EP3105804A1 - Éléments galvaniques et anodes pour batterie au lithium (partiellement) lithiées et à capacité accrue, et procédé de production de composés d'intercalation du graphite de synthèse - Google Patents

Éléments galvaniques et anodes pour batterie au lithium (partiellement) lithiées et à capacité accrue, et procédé de production de composés d'intercalation du graphite de synthèse

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Publication number
EP3105804A1
EP3105804A1 EP15706396.7A EP15706396A EP3105804A1 EP 3105804 A1 EP3105804 A1 EP 3105804A1 EP 15706396 A EP15706396 A EP 15706396A EP 3105804 A1 EP3105804 A1 EP 3105804A1
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EP
European Patent Office
Prior art keywords
lithium
graphite
powder
partially
lithiated
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Withdrawn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
EP15706396.7A
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German (de)
English (en)
Inventor
Ulrich Wietelmann
Vera NICKEL
Stefan Scherer
Ute Emmel
Thorsten Buhrmester
Steffen Haber
Gerd Krämer
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.)
Albemarle Germany GmbH
Original Assignee
Rockwood Lithium GmbH
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Filing date
Publication date
Application filed by Rockwood Lithium GmbH filed Critical Rockwood Lithium GmbH
Publication of EP3105804A1 publication Critical patent/EP3105804A1/fr
Withdrawn legal-status Critical Current

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/22—Intercalation
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/0569—Liquid materials characterised by the 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/08—Intercalated structures, i.e. with atoms or molecules intercalated in their structure
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • H01M2004/027—Negative electrodes
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • Electrochemical cells for lithium-ion batteries are built by default in the discharged state. This has the advantage that both electrodes are in air and water stable form.
  • the electrochemically active lithium is introduced exclusively in the form of the cathode material.
  • the cathode material contains lithium metal oxides such as lithium cobalt oxide (LiCo0 2 ) as an electrochemically active component.
  • the anode material in the currently commercial batteries contains in the discharged state as active material a graphitic material with a theoretical electrochemical capacity of 372 Ah / kg. It is usually completely lithium free.
  • (also lithium-free) materials with higher specific capacitance for example alloy anodes, often silicon- or tin-based, can be used.
  • lithium-free potential cathode materials eg Mn0 2
  • SLMP stabilized metal powder
  • the lithium powders coated according to WO2012 / 052265 are kinetically stable up to about 80 ° C. in NMP, they but decompose at temperatures beyond exothermic, mostly under runaway-like phenomena. For mainly this reason, the use of lithium powders as a lithium reservoir for lithium-ion batteries or for the prelithiation of electrode materials has not been able to prevail commercially.
  • additional electrochemically active lithium can also be introduced by the addition of graphite lithium intercalation compounds (LiC x ) to the anode in a lithium electrochemical cell.
  • Li intercalation compounds can be prepared either electrochemically or chemically.
  • the electrochemical production takes place automatically when charging conventional lithium-ion batteries.
  • materials with lithium: carbon stoichiometries of at most 1: 6.0 can be obtained (see, for example, N. Imanishi, "Development of the Carbon Anode in Lithium Ion Batteries", in: M. Wakihara and O. Yamamoto (ed Lithium Ion Batteries, Wiley-VCH, Weinheim 1998.)
  • the partially or completely lithiated material prepared in this way can in principle be taken from a charged lithium-ion cell under a protective gas atmosphere (argon) and, after appropriate conditioning (washing and drying with suitable solvents), for new battery cells Because of the high associated costs, this procedure is chosen only for analytical investigation purposes and the method has no practical relevance for economic reasons.
  • lithiated natural graphite (Ceylon graphite) by high energy milling in a ball mill
  • the predominantly hexagonally structured natural graphite from present day Sri Lanka was treated with lithium powder (170 ⁇ average particle size) in the Li: C ratios of 1: 6; 1: 4 and 1: 2 implemented.
  • Complete lithiation to the final molar ratio LiC 6 could only be achieved with the molar ratio 1: 2 (R. Janot, D. Guerard, Progr. Mat. Sci. 50 (2005) 1 -92).
  • This synthesis variant is technically-commercially disadvantageous.
  • a very high lithium excess is needed to achieve sufficient or complete lithiation.
  • the electrode production takes place by simply pressing the graphite onto a copper net.
  • the counter and reference electrodes are lithium bands, and the electrolyte used is a 1 M LiClO 4 solution in EC / DMC.
  • the type of electrode preparation by simple pressing is not the prior art, as it is used in the commercial battery electrode production.
  • Simple compression without binder and if necessary addition of conductivity additives does not lead to stable electrodes, since the volume changes taking place during charging / discharging must inevitably lead to crumbling of the electrodes, whereby the functionality of the battery cell is destroyed.
  • the invention has for its object to show a partially or completely lithiated anode graphite for lithium battery cells and to provide a built-lithium cell available whose capacity is increased by the additional lithium reservoir over the prior art.
  • the object is achieved in that a lithium battery cell is used, the lithiated in the anode before the first charging cycle partially or fully lithiated to the thermodynamically stable boundary stoichiometry LiC 6 (hereinafter referred to as "(partially) lithiated") contains synthetic graphite or the (That is, the anode) consists thereof and wherein the lithiation of the synthetic graphite was effected by non-electrochemical means under normal pressure or a slight pressure of ⁇ about 10 bar.
  • Synthetic anode graphites are offered by a number of manufacturers, including: SGL Carbon, Hitachi and Timcal. These products are particularly important for use as anode materials for lithium-ion batteries.
  • the synthesis graphite SLP 30 from Timcal consists of particles having an average particle size of 31.5 ⁇ and has an irreversible capacity of 43 mAh / g (based on the reversible capacity of 365 mAh / g corresponds to about 12%) C. Decaux et al., Electrochim. Acta 86 (2012) 282).
  • the introduced via the Grenzstöchiometrie LiC 6 lithium is presumably in finely divided form the graphite surface.
  • the reaction takes place in the temperature range between 0 and 180 ° C, preferably 20 to 150 ° C either in vacuo or under an atmosphere whose components are not or only slowly acceptable with metallic lithium and / or lithium graphite intercalation react. This is preferably either dry air or a noble gas, more preferably argon.
  • the Lithi istsvorgang takes place at normal or only moderately elevated ambient pressures (maximum 10 bar).
  • the lithium is in powder form, consisting of particles having an average particle size between about 5 and 500 ⁇ , preferably 10 and 200 ⁇ used.
  • Both coated powders e.g. a stabilized metal powder offered by FMC (Lectromax powder 100, SLMP) having a lithium content of at least 97% by weight or, for example, an alloying element-coated powder having metal contents of at least 95% by weight (WO2013 / 104787A1).
  • FMC Lectromax powder 100, SLMP
  • SLMP Zinctromax powder 100, SLMP
  • WO2013 / 104787A1 an alloying element-coated powder having metal contents of at least 95% by weight
  • uncoated lithium powders having a metal content of> 99% by weight.
  • the purity with respect to metallic impurities must be very high.
  • the sodium content must not be> 200 ppm.
  • the Na content is preferably ⁇ 100 ppm, particularly preferably ⁇ 80 ppm.
  • synthesis graphite come all powdered graphite grades, which are industrially produced and not obtained from natural resources (mines) in question.
  • Starting materials for synthesis graphites are graphitizable carbon carriers, such as petroleum coke, needle coke, industrial carbon black, plant wastes, etc., as well as graphitizable binders, in particular coal tar pitch or thermosetting synthetic resins.
  • the synthesis graphites used are characterized by average particle sizes in the range of about 1 to 200 ⁇ , preferably 10 to 100 ⁇ .
  • the synthesis graphites used generally have a lower degree of graphitization or order (and a lower crystallinity) than typical natural graphites, for example the graphite from Ceylon / Sri Lanka.
  • the degree of graphitization of a graphitic material can be characterized by accurate measurement of the coherent domain diameter L a (ie, the in-plane crystallite diameter) by X-ray or (more simply) by Raman spectroscopic measurements.
  • Graphites exhibit typical Raman absorption at about 1575-1581 cm “1 (" G-band "). This absorption is due to in-plane vibration vibrations (E 2g G-mode) of the sp 2 -bonded carbons of the undisturbed lattice.
  • the domain diameter L a can be calculated, which describes the degree of crystallinity and thus the degree of graphitization (AC Ferrari and J. Robertson, Phys. Rev. B, Rhim et al., Carbon 48 (2010) 1012-1024) Highly crystalline graphite (HOPG) and well-ordered natural graphites have a 1: D G ratio of 0 - ca Guoping et al., Solid State Ionics 176 (2005) 905-909)
  • the natural graphite from Ceylon / Sri Lanka has an ID: IG ratio of about 0.1 (corresponding to a domain diameter L a of about 40 nm, s.
  • synthesis graphites which have a L D : I G ratio of at least 0.2, more preferably at least 0.5 (corresponding to domain diameter L a of not more than 29 nm, particularly preferably not more than 12 nm).
  • the reaction takes place during mixing or grinding of the two components lithium powder and graphite powder.
  • the grinding can be done by mortar and pestle.
  • the reaction preferably takes place in a mill, for example a rod, vibration or ball mill.
  • the reaction is carried out in a planetary ball mill.
  • the planetary ball mill Pulverisette 7 premium line from Fritsch can be used on a laboratory scale.
  • When using planetary ball mills can surprisingly very short reaction times of ⁇ 10 h, often even ⁇ 1 h realize.
  • the mixture of lithium and graphite powder is preferably ground in the dry state.
  • the inert fluid is preferably an anhydrous hydrocarbon solvent, eg a liquid alkane or alkane mixture or an aromatic solvent.
  • the addition of solvents dampens the severity of the grinding process and less grazes the graphite particles.
  • the grinding time depends on different requirements and process parameters:
  • Type of grinding balls e.g., hardness and density
  • Reactivity of lithium powder e.g., type of coating
  • the milling times vary between 5 minutes and 24 hours, preferably 10 minutes and 10 hours.
  • the lithium-containing surface zone it finds an implementation of the lithium-containing surface zone to form no or little air-reactive (ie thermodynamically stable) lithium salts (such as lithium carbonate, lithium fluoride, lithium hydroxide, lithium alcoholates, lithium carboxylates etc) instead.
  • lithium salts such as lithium carbonate, lithium fluoride, lithium hydroxide, lithium alcoholates, lithium carboxylates etc.
  • most of the lithium not present on the particle surface eg the intercalated portion
  • remains in active form ie with an electrochemical potential of ⁇ approximately 1 V vs.. Li / Li " * " received.
  • Such coating agents are known from the lithium-ion battery technology as in situ film former (also referred to as SEI-formers) for the negative electrode and described, for example, in the following review article: A. Lex-Balducci, W. Henderson, S.
  • Suitable liquid coating agents are, for example: carbonic acid esters (eg vinylene carbonate (VC), vinyl ethylene carbonate (VEC), ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), fluoroethylene carbonate (FEC)); Lithium chelatoborate solutions (eg lithium bis (oxalato) borate (LiBOB); lithium bis (salicylato) borate (LiBSB); lithium bis (malonato) borate (LiBMB); lithium difluorooxalatoborate (LiDFOB), as solutions in organic solvents, preferably selected from: oxygen-containing Heterocycles such as tetrahydrofuran (THF), 2-methyl-tetrahydrofuran (2-methyl-THF), dioxolane, carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, dieth
  • the coating not only improves handling properties and safety in electrode (generally anode) fabrication, but also application properties in the electrochemical battery cell.
  • the use of precoated anode materials eliminates the formation of an SEI (solid electrolyte interface) during contact of the (partially) lithiated graphite anode material with the liquid electrolyte of the battery cell.
  • SEI solid electrolyte interface
  • the trained outside the electrochemical cell stabilizing coating layer corresponds in its properties to a so-called artificial SEI. Ideally, the necessary prior art forming process of the electrochemical cell is eliminated or it is at least simplified.
  • the coating process is generally carried out under inert gas atmosphere (e.g., argon protective atmosphere) at temperatures between 0 and 150 ° C.
  • inert gas atmosphere e.g., argon protective atmosphere
  • mixing or stirring conditions are advantageous.
  • the necessary contact time between coating agent and (partially) lithiated synthesis graphite powder depends on the reactivity of the coating agent, the prevailing temperature and other process parameters. In general, times between 1 minute and 24 hours make sense.
  • the gaseous coating agents are used either in pure form or, preferably, in admixture with a carrier gas, e.g. a noble gas such as argon.
  • the (partially) lithiated (and optionally pre-coated) synthesis graphite powder can be used to make battery electrodes by the method described above. This is done under inert or dry space conditions with at least one binder material and optionally one or more further powdery lithium-storable material (s) with an electrochemical potential ⁇ 2 V vs Li / Li " * " and also optionally with a conductivity-improving additive (eg carbon blacks or nickel powder ) and an organic solvent and homogenized and this dispersion is applied by a coating method (casting method, spin coating or air-brush method) on a current collector and dried.
  • a coating method casting method, spin coating or air-brush method
  • the (partially) lithiated graphite powder produced by the process according to the invention is surprisingly only moderately reactive toward N-methylpyrrolidone (NMP).
  • NMP N-methylpyrrolidone
  • lower molar C: Li ratios (ie higher Li contents) of up to min. 3 are used.
  • the (partially) lithiated graphite powders can be processed into a castable or sprayable dispersion without any problems with NMP and the binder material PVdF (polyvinylidene difluoride).
  • the solvents N-ethylpyrrolidone, dimethyl sulfoxide, cyclic ethers (eg tetrahydrofuran, 2-methyltetrahydrofuran), ketones (eg acetone, butanone) and / or lactones (eg ⁇ -butyrolactone) can be used.
  • binder materials are: carboxymethylcellulose (CMC), alginic acid, polyacrylates, Teflon and polyisobutylene (for example Oppanol from BASF
  • CMC carboxymethylcellulose
  • alginic acid for example toluene or saturated hydrocarbons, eg hexane, cyclohexane, heptane, octane).
  • polyacrylates for example toluene or saturated hydrocarbons, eg hexane, cyclohexane, heptane, octane).
  • hydrocarbons aromatics, for example toluene or saturated hydrocarbons, eg hexane, cyclohexane, heptane, octane
  • the optionally used further pulverulent lithium-storable material is preferably selected from the groups graphites, graphene, layer-structured lithium transition metal nitrides (eg Li 2.6 Co 0 , 4N, LiMoN 2 , Li 7 MnN 4 , Li 2,7 Fe 0 , 3N), with lithium alloyable metal powder (eg, Sn, Si, Al, Mg, Ca, Zn or mixtures thereof), main group metal oxides with a metal which in reduced form (ie as metal) with lithium alloyed (eg Sn0 2 , Si0 2 , SiO, Ti0 2 ), metal hydrides (eg MgH 2 , LiH, TiNiH x , AlH 3 , L1AlH 4 , LiBH 4 , Li 3 AlH 6, LiNiH 4 , TiH 2 , LaNi 4.25 Mno, 75H5, Mg 2 NiH 3.7 ), lithium amide , lithium imide, Tetralithiumnitridhydrid
  • the anode dispersion prepared according to the invention containing a non-electrochemical (partially) lithiated synthesis graphite powder is applied to a current collector foil preferably consisting of a thin copper or nickel sheet, dried and preferably calendered.
  • the anode foil produced in this way can be produced by combination with a lithium-conducting electrolyte separator system and a suitable cathode foil containing a lithium compound with a potential of> 2 V vs.
  • Li / Li " * (eg lithium metal oxides such as LiCoO 2 , LiMn 2 O 4 , LiNi 0, 5 Mn 1 5 O 2 or sulfides such as Li 2 S, FeS 2 ) to a lithium battery with respect to the prior art increased capacity combine.
  • the technical production of such galvanic cells is well known and described, for example P. Kurzweil, K. Brandt, Secondary Batteries, Lithium Rechargeable Systems: Overview, in: Encyclopedia of Electrochemical Power Sources, ed. J. Garche, Elsevier, Amsterdam 2009, Vol. 5, p. 1 -26).
  • a powdered (partially) lithiated synthesis graphite prepared by an electroless process is treated under inert or dry space conditions with at least one binder material and optionally one or more further powdery lithium-storable material (s) with an electrochemical potential ⁇ 2 V vs Li / Li + and also optionally mixed with a conductivity-improving additive and a solvent and homogenized and this dispersion is applied by a coating process on a Stromabieiterfolie and dried.
  • the optionally used further powdery lithium-insertable material is preferably selected from the groups graphites, graphene, layered lithium transition metal nitrides, lithium alloyable metal powders, main group metal oxides with a metal which alloys with lithium in reduced form (ie as metal), metal hydrides , Lithium amide, lithium imide, tetralithium nitride hydride, black phosphorus, as well as transition metal oxides that can react with lithium according to a lithium conversion mechanism.
  • the uncoated lithium metal powder has a purity (i.e., a proportion of metallic lithium) of at least 99% by weight.
  • the coating agents are selected from: N 2 , CO 2 , CO, O 2 , N 2 O, NO, NO 2 , HF, F 2 , PF 3 , PF 5 , POF 3 , carbonic acid esters, lithium chelatoborate solutions, sulfur organic compounds, nitrogen-containing organic compounds, phosphoric acid, organic phosphorus-containing compounds, fluorine-containing organic and inorganic compounds, silicon-containing compounds.
  • Galvanic cell containing a cathode, a lithium-conductive electrolyte separator system and a synbium-containing anode, wherein the anode contains or consists of a (partially) lithiated graphite powder produced from synthesis graphite and lithium powder by non-electrochemical means during cell production (i.e., prior to the first charge cycle).
  • Galvanic cell in which the synthesis graphite used for the lithiation has an ID: IG ratio of at least 0.2, more preferably at least 0.5, determined by Raman spectroscopy.
  • Galvanic cell at which the molar ratio between graphite (C) and electrochemically active lithium (Li) min. 3: 1 and max. 600: 1.
  • the milled product was sieved in the glove box and 4.6 g of a black, gold shimmering and flowable powder were obtained.
  • the milled product was sieved in the glove box and 4.9 g of a black, flowable powder was obtained.
  • Example 3 Stability of the lithiated synthesis graphite from Example 1 in contact with NMP and EC / EMC
  • the investigation of the thermal stability was carried out with the aid of an apparatus from Systag, Switzerland, the Radex system.
  • the substances or substance mixtures to be investigated are weighed into steel autoclaves with a capacity of about 3 ml and heated. From temperature measurements of the furnace and vessel thermodynamic data can be derived.
  • 0.1 g of Li / C mixture or compound was weighed with 2 g of EC / EMC under inert gas conditions and heated to a final furnace temperature of 250 ° C. Only when exceeding about 190 ° C, the mixture of inventive LiC x - material and EC / EMC begins to decompose.
  • thermolyzed mixtures are predominantly solid or polymerized. Even the analogous mixture of uncoated lithium powder with a 1: 1 mixture of EC / EMC reacts violently when it exceeds about 170 ° C.
  • Example 4 Coating of a Lithiated Synthetic Graphite Powder According to the Invention Produced by Stoichiometry LiC 6 Using a LiBOB Solution in EC / EMC
  • Example 6 Stability of the Coated Product of Example 4 in EC / EMC and NMP
  • Example 5 The coated material from Example 5 and a sample of the untreated lithiated graphite powder (prepared analogously to Example 1) were investigated in the Radex apparatus for thermal stability in the presence of an EC / EMC mixture.
  • the uncoated material begins to decompose already from about 130 ° C, while the coated powder reacts exothermally above about 170 ° C.
  • the mixture remains liquid.

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Abstract

L'invention concerne un élément galvanique comprenant une cathode, un système séparateur d'électrolyte conducteur de lithium et une anode contenant du graphite de synthèse, l'anode contenant ou étant constituée d'une poudre de graphite (partiellement) lithiée constituée de graphite de synthèse et de poudre de lithium et produite par voie non-électrochimique lors de la fabrication de l'élément (c-à-d avant le premier cycle de charge). L'invention concerne également un procédé de lithiation (partielle) sans courant de graphite synthétique, caractérisé en ce que la lithiation (partielle) sans courant du graphite synthétique pulvérulent se produit après le mélange avec une poudre métallique de lithium et est obtenue par brassage et/ou pulvérisation avec formation d'intercalaires du graphite lithium de composition LiCx (où x = 6 –600).
EP15706396.7A 2014-02-13 2015-02-13 Éléments galvaniques et anodes pour batterie au lithium (partiellement) lithiées et à capacité accrue, et procédé de production de composés d'intercalation du graphite de synthèse Withdrawn EP3105804A1 (fr)

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PCT/EP2015/053039 WO2015121391A1 (fr) 2014-02-13 2015-02-13 Éléments galvaniques et anodes pour batterie au lithium (partiellement) lithiées et à capacité accrue, et procédé de production de composés d'intercalation du graphite de synthèse

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CN106663775A (zh) 2017-05-10
JP6738276B2 (ja) 2020-08-12
KR20160121564A (ko) 2016-10-19
JP2017513177A (ja) 2017-05-25
US20160351893A1 (en) 2016-12-01
BR112016018582B1 (pt) 2022-11-29
CN106663775B (zh) 2020-07-24
WO2015121391A1 (fr) 2015-08-20
CA2939157A1 (fr) 2015-08-20
BR112016018582A2 (fr) 2017-08-08
DE102015202611A1 (de) 2015-08-13

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