batteries.
  • the boron compound is in particular a non-ionic compound, that is to say preferably not a salt of a boron-containing acid.
  • the boron compound is a compound according to formula (1), (2), (3), (4), (7) or (8):
  • RI, R2, R3, R4 and R5, independently of one another, are selected from the group comprising hydrogen, alkyl, alkenyl, cycloalkyl, thioether-heterocycles, aryl and heteroaryl, where RI, R2, R3, R4 or R5 is not thiophene.
  • RI, R2, R3, R4 and R5 are independently unsubstituted or substituted one or more times with at least one substituent selected from the group comprising: alkyl, fluoroalkyl, alkoxy, carbonyl, carboxyl, thiol, Thioalkoxide, aryl, ether, thioether, nitro, cyano, amino, azido, amidino, hydrazino, hydrazono, carbamoyl, sulfo, sulfamoyl, sulfonylamino, alkylaminosulfonyl, alkylsulfonylamino and / or halogen.
  • Preferred substituents include halogens, fluoroalkyls and cyano or nitrile groups, where RI, R2, R3, R4 or R5 is not thiophene.
  • the boron bond is a compound according to formula (1), where RI is an alkyl, in particular a Ci-C ö -alkyl, in particular methyl, cyclopropyl or cyclohexyl, or an aryl, in particular a phenyl, is a benzyl or a naphthyl which is unsubstituted or substituted by one or more Ci-C4-alkyl, -F, -CI, -Br, -I, -CN, -CF 3 or -OCF 3 , and R2 to R4 and R5 are independently a Ci-C4 alkyl.
  • RI is an alkyl, in particular a Ci-C ö -alkyl, in particular methyl, cyclopropyl or cyclohexyl, or an aryl, in particular a phenyl, is a benzyl or a naphthyl which is unsubstituted or substituted by one
  • the primary cell of the invention it is provided that the Boritati is a compound according to formula (2) wherein RI is to R4 and R5, independently, a Ci-C 4 alkyl.
  • the boron bond is a compound according to formula (3), where RI is an alkyl, an alkenyl, in particular an allyl, or an aryl, in particular a benzyl, phenyl, or benzoate, which is unsubstituted or is substituted with one or more Ci-C4-alkyl, -F, -CI, -Br, -I, -CN, -CF 3 or -OCF 3 or a compound according to formula (3), and R2 and R3 are independent of one another are a Ci-C 4 alkyl.
  • the boron bond is a compound according to formula (4), where RI, R2 and R3 are, independently of one another, a Ci-C 4 alkyl.
  • the boron bond is a compound according to formula (7), where RI to R 3 independently of one another are an alkyl, in particular a Ci-C4-alkyl, in particular methyl, or an aryl, in particular a phenyl, which is unsubstituted or substituted by one or more -F, -CI, -Br, -I, -CN, -CF 3 or -OCF 3 .
  • the boron bond is a compound according to formula (8), where RI to R3 are, independently of one another, a C 1 -C 4 alkyl.
  • the compound according to formula (8) is 2,4,6-trimethoxyboroxine.
  • the boron compound in the electrolyte in a concentration in the range of 0.001 1 to 0.5 moPl mo l 1 is present.
  • the alkali metal is lithium as the active electrode material
  • the primary cell is a lithium battery.
  • the electrolyte is a non-aqueous electrolyte.
  • - comprises a first solvent which is selected from the group consisting of an ester, an ether, a dialkyl carbonate and a mixture thereof, in particular tetrahydrofuran, methyl acetate, diglyme (bis (2-methoxyethyl) ether), triglyme (tris (2-methoxyethyl) ) ether), tetraglyme (tetra (2-methoxyethyl) ether), 1,2-dimethoxyethane, 1,2-diethoxyethane, 1-ethoxy, 2-methoxyethane, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate or a mixture thereof , and
  • - comprises a second solvent which is selected from the group consisting of a cyclic carbonate, a cyclic ester, a cyclic amide and a mixture thereof, in particular propylene carbonate, ethylene carbonate, butylene carbonate, g-butyrolactone, N-methylpyrrolidinone or a mixture thereof, or from a polar non-aqueous solvent such as acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, or a mixture thereof.
  • a second solvent which is selected from the group consisting of a cyclic carbonate, a cyclic ester, a cyclic amide and a mixture thereof, in particular propylene carbonate, ethylene carbonate, butylene carbonate, g-butyrolactone, N-methylpyrrolidinone or a mixture thereof, or from a polar non-aqueous solvent such as acetonitrile, dimethyl sulfoxide, dimethylformamide, di
  • the electrolyte has an anhydrous alkali salt, in particular an anhydrous lithium salt, preferably LiC10 4 , LiPF 6 , LiBF, LiAsF 6 , LiSbF 6 , LiC10 4 , LiAlCU, LiGaCU, LiC (S0 2 CF 3 ) 3 , LiN (S0 2 CF 3 ) 2 , LiSCN, Li0 3 SCF 2 CF 3 , LiC 6 F 5 S0 3 , Li0 2 CF 3 , LiS0 3 F, LiB (C 6 H 5 ) 4 , LiCF 3 S0 3 or a mixture thereof.
  • an anhydrous alkali salt in particular an anhydrous lithium salt, preferably LiC10 4 , LiPF 6 , LiBF, LiAsF 6 , LiSbF 6 , LiC10 4 , LiAlCU, LiGaCU, LiC (S0 2 CF 3 ) 3 , LiN (S0 2 CF 3 ) 2 ,
  • the primary cell according to the invention furthermore comprises a carbon monofluoride as active electrode material, in particular as active cathode material.
  • the carbon monofluoride can be present per se or form mixed cathodes with metal oxides, preferably of transition metals, for example Mn0 2 , SVO (silver oxide and vanadium pentoxide) Copper silver vanadium oxide, cobalt oxide, nickel oxide, copper oxide, copper sulfide, iron sulfide, iron disulfide, titanium disulfide, or mixtures thereof.
  • the primary cell according to the invention comprises a cathode binder, in particular polytetrafluoroethylene, polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), polyolefins, preferably thermoplastic elastomers, in particular ethylene / propylene-diene terpolymers, or mixtures thereof.
  • a cathode binder in particular polytetrafluoroethylene, polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), polyolefins, preferably thermoplastic elastomers, in particular ethylene / propylene-diene terpolymers, or mixtures thereof.
  • the primary cell according to the invention comprises carbon, in particular in the form of graphite, graphite powder or soot, or aluminum, in particular aluminum powder, titanium, in particular titanium powder, stainless steel, in particular stainless steel powder, or mixtures thereof as a conductive additive.
  • a boron compound is provided for use as an electrolyte additive in a primary cell with an alkali metal as the active electrode material, in particular an organic boron compound.
  • the boron compound is a compound according to formula (1), (2), (3), (4), (7) or (8):
  • RI, R2, R3, R4 and R5 are independently selected from the group comprising hydrogen, alkyl, alkenyl, cycloalkyl, thioether, heterocycles, aryl and heteroaryl, where RI, R2, R3, R4 or R5 is not thiophene.
  • RI, R2, R3, R4 and R5 are independently unsubstituted or substituted one or more times with at least one substituent selected from the group comprising: alkyl, fluoroalkyl, alkoxy, carbonyl, carboxyl, thiol, Thioalkoxide, aryl, ether, thioether, nitro, cyano, amino, azido, amidino, hydrazino, hydrazono, carbamoyl, sulfo, sulfamoyl, sulfonylamino, alkylaminosulfonyl, alkylsulfonylamino and / or halogens, where RI, R2, R3, R4 or R5 are not thiophene is.
  • the boron bond is a compound according to formula (1), where RI is an alkyl, in particular a Ci-C ö -alkyl, in particular methyl, cyclopropyl or cyclohexyl, or an aryl, in particular a phenyl, is a benzyl or a naphthyl which is unsubstituted or substituted by one or more Ci-C -Alky, -F, -CI, -Br, -I, -CN, -CF 3 or -OCF 3 , and R2 to R4 and R5 are independently a Ci-C4 alkyl.
  • RI is an alkyl, in particular a Ci-C ö -alkyl, in particular methyl, cyclopropyl or cyclohexyl, or an aryl, in particular a phenyl, is a benzyl or a naphthyl which is unsubstituted or substituted by one
  • the boron bond is a compound according to formula (2), where RI to R4 and R5 are, independently of one another, a C1-C4 alkyl.
  • the boron bond is a compound according to formula (3), where RI is an alkyl, an alkenyl, in particular an allyl, or an aryl, in particular a benzyl, phenyl, or benzoate, which is unsubstituted or is substituted by one or more Ci-C4-alkyl, -F, -CI, -Br, -I, -CN, -CF 3 or -OCF3, and R2 and R3 are, independently of one another, a C1-C4 alkyl.
  • the boron bond is a compound according to formula (4), where RI, R2 and R3 are, independently of one another, a C1-C4 alkyl.
  • the boron bond is a compound according to formula (7), where RI to R3 are, independently of one another, an alkyl, in particular a Ci-C4-alkyl, in particular methyl, or an aryl, in particular a phenyl which is unsubstituted or substituted by one or more -F, -CI, -Br, -I, -CN, -CF 3 or -OCF 3 .
  • Trimethylboroxine - 2,4,6-triphenylboroxine
  • the boron bond is a compound according to formula (8), where RI to R3 are independently C 1 -C 4 alkyl.
  • the compound according to formula (8) is 2,4,6-trimethoxyboroxine.
  • the alkali metal is lithium as the active electrode material
  • the primary cell is a lithium battery.
  • LiBOB lithium bis (oxalato) borate
  • Electrolyte additive (4,4,5,5-tetramethyl-2- (3,4,5-trifluorophenyl) -l, 3,2-dioxaborolane (TMTFPDDB),
  • Electrolyte additive trimethylboroxine (TMB)
  • Lithium carbon monofluoride cells Li / CFx
  • Lithium carbon monofluoride cells Li / CFx
  • the overall equation of the discharge is as follows:
  • the LiF is an anionic and electrical insulator, which on the one hand adheres to the surface of the cathode pores and on the other hand partially dissolves in the electrolyte.
  • the fluoride concentration in the electrolyte increases, which leads to a high-resistance top layer of lithium fluoride compounds on the anode surface (Table 1). Under certain pulse discharge conditions, this can lead to a voltage delay or non-monotonous behavior.
  • the present invention relates generally to an alkali metal electrochemical cell and, more particularly, to a lithium / carbon monofluoride or a lithium / carbon monofluoride metal oxide cell, which are suitable for applications with current pulse discharge and without voltage delay. More precisely, the present invention relates to an electrochemical lithium metal cell with a non-aqueous electrolyte which prevents the voltage delay by adding an electrolyte.
  • the present invention relates in particular to dioxaborolane, diboron and boroxine electrolyte additives for alkali-metal electrochemical cells with carbon monofluoride (CFx) or CFx transition metal oxide mixed cathodes (e.g.
  • the Li / CFx system shows a voltage delay under pulse conditions before the end of life "EOL" state.
  • dioxaborolane diboron and boroxine additives are added to the electrolyte.
  • the advantage of this invention is the formation of an SEI film (Solid Electrolyte Interface) on the negative electrode (for example a lithium metal), which protects the electrode surface, i.e. the addition of electrolyte is reduced on the anode surface and protects it from the formation of a high-resistance coating, which in turn Stabilization of the internal battery resistance is used, the discharge performance is improved and the voltage delay is eliminated (Table 2).
  • Table 2 Boron content on lithium anode surface in the EOL state
  • the invention preferably relates to the above-described electrochemical alkali metal cell with non-aqueous, ionically conductive electrolytes and at least one compound according to the general formula (1), (2), (3), (4), (5), (6), (7) ), and (8).
  • the electrochemical cells for the working examples and comparative examples were produced with the following components:
  • Example 1 (Comparative Example: FIG. 3 shows the impedance curves of the discharge under 12.7 KOhm and a daily pulse load of 10 mA / 156 s, with a standard electrolyte (without added electrolyte) and a standard electrolyte with 0.075 M lithium bis (oxalato) borate
  • LiBOB is an electrolyte additive known in the prior art.
  • an increase in the internal battery resistance with increasing discharge can be clearly seen.
  • Example 2 Example 2:
  • FIG. 4 shows the discharge data under 12.7 KOhm and a daily pulse load of 10mA / 156s, the impedance curve of the batteries during discharge being shown in (a) and the pulse curve at 180 mAh in (b).
  • Standard electrolyte and the standard electrolyte with 0.075 M of an electrolyte additive according to the invention in this case 4,4,5,5-tetramethyl-2- (3,4,5-trifluorophenyl) -1,3,2-dioxaborolane (TMTFPDDB). It can be clearly seen that the internal battery resistance does not increase over wide discharge ranges due to the addition of electrolyte according to the invention.
  • FIG. 5 shows the discharge data below 12.7 KOhm and a daily pulse load of 10 mA / 156 s, with the impedance curve of the batteries during discharge in
  • the total discharge capacity of the implantable batteries can be made usable by adding dioxaborolane, diboron and boroxin electrolytes.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Primary Cells (AREA)

Abstract

La présente invention concerne une cellule primaire comprenant un métal alcalin comme matériau d'électrode actif, en particulier comme matériau d'anode actif, et un électrolyte pourvu d'un composé bore, le composé bore étant un composé de formule (1), (2), (3), (4), (7) ou (8).
EP20734772.5A 2019-07-10 2020-07-01 Élimination des retards de tension et stabilisation de l'impédance au moyen d'additifs électrolytiques dans des cellules électrochimiques de métal alcalin Pending EP3997748A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19185488.4A EP3764434A1 (fr) 2019-07-10 2019-07-10 Élimination du retard de tension et stabilisation de l'impédance à l'aide des ajouts d'électrolyte dans les éléments électrochimiques en métaux alcalins
PCT/EP2020/068552 WO2021004862A1 (fr) 2019-07-10 2020-07-01 Élimination des retards de tension et stabilisation de l'impédance au moyen d'additifs électrolytiques dans des cellules électrochimiques de métal alcalin

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EP3997748A1 true EP3997748A1 (fr) 2022-05-18

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EP20734772.5A Pending EP3997748A1 (fr) 2019-07-10 2020-07-01 Élimination des retards de tension et stabilisation de l'impédance au moyen d'additifs électrolytiques dans des cellules électrochimiques de métal alcalin

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KR20230087715A (ko) * 2021-12-10 2023-06-19 에스케이온 주식회사 신규한 보론 함유 화합물 및 이를 포함하는 이차전지용 전해액 첨가제

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4654280A (en) * 1984-12-27 1987-03-31 Eveready Battery Company Nonaqueous cell employing a cathode-electrolyte solution containing a boron-containing additive
EP0186200A3 (fr) * 1984-12-27 1988-03-23 Eveready Battery Company, Inc. Pile non aqueuse à solution cathode-électrolyte contenant un additif au bore
CA2196493C (fr) * 1997-01-31 2002-07-16 Huanyu Mao Additifs ameliorant le cycle de vie des batteries au lithium rechargeables a electrolyte non aqueux
US6022643A (en) * 1997-12-08 2000-02-08 Brookhaven Science Associates Boron compounds as anion binding agents for nonaqueous battery electrolytes
CA2344243C (fr) * 1999-09-02 2006-05-09 Dai-Ichi Kogyo Seiyaku Co., Ltd. Polyelectrolyte, electrolyte non aqueuse et dispositif electrique les renfermant
JP4092631B2 (ja) * 2001-09-20 2008-05-28 トヨタ自動車株式会社 非水電解質二次電池
US7740986B2 (en) 2002-09-03 2010-06-22 Quallion Llc Battery having electrolyte with organoborate additive
JP4462012B2 (ja) * 2004-08-18 2010-05-12 ダイソー株式会社 電解質組成物および電池
WO2006101779A2 (fr) * 2005-03-15 2006-09-28 The University Of Chicago Electrolytes non aqueux destines a des batteries au lithium-ion
KR20080062671A (ko) * 2006-12-29 2008-07-03 제일모직주식회사 리튬 2차전지용 비수성 전해액 및 이를 포함하는 리튬2차전지
CN101567472B (zh) * 2008-04-25 2012-09-05 中国科学院物理研究所 一种电解质溶液及其制备方法和应用
JP5463581B2 (ja) * 2009-03-11 2014-04-09 三井化学株式会社 非水電解質及び該非水電解質を含む非水電解質二次電池
US20100279155A1 (en) * 2009-04-30 2010-11-04 Medtronic, Inc. Lithium-ion battery with electrolyte additive
US10411299B2 (en) * 2013-08-02 2019-09-10 Zenlabs Energy, Inc. Electrolytes for stable cycling of high capacity lithium based batteries
JP6372823B2 (ja) * 2015-02-18 2018-08-15 株式会社日立製作所 リチウム二次電池、リチウム二次電池用電解液、及び、リチウム二次電池の電解液用添加剤
US20160372790A1 (en) * 2015-06-22 2016-12-22 Johnson Controls Technology Company Electrolyte formulations for lithium ion batteries

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WO2021004862A1 (fr) 2021-01-14
JP2022540337A (ja) 2022-09-15
US20220263102A1 (en) 2022-08-18
EP3764434A1 (fr) 2021-01-13
CN114342141A (zh) 2022-04-12

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