EP3427317A1 - Utilisation de complexes métalliques à base de trialkylsiloxy en tant qu'additif dans des batteries au lithium-ion - Google Patents

Utilisation de complexes métalliques à base de trialkylsiloxy en tant qu'additif dans des batteries au lithium-ion

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Publication number
EP3427317A1
EP3427317A1 EP17708812.7A EP17708812A EP3427317A1 EP 3427317 A1 EP3427317 A1 EP 3427317A1 EP 17708812 A EP17708812 A EP 17708812A EP 3427317 A1 EP3427317 A1 EP 3427317A1
Authority
EP
European Patent Office
Prior art keywords
lithium
group
electrode
electrolyte
cathode
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.)
Withdrawn
Application number
EP17708812.7A
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German (de)
English (en)
Inventor
Laura IMHOLT
Stephan RÖSER
Babak REZAEI RAD
Isidora CEKIC-LASKOVIC
Martin Winter
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.)
Westfaelische Wilhelms Universitaet Muenster
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Westfaelische Wilhelms Universitaet Muenster
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Application filed by Westfaelische Wilhelms Universitaet Muenster filed Critical Westfaelische Wilhelms Universitaet Muenster
Publication of EP3427317A1 publication Critical patent/EP3427317A1/fr
Withdrawn legal-status Critical Current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
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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 the field of lithium-ion batteries.
  • Lithium-ion batteries are currently the leading technology in the field of rechargeable batteries, especially in the field of portable electronics. Due to their high energy and power density as well as low energy
  • Self-discharge lithium-ion batteries also show a high potential for
  • the document US 201 1/0027663 A 1 discloses an electrolytic battery having an anode of tungsten oxide, molybdenum oxide, iron sulfide, titanium sulfide or lithium titanate, and an electrolyte containing boron, phosphorus or titanium triaquine 1 oxy 1 - contains additives. These prevent an improvement in the retention rate of the anodes mentioned
  • a further disadvantage is that not every compound which contains one or more silyl groups is suitable as an additive due to different stability of the compounds and the formation of possible decomposition products. Especially in the case of boron trialkylsiloxyl compounds, the effect is strongly concentration-dependent. Thus, when the concentration is too high, their effect as an anion acceptor comes into play, which has a negative effect on the performance of the electrodes, which limits the use of this additive to only very small amounts.
  • the present invention was therefore based on the object to overcome at least one of the aforementioned disadvantages of the prior art.
  • the present invention was based on the object of providing means that enable the use of carbonate electrolytes on high-voltage cathode materials.
  • the electrolyte comprises at least one metal compound of the formula M (OSiR and / or
  • LiAl (OSiR;) 4 where x is 2, 3 or 4, M is selected from the group comprising Mg 2 ' , AF and / or Ti 4+ , and R is each the same or independently selected from the group comprising C iC ⁇ -alkyl, ( ⁇ 7 -cycloalkyl. (-C ⁇ -alkenyl, CVCn-alkynyl and / or CV io-aryl, each unsubstituted or mono- or polysubstituted with at least one substituent selected from the group comprising F, C ' i j-alkyl and / or CN, and
  • the object is further achieved by the use of an electrolyte containing at least one metal compound of the formula M (OSiR . ) And / or LiAl (OSiR 5) _t
  • Form cathode materials At the same time can be intercepted by the additive directly contained in the electrolyte, or formed by oxidative electrolyte decomposition HF and the electrolyte thus be cleaned.
  • the cycle stability of a lithium-ion battery can be significantly increased. It is also advantageous that the usable specific capacity of the high-voltage cathode materials is significantly increased at an increased turn-off voltage.
  • the practical capacity of 135 mAh / g at one Shutdown voltages of 4.3 V vs. Li / Li to 1 50 mAh / g at 4.6 V vs. Li / Li can be increased at 1 C. Due to the increased practical capacity as well as the increased working potential of the
  • Cathode material can be obtained lithium-ion batteries with significantly increased energy density.
  • M is selected from Mg 2 ' , Al 3 * or Ti 4 * and x is 2, 3 or 4, respectively.
  • M Al " or Ti 4 and x
  • R is in each case the same or independently selected from the group formulas M (OSiR x and LiAl (OSiR 3 ) 4 from the group consisting of C 1 -C 12 -alkyl, C 3-7 -cycloalkyl, C 2 -C 12 -alkenyl , C2-Ci2-alkynyl and / or C0-Cio-Aryi, where these groups are each unsubstituted or mono- or polysubstituted with at least one
  • i-alkyl and / or CN may be.
  • C 1 -C -alkyl includes straight-chain or branched alkyl groups having 1 to 12 carbon atoms.
  • Ce-Cio-aryl is to be understood as meaning aromatic radicals having 6 to 10 carbon atoms.
  • aryl preferably includes carbocycles.
  • R is the same or independent of each other and is a linear or branched C i -CCalkylrios or pheny.
  • R is an alkenyl or
  • R is also preferably a CyCVAIkenyl- or CY A I i nyl group.
  • the groups R are each consistently linear or branched C 1 -CV alkyl.
  • CV.-C 1 D-aryl groups are preferably selected from the group comprising phenyl and / or naphthyl, preferably phenyl.
  • C s -C 7 -cycloalkyl groups are preferably selected from the group comprising cyclopentyl and / or cyclohexyl.
  • R is substituted R is preferably single or multiple substituted by fluorine.
  • the etall compound is selected from the group consisting of M (OSiR,) x wherein x is 3 or 4 and M is Al " or Ti 1 and / or LiAl (OSiR;) 4 , wherein R are each the same or independently selected is selected from the group consisting of methyl, ethyl, propyl, butyl, tert-butyl and / or phenyl
  • R is the same or independent of each other linear or branched C] -C 4 alkyl.
  • small alkyl groups can lead to compounds which are identified at higher potentials.
  • Particularly preferred compounds are selected from the group comprising
  • Tetrakis (trimethylsiloxy) titanium Ti (OSiCU L)) .i, TMST), tris (tri m et hy I si lox y) a 1 uminium (Al (OSiC; Hy) !, TM SA) and / or lithium tetrakis (trimethyisiloxy) aluminate
  • LiAl (OSiC ⁇ H >>) _i, LiTMSA LiAl (OSiC ⁇ H >>) _i, LiTMSA
  • the electrolyte contains the metal compound of the formula M (OSiR;) and / or LiAi (OSiR 3 ) 4 in a range of> 0.001% by weight to ⁇ 10% by weight,
  • electrolytes comprising such amounts of the compounds exhibit very good Fcst redesign-Elektrolyt Phasengrenzc (CEI) formation on high-voltage cathodes.
  • the electrolyte contains
  • Tetrakis (trimethylsiloxy) titanium Ti (OSiC sH.)), TMST) in a range of> 0.5 wt. to ⁇ 1% by weight, tris (trimethylsiloxy) aiuminium (AI (OSiC sI lu) ;, TMSA) in a range of> 0.5 wt .-% to ⁇ 1 wt .-% and / or lithium Tct kra s (tri m cth y I si lox y) a 1 umin at (LiAliOSiC U l.))!, LiTMSA) in one Range of> 3 wt .-% to ⁇ 4 wt .-%, each based on the total weight of the electrolyte. In particular, in these areas Elektroiyte containing such amounts of compounds showed high conductivity.
  • the electrolyte is a preferably substantially anhydrous, organic liquid or liquid electrolyte comprising a lithium salt dissolved in a solvent.
  • the solvent is an eyeball or linear carbonate or a mixture of cyclic and / or linear carbonates.
  • Preferred cyclic carbonates are selected from ethylene carbonate (EC) and / or propylene carbonate (PC), preferably linear carbonates, preferably from diethyl carbonate (DEC), dimethyl carbonate (DMC) and / or et h y I m e t h y 1 c a rbo n t (EMC).
  • Preferred mixtures of cyclic and / or linear carbonates are mixtures of ethylene carbonate and dimethyl carbonate, ethylene carbonate and ethylene glycol or ethyl carbonate and diethyl carbonate.
  • Other suitable solvents are nitrile, e.g. Acetone, tri 1 (AN), dinitrile, e.g. Glutaronitrile (G EN), adiponitrile (ADN) and / or pimelonitrile (PIN), and lactones, e.g. ga m m a - B u t y ro 1 a c t o n (GBL) and / or gamma-vaierolactone (GVL).
  • GNL Glutaronitrile
  • ADN adiponitrile
  • PIN pimelonitrile
  • lactones e.g. ga m m a - B u t y ro 1 a c t o n (GBL)
  • Electrolyte additive the use of cycliccn. and linear carbonates based electrolyte in combination with high-voltage cathode materials, for example of commercially available Standardeiektroiyten as LP30, LP50 and LP47, M ischungen of ethylene carbonate with dimethyl carbonate, e thy 1 m et hy I ca bo nat or diethyl earbonat each containing 1 M LiPF 6 as conducting salt ,
  • the lithium salt may be selected from the group consisting of LiAsF 6 , LiClO.sub.t, LiSbF 6 , LiPtCie, LiAlCli, LiGaCl 4 , LiSCN, LiAlO 4 , LiCF 3 CF 2 SO 3 , Li (CF 3 ) SO 3 (LiTf),
  • LiC (S0 2 CF 3 ) 3 phosphate-based lithium salts, preferably LiPF ( "LiPF 3 (CF 3 ) 3 (Li FAP) and LiPF i (C 10) (LiTFOB), borate-based lithium salts, preferably LiBF 4 , LiB (C 2 0 4 ) 2 (LiBOB), LiBF 2 (C 2 O 4 ) (LiDFOB), LiB (C 2 O 4 ) (C 3 O 4 ) (LiMOB), Li (C 2 F 5 BF 3 ) (LiFAB ) and Li 2 B 12 F 12 (LiDFB) and / or lithium salts of sulfonylimides, preferably LiN (S0 2 CF 3 ) 2 (LiTFSI) and / or LiN (S0 2 C 2 F 5 ) 2 (UB ETI).
  • a preferred lithium conducting salt is LiPF 6 .
  • Electrodes can be one
  • the active material is usually made of a dispersion, which in one.
  • Dispersion medium further contains a binder and optionally additives such as conductive carbon and also as
  • Electrode paste is applied to the current conductor.
  • active material refers to a material which can absorb and release lithium ions reversibly.
  • the active material thus “actively” participates in the elec- tronic reactions that occur during charging and discharging, in contrast to the other possible constituents of an electrode.
  • the so-called active material thus corresponds to the active electrode mass.
  • the cathode has an active material with an electrode potential E> 4 V. Li / Li, preferably an active material with an electrode potential E> 4.3 V vs. Li I i. a so-called high-voltage cathode material.
  • the active material of the electrode is in particular cathode selected from the group comprising lithium-manganese-nickel-oxides (LMNO); Lithium nickel manganese cobalt composite oxides
  • NMC NMC
  • LiM0 2 with M Mn, Co, Ni
  • x, y or z can also assume the value 0, so that the ischo ide strictly speaking also include the lithium metal oxides such as LiCo0 2 , LiNi0 2 and LiMn0 2 .
  • at least two of x, y and z are not equal to zero.
  • This voltage results when using carbon anodes. to a potential of> 4 V vs. Li Li, preferably> 4.3 V vs. Li Li at the cathode.
  • cells or lithium-ion batteries are usually operated with high-voltage cathodes.
  • a further aspect of the invention relates to the use of an electrolyte comprising at least one metal compound of the formula M (OSiR; k and / or LiAl (OSiR.-j.wherein x is 2, 3 or 4, M is selected from the group comprising Mg ).
  • R is the same or independently v onden ählt Selected from the group comprising Ci-Cjo alkyl, C 3- 7 cycloalkyl, C 2 -C 12 alkenyl, C 6 -C ] .-> - alkynyl and / or CVC iu-aryl, each unsubstituted or mono- or polysubstituted with at least one substituent selected from the group comprising F, C'i .i-alkyl and / or CN, for the preparation of a solid electrolyte Phase interface on an electrode, in particular the cathode, of a lithium-based electrochemical energy store.
  • MiOSiR x and the compounds LiAl (OSiR 3 ) 4 are the same or independent
  • one another is a linear or branched C 1 -C 6 -acyl group or phenyl.
  • R an alkenyl or alkynyl group
  • R is also preferably a CVCVAlkcnyl- or CVCV Aikinyi juxtapos.
  • the groups R are each consistently linear or branched Ci -CVAlkyl.
  • CV, C 1 -C aryl groups are preferably selected from the group comprising phenyl and / or naphthyl, preferably phenyl.
  • CC 7-C 1 -C 1 -alkyl groups are preferably selected from the group comprising cyclopentyl and / or cyclohexyl.
  • the metal compound is selected from the group consisting of M (OSiR 3 wherein x is 3 or 4 and M is Al 3+ or Ti 1 and / or LiAl (OSiR 4 , wherein each R is the same or independently selected from the group group
  • R is the same or independent of each other linear or branched C] -C alkyl
  • methyl or ethyl preferably methyl.
  • small alkyl groups can lead to compounds that are oxidized at higher potentials.
  • Particularly preferred compounds are selected from the group comprising
  • Tetrakis (trimethylsiloxy) titanium Ti (OSIC;. H>), TMST.), Tris (trimethylsiloxy) aluminum
  • LiAi (OSiC 3 H 9 ) 4 LiTMSA
  • an electrolyte is usable containing the metal compound of
  • an electrolyte is used containing TMST in a range of> 0.5 wt ..
  • TMSA in a range of> 0.5 wt .-% to ⁇ 1 wt % and / or LiTMSA in a range of> 3 wt .-% to ⁇ 4 wt .-%, each time based on the total weight of the electrolyte.
  • cyclic or linear carbonates Preferably used as solvent are cyclic or linear carbonates or a mixture of cyclic and / or linear carbonates.
  • Preferred cyclic carbonates are selected from ethylene carbonate (EC) and / or propylene carbonate (PC), preferred linear Carbonates of diethyl carbonate (DEC), dimethyl carbonate (DMC) and / or
  • EMC Ethyl methyl carbonate
  • Preferred mixtures of cyclic and / or linear carbonates are mixtures of ethylene carbonate and dimethyl carbonate, of ethylene carbonate and ethyl methyl carbonate or of ethylene carbonate and diethyl carbonate.
  • Other suitable solvents are nitriles, e.g. Acetonitrile (AN), dinitriles, e.g. Glutaronitrile (GLN), adiponitrile. (ADN) and / or pimelonitrile (PIN), and lactones, e.g.
  • the active material of the electrode in particular the cathode, are those with an electrode potential E> 4 V vs.. Li / Li + on, preferably an active material having an electrode potential E> 4.3 V, a so-called I lochvolt cathode material.
  • the active material is selected from the group comprising lithium manganese nickel oxides (LMNO); Lithium-nickel-manganese-cobalt mixed oxides (NMC);
  • Transition metal oxides of the type x Li MnO? - (1 -x) Li M O2 with M Ni, Mn, Co and 0 ⁇ x ⁇ l.
  • x, y or z can also assume the value 0, so that strictly speaking the M ischo idc also include the lithium metal oxides such as LiCoC LiNiO 2 and LiMnO 2 .
  • at least two of x, y and z are not equal to zero.
  • anodes for example, those based on materials such as graphite, lithium or lithium titanate are usable.
  • Another object of the invention relates to an electrode, in particular a cathode, obtainable by the method according to the invention.
  • a further subject relates to an electrode, in particular cathode, for a lithium-based electrochemical energy store, comprising an active material with a
  • Electrode potential E> 4 V vs. Li Li the electrode having a solid-state control phase interface (CEI), wherein the surface of the active material s, at least in a thickness of thickness in the range of> 1 nm to ⁇ 5 nm, is a metal selected from the group containing Mg, Al and / or Li.
  • the metal is in the range of> 0.05 atomic% to ⁇ 5 atomic%, preferably in the range of> 0.1 atomic% to ⁇ 3 atomic%, preferably in the range Range of from 0, 1 5 atomic% to ⁇ 2 atomic%, based on a total sum of the atoms of the active material of the layer of 100 atomic%.
  • the proportion of metal I can be determined by X-ray photoelectron spectroscopy (XPS).
  • atomic% means the percentage of a defined amount of atoms relative to one defined
  • the electrode preferably comprises a so-called high-voltage cathode material.
  • the active material of the electrode in particular the cathode, a
  • LMNO lithium manganese nickel oxide
  • MC Lithium-nickel-manganese-cobalt mixed oxides
  • Preferred lithium manganese nickel oxide (LMNO) are
  • LiNi x Mn y 0 4 m with x ⁇ 0.5 and y 2-x.
  • x, y or z can also assume the value 0, so that the mixed oxides strictly speaking also the Include lithium metal oxides such as LiCo0 2 , LiNi0 2 and LiMn0 2 .
  • at least two of x, y and z are not equal to zero.
  • a further subject matter of the invention relates to a lithium-based electrochemical energy store comprising an inventive method or inventively manufactured according to the invention
  • Electrode in particular a cathode.
  • energy storage for the purposes of the present invention includes primary and secondary electrochemical
  • the lithium-based electrochemical energy store is preferably a lithium battery, lithium-ion battery, a lithium-ion battery, lithium-polymer battery or lithium-ion capacitor.
  • the energy store is preferably a lithium-ion furnace or a lithium-ion battery.
  • anodes based on materials such as graphite, lithium or lithium titanate usable As expressedeiektroden ind example, anodes based on materials such as graphite, lithium or lithium titanate usable.
  • the compounds of the formula M (OSiRs) x can be prepared by customary synthesis methods.
  • Another object of the invention relates to a process for the preparation of lithium Te takis (trimethylsiloxy) a I ininate, comprising the following steps:
  • Tetrakis (trimethyisiloxy) aluminate is obtained.
  • step a) the reaction of Trimethyisiianoi with n-butyllithium in step a) with cooling, in particular at a temperature in the range of -80 ° C to -90 C.
  • Solvents for the reaction are, for example, toluene, benzene, n-pentane, n-hexane, n- Fleptane or cyclohexane suitable. After the reaction, the solvent becomes
  • lithium trimethylsilanolate can be obtained as a solid.
  • step b) AlCh is added to lithium trimethylsilanolate from step a).
  • a suspension of AlCh in a solvent such as toluene can be added to the lithium silanolate.
  • Tetrakis (trimethylsiioxy) aiuminat obtained.
  • the lithium silanolate is not added to the suspension of AICI 3 , as this neutralizes the
  • Tri s (t i meth y I si iox y) a I u mini u m is obtained.
  • FIG. 1 shows the conductivity of the electrolyte LP47 (EC: DEC 3: 7, 1 M LiPF 6 ),
  • FIG. 2 shows the efficiency (top) and discharge capacity (bottom) against the cycle number for the cyclizations of a NMC cathode in LP47 containing 0.5, 1 or 3% by weight T ST.
  • FIG. 3 shows the efficiency (top) and discharge capacity (bottom) against the number of cycles for the cyclizations of an NMC cathode in LP47 containing 0.5, 1 or 3
  • FIG. 4 shows the capacity (in-ordinate) and the efficiency (right ordinate)
  • Figure 6 shows the efficiency (top) and discharge capacity (bottom) against the number of cycles
  • Figure 7 shows the insertion capacity (left ordinate) and the co-efficient
  • Figure 8 shows in Figure 8a) shows the impedance spectrum of a NMC Halbzel le before
  • FIG. 9 shows scanning electron micrographs of the surface of an MC cathode after 100 cycles in LP47 in FIG. 9a), in 1.P47 containing 0.5% by weight TMST in FIG. 9b), in LP47 containing 0.5% by weight TM SB in FIG Figure 9c), and in LP47 containing 3 wt .-% LiTMSA in Figure 9d).
  • FIG. 10 shows the Coulomb efficiency (top), the energy efficiency (M itte) and the
  • a first step trimethylsilanol (7.41 g, 0.082 mol) was added dropwise with cooling at -80 ° C to a mixture of n-butyl lithium (56 m L) in toluene. Toluene was removed by distillation and lithium trimethylsilanoate remained as a white crystalline solid.
  • a suspension of AICH (3.48 g, 0.026 mol) in toluene was added to a solution of lithium silanolate in toluene and stirred overnight. A white solid formed, which was isolated and purified by vacuum at 200 ° C, 0.2 mbar. The successful synthesis of the compound was confirmed by NMR spectroscopy, elemental analysis, and mass spectrometry.
  • Lithium trimethylsilanolate (1.961 g, 0.02 mol) in toluene was slowly added dropwise at a temperature of from -80 ° C. to a solution of AlCh (0.906 g, 0.0067 mol) in toluene.
  • Tetra kis (tri-methylsiloxy) titanium (TMST, Example 1), 0.5% by weight T ris (trim et hy! Si! Oy) bo (TMSB, A BCR GmbH & Co KG), 1 % By weight of Tctrak is (tri m ethy I si I oy) a I uminium (TM SA, Example 3) or 3% by weight of lithium tetra kis (tri m et hy I si I ox y) a I uminate (LiTMSA, Example 2).
  • the electrolyte LP47 was used as a control without additives.
  • the conductivity of the electrolyte was measured in polyether ether ketone (PEEK) conductivity cells (cell constant 2.64 cm -1 ) with Edeistahl electrodes, using a potentiostat (Solartron 1287A) in conjunction with an I m ped anm e s e s t (Solartron).
  • PEEK polyether ether ketone
  • Solartron 1287A potentiostat
  • I m ped anm e s e s t Solartron
  • the impedance of the cell was measured in a frequency range from 1 kHz to 1 MHz and the conductivity was read at a phase angle of 0 ° C.
  • the measurement was performed at a temperature of -40 ° C to + 60 ° C ° C (climatic chamber, Binder MK53), and the heat-tracing measurements were first heated to 60 ° C and then in
  • FIG. 1 shows the course of the conductivity of the electrolyte LP47 without and with 0.5% by weight of tetrakis (trimethylsiloxy) titanium (TMST), 0.5% by weight of tris (trimethylsiloxy) boron (TMSB), 1% by weight of tetrakis (Trimethylsiioxy) aiuminium (TMSA) or 3 wt .-% lithium
  • the conductivity was due to the addition of the respective element
  • electrolyte compounds containing the compounds are useful as additives for use in lithium batteries.
  • the oxidative stability of the electrolyte LP47 containing the various additives was determined by linear sweep voltammetry. In this method, a
  • Platinum Elektrodc performed as a working electrode and Lithiumfol ie (Rockwood, lithium, battery grade) as a counter and Referenzelektrodc. To determine the o idativen stability, the potential between the working and Refercnzelektrode of the open circuit voltage to 6.5 V.
  • the limit for the current density was set to 0.01 mA cm.
  • the stability window of the electrolyte LP47 was determined without and with 0.5% by weight of tris (trimethylsiloxy) boron (TM SB), 0.5% by weight of tetrakis (tri-methylsilyloxy) titanium (EMST), 1% by weight. -% Tri s (t ri m et hy 1 si I ox y) a I uminiu m. (TMSA, Example 3) and 3 wt% M. lithium
  • PVdF Pol yvinyl idenfl uorid
  • Toda working electrode
  • lithium foil Rockwood lithium, battery grade
  • the electrodes were separated with a Gias fiber separator (Whatman GF / D) or a nonwoven separator based on polyolefins (Freudenberg FB2 1 90), which was impregnated with the respective electrolyte.
  • the cyclization of the NMC half-lines was carried out in a voltage range of 3.0 V to 4.6 V versus Li / Li. Constant current measurements were performed on a Series 4000 (Maccor) battery tester at 20 ° C ⁇ 2 ° C. After three
  • Electrolytes containing 0.5% by weight, 1% by weight or 3% by weight of tetrakis (trimethylsiloxy) titanium (TMST) were prepared by mixing the respectively required amount of the compound in the electrolyte LP47 (EC: DEC 3 : 7, 1 M LiPF 6 ) were dissolved. As a comparison served the
  • Electrolyte LP47 containing 0.5 wt .-%, 1 wt .-% or 3 wt .-% tris (trimethylsiioxy) boron (TMSB) was used.
  • FIG. 3 shows in the upper part the efficiency and in the lower part the discharge capacity versus the number of cycles for T ris (t ri methyl alcohol) bo (TMSB). As can be seen from Figure 3, showed the
  • electrochemical cyclization was carried out as described above, wherein as the electrolyte LP47 containing 0.5 wt .-%, 1 wt .-%, 3 wt .-% or 5 wt .-% lithium
  • Tetrakis (trimethylsiloxy) aluminate (LiTMSA) was used. LP47 was used without additives as the receptor.
  • the capacity and the efficiency against the number of cycles dargestel lt.
  • the electrolyte containing 3 wt .-% LiTMSA showed the electrolyte containing 3 wt .-% LiTMSA the best behavior during cyclization. No capacity loss was observed during 100 cycles, and the efficiency remained 99.6% after 100 cycles.
  • Electrochemical cyclization was carried out as described in Example 6, using a polynucleotide trap (FS2 1 90, Friendsberg) has been. Electrolytes containing 0.5% by weight of tris (trimethylsiloxy) boron (TM SB), 0.5% by weight
  • Tetrakis (trimethylsioxy) titanium (TMST), 1 wt% tetrakis (t ri m et h ylsilo y) a I uminium (TMSA) and 3 wt% lithium tris (trimethylsiloxy) aluminum (LiTMSA) were prepared By dissolving the required amount of the compound in the electrolyte LP47 (EC: DEC 3: 7, 1 M LiPF 6 ). As a comparison, the electrolyte was used without addition.
  • FIG. 6 shows in the upper part the efficiency and in the lower part the discharge capacity versus the number of cycles for the cyclizations using the respective electrolytes containing TM SB, TMST, TMSA and LiTMSA as well as the control LP47.
  • the electrolyte containing 3 wt .-% LiTMSA showed the best behavior during the cyclization. Also in this comparison it becomes clear that the electrolytes containing LiTMSA, and TMST show a better efficiency and discharge capacity than TMSB.
  • T44 Imerys
  • lithium foil Rockwood lithium, battery grade
  • the scan rate was set to 0.02 mV / s.
  • the electrolyte 1.P47 was used without additives as a reference and with 0.5% by weight of tris (trimethylsiloxy) boron (TMSB).
  • TMSB, TM SA and LiTMSA and 0.5 wt% TMST had no effect on the formation of the solid electrolyte phase interface (SEI) on the anode and thus are compatible with graphite anodes.
  • SEI solid electrolyte phase interface
  • the electrolyte containing 3 wt% TMST showed a broad reductive peak indicating the formation of an SEI involving the additive. Thus, it can also be assumed for TMST that this does not have any negative influence on the formation of the SEI on the anode.
  • FIG. 7 shows, for the electrolytes containing 0.5% by weight TMST, 0.5% by weight TMSB and 3% by weight LiTMSA, the Coulomb efficiency (top) and the insertion capacity (bottom) plotted against the number of cycles.
  • the additives showed kcinen negative influence on the anode of the lithium half-cell. Thus, these are usable in full cells.
  • EIS Electrochemical impedance spectroscopy
  • Resistors e.g. for this purpose, NMC active material from Example 6 was measured before the cyclization and after the 10th, 30th, 50th and 100th cycles by the cell after When these cycles were reached, the battery was charged to 3.9V vs. Li / Li with constant current and constant voltage for 24 hours to ensure that a similar state of charge was obtained, and each impedance measurement was performed twice.
  • FIG. 8a shows the impedance spectrum of the NMC sheath cell before the cyclization
  • FIG. 8b after the 50th cycle using the electrolyte LP47 containing in each case 0.5% by weight of tris (tri-methylsiloxy) boron (TMSB ) or tetrak is (tri methyl ethoxy) oxytitanium (TMST).
  • TMSB tris (tri-methylsiloxy) boron
  • TMST tri methyl ethoxy) oxytitanium
  • the NMC athodes of Example 6 were examined after 1 00 cycles by scanning electron microscopy and X-ray photoelectron spectroscopy. Electrodes were examined cyclized using the electrolyte LP47 containing in each case 0.5% by weight.
  • T SB Tris (trimethylsilyl) boron
  • TMST tetrakis (trimethylsiloxy) titanium
  • LiTMSA lithium tetrakis (trimethylsiloxy) aluminate
  • FIG. 9 shows the scanning electron micrographs of the surface of the NMC cathode after 1,00 cycles in I.P47 in FIG. 9a), in LP47 containing 0.5% by weight TMST in FIG. 9b), in LP47 containing 0.5% by weight TM SB in FIG. 9c). and in LP47 containing 3% by weight LiTMSA in Figure 9d) at 25,000 magnification.
  • CEI cathode electrolyte interphase
  • X-ray photoelectron spectroscopy was performed using an Ax is Ultra HAS spectroscope (K.RATOS), which was probed with a monochromatic AI ⁇ source (10 mA
  • Heating wire current 1 2 kV heating wire voltage source, 20 eV, 0 ° emission level). examined.
  • the examined sample area was about 300 x 700 mm.
  • the detected layer thickness at the surface of the investigated particles was about 0. 1 nm to 40 ⁇ m.
  • Tabel le 2 shows the detected play in atomic 0th, cobalt, manganese, carbon, boron, titanium and aluminum, based on the total number of atoms which, in the examined layer of the electrodes of a thickness of about 0 1 nm to 40 nm were:
  • titanium and aluminum were identifiable as part of the CEI layer. That boron could not be detected, it is on
  • the layer thickness of the CEI was determined by residual signals of PVdF, Co, Mn, C as described in Langmuir 2013, 29, 15813-15821. Table 3 shows the respective ones
  • Table 4 shows the relative composition of the CEI layer. From this one deduces that the CEI layer had a common composition.
  • FIG. 10 shows the Coulomb efficiency (top), the energy efficiency (center) and the specific discharge capacity (bottom) versus the number of cycles for the cyclization of the bulk in LP47 containing 0.5% by weight TMST (Std + 0.5% TMST ) as well as in LP47 (Std) as
  • Tet raki s tri-methyl-i-siloxy titanium (TMST) achieved as an additive an improvement in cycle stability of 123%.
  • TMST tri-methyl-i-siloxy titanium
  • electrolytes containing T ST exhibit better efficiency and discharge capacity even in bulk cells, and the results of the half cells in lithium ion volumes were confirmed.
  • the results show that the compounds TMST, TMSA and LiTMSA form a passivating, lithium-ion-conducting protective layer on the surface of high-voitage cathode materials.
  • the cells used showed a good cycle stability. Due to the high capacity and working potential of the cathode material, lithium-ion batteries can thus be obtained with a significantly increased energy density.

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Abstract

L'invention concerne l'utilisation d'un électrolyte contenant une liaison métallique de la formule M(OSiR3)x et/ou LiAl(OSiR3)4, dans laquelle x est 2, 3 ou 4 et M est choisi dans le groupe comprenant Mg2+, Αl3+ et/ou Ti4+ pour la production d'une surface limite de phase d'électrolyte solide (CEI) sur la cathode d'un accumulateur d'énergie électrochimique à base de lithium.
EP17708812.7A 2016-03-08 2017-03-06 Utilisation de complexes métalliques à base de trialkylsiloxy en tant qu'additif dans des batteries au lithium-ion Withdrawn EP3427317A1 (fr)

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DE102016104210.2A DE102016104210A1 (de) 2016-03-08 2016-03-08 Verwendung von Trialkylsiloxy-basierten Metallkomplexen als Additiv in Lithium-Ionen-Batterien
PCT/EP2017/055206 WO2017153349A1 (fr) 2016-03-08 2017-03-06 Utilisation de complexes métalliques à base de trialkylsiloxy en tant qu'additif dans des batteries au lithium-ion

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