Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
  • C07F5/02—Boron compounds
  • C07F5/022—Boron compounds without C-boron linkages
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
  • C07F5/02—Boron compounds
  • C07F5/04—Esters of boric acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
  • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
  • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
  • C07F9/6574—Esters of oxyacids of phosphorus
  • C07F9/65748—Esters of oxyacids of phosphorus the cyclic phosphorus atom belonging to more than one ring system
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0567—Liquid materials characterised by the additives
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0568—Liquid materials characterised by the solutes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
• • 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
  • H01M4/134—Electrodes based on metals, Si or alloys
• • 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
• • 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
• • 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 invention relates to a galvanic cell with a lithium metal or a lithium metal-containing alloy as the anode material.
• lithium batteries are particularly suitable for these purposes, which have a significantly higher energy density compared to the former systems.
• large-format lithium batteries should also be used eg for stationary applications (power back-up) as well as in the automotive sector for traction purposes (hybrid drives or purely electric drive).
• lithium-ion batteries are developed and used for this purpose, in which a graphite-containing substance is used as the anode.
• Graphite anodes in the charged state generally can not intercalate (intercalate) more than 1 lithium per 6 carbon atoms corresponding to a LiC 6 cutoff stoichiometry. This results in a lithium density of max. 8.8 wt .-%. Therefore, the anode material causes an undesirable limitation of the energy density of such battery systems.
• lithium metal or a lithium metal-containing alloy eg alloys of lithium with aluminum, silicon, tin, titanium or antimony
• This principle would allow a significantly higher specific lithium loading and thus energy density compared to the common graphite intercalation cathode.
• lithium metal-containing systems have unfavorable safety properties. Under unfavorable operating conditions (eg elevated temperatures), decomposition reactions can occur which lead to a dangerous run-away situation. The battery then gets on a self-heating path, which can lead to an explosive gas formation and destruction of the battery case.
• the invention has the object to overcome the above-described disadvantages of the prior art and to propose a safe rechargeable battery system with an energy density exceeding lithium ion technology.
• the object is achieved by a galvanic cell with a lithium metal or a lithium metal-containing alloy as the anode material containing an electrolyte containing lithium bis (oxalato) borate and at least one further lithium complex salt of the formulas I and / or II in an aprotic solvent or solvent mixture, wherein
• only one of the compounds of the formula I and / or II is present in the galvanic cell in an amount of from 0.1 to 10% by weight.
• only one of the compounds according to formula I and / or II is present in an amount of from 0.2 to 5% by weight in the galvanic cell.
• a galvanic cell in which only fluorine-free materials are contained in the electrolyte.
• electrolyte is present as a liquid or gel electrolyte.
• the solvent in the electrolyte of the galvanic cell is propylene carbonate or a mixture of ethylene carbonate and ethyl methyl carbonate.
• the galvanic cell is used for the production of large-sized batteries for electric traction or for stationary applications.
• Fig. 1 the behavior of fluorine-free, LiBOB-based electrolyte solutions in the presence of Li metal
• Fig. 4 DSC test with simultaneous print tracking of a PC solution containing 14
• Fig. 5 DSC tests of LiBOB-containing, fluorine-free solutions in EC-EMC (50:50) in
• FIG. 1 shows the behavior of fluorine-free, LiBOB-based electrolyte solutions in the presence of Li metal examples 1 to 3 and a comparative example 1.
• Comparative Example 2 shows the pressure / temperature behavior of a pure LiPF ⁇ -based electrolyte solution.
• a furnace temperature of about 210 0 C sets a highly exothermic decomposition event, which is accompanied by an explosive gas formation.
• the pressure (blue curve) increases within seconds from ⁇ 10 bar to> 250 bar:

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Manufacturing & Machinery (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• General Physics & Mathematics (AREA)
• Inorganic Chemistry (AREA)
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• Molecular Biology (AREA)
• Health & Medical Sciences (AREA)
• Secondary Cells (AREA)
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• Battery Electrode And Active Subsutance (AREA)

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• 2010
  • 2010-02-17 JP JP2011550468A patent/JP5791522B2/ja active Active
  • 2010-02-17 WO PCT/EP2010/000992 patent/WO2010094467A1/de not_active Ceased
  • 2010-02-17 CN CN201080008412XA patent/CN102484293A/zh active Pending
  • 2010-02-17 EP EP10705802.6A patent/EP2399318B1/de active Active
  • 2010-02-17 CN CN201710099760.6A patent/CN107046148A/zh active Pending
  • 2010-02-17 DE DE102010008331A patent/DE102010008331A1/de not_active Withdrawn
  • 2010-02-17 US US13/201,640 patent/US9509014B2/en active Active

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