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
  • H01M4/36—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
• • 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
  • 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
  • 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
  • H01M4/40—Alloys based on alkali metals
  • H01M4/405—Alloys based on 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
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/46—Alloys based on magnesium or aluminium
  • H01M4/463—Aluminium based
• • 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
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T29/00—Metal working
  • Y10T29/49—Method of mechanical manufacture
  • Y10T29/49002—Electrical device making
  • Y10T29/49108—Electric battery cell making

Definitions

• Aluminum-based hydride anodes and galvanic elements containing aluminum-based hydride anodes are aluminum-based hydride anodes and galvanic elements containing aluminum-based hydride anodes
• the currently used rechargeable lithium batteries contain graphite as the anode material.
• Graphite acts as a lithium insertion material and it has according to the equation
• electrochemical cell decreases in capacity accordingly. Even more serious are the consequences if needle-shaped dendrites penetrate the separator. As a result, the battery cell can be short-circuited with often catastrophic consequences: thermal run-away, usually accompanied by fire phenomena.
• lithium alloys As the anode material rather than pure lithium metal.
• lithium alloys show extremely high volume fluctuations during lithium insertion and removal (in some cases several 100%, eg LigAI 4 : 238%). Therefore, alloy anodes with the
• M La, Mg, Ni, Na, Ti
• Mg-based system described in the aforementioned patent has a pronounced hysteresis and its operability in a real
• Lithium battery could not be demonstrated so far.
• Hexahydridoaluminatanion ( ⁇ 3 " ) are insoluble in the said electrolyte and are compatible with them, ie there is no spontaneous reaction.
• Hexahydridoaluminate salts can therefore be used in galvanic cells with aprotic electrolytes, for example lithium batteries. Due to their low potential compared to Li / Li + , they can preferably be used as anodes (negative electrode).
• M 1 and M 2 are independently an alkali element selected from Li, Na and K; m is a number between 1 and 3;
• Embodiment of the invention i. when discharged, the anode contains LiaAlHe.
• U3AIH6 as an anode for galvanic elements.
• this hydride anode can be switched to a lithiated insertion material, for example a lithium metal oxide Li x M 3 O y .
• M 3 is a redox-active metal selected from the group Co, Ni, Mn, Fe, V, Cr, Ti; x is an integer between 1 and 3 and
• y and z are integers between 1 and 4.
• lithium metal oxides are: L1C0O2, LiNiO2, LiMn20 4, Li 2 Mn0 3, L1VO2 and mixed metal oxides such as Li (Nii / 3Mni / 3 Coi 3) 02,
• lithium insertion materials for example lithium phosphates (eg LiFePO, L1VPO4, LiMnPO 4 ), lithium silicates (eg Li 2 FeSiO 4 , Li 2 MnSiO 4 , Li 2 CoSiO 4 ) and mixed lithiated fluorometal oxides.
• lithium phosphates eg LiFePO, L1VPO4, LiMnPO 4
• lithium silicates eg Li 2 FeSiO 4 , Li 2 MnSiO 4 , Li 2 CoSiO 4
• mixed lithiated fluorometal oxides e.g Li 2 FeSiO 4 , Li 2 MnSiO 4 , Li 2 CoSiO 4
• lithium is used in excess in equation (4), in addition to lithium hydride, a mixture of the metals Li and Al and / or an alloy of elemental aluminum and lithium forms:
• LisAIHe + (3 + a) Li 6 LiH + AILi a (6) a is a number between 0 and 5, preferably between 0 and 2.
• the electrode redox reaction is then as follows:
• the galvanic cell When connected to a lithium-loaded insertion cathode, it is preferred that the hydride anode be in the discharged state, i. in the form of L13AIH6.
• the galvanic cell When using, for example, lithium manganese spinel, the galvanic cell then has the following electrode configuration according to the general equation (3)
• the lithiation of the cathode material can be done either ex-situ (ie outside the galvanic cell) or in the final assembled cell during cycling.
• ex-situ ie outside the galvanic cell
• aluminum-based hydride anode it is preferred to use these in the charged state. For example, this can be switched to a cathode consisting of a brownstone modification:
• Al-containing hydride anode 6 LiH according to the invention 1 Al. If less LiH is used relative to Al, for example only a 4: 1 molar ratio, then not all aluminum can be converted to the discharged form, the hexahydride. Rather, a part of the aluminum remains even after the charge in elemental form.
• the electrode configuration and the charge-discharge equation then look as follows when using manganese dioxide as a cathode:
• the molar ratio between LiH and Al or AILi a can assume values between 0.5: 1 and 10: 1.
• the molar ratio between U3AIH6 and Li can be between 1: 1 to 1:20.
• Al-containing hydride anode material according to the invention used in a discharged form (ie as Li 3 AIH 6 ), so it is also possible to mix it with
• molar ratios according to the invention between L1 3 AlH 6 , Al and LiH are in the range between 1: 0: 0 and 1: 0.1 -2: 0.1-12.
• the Al-containing hydride anode material according to the invention is preferably in
• the particles ⁇ 100 ⁇ , more preferably ⁇ 30 ⁇ large. It is preferable to add to the hydride anode materials of the invention conductivity-improving additives, for example, graphite, carbon black or finely divided metals (e.g., Ti powder).
• conductivity-improving additives for example, graphite, carbon black or finely divided metals (e.g., Ti powder).
• Suitable electrolytes are those familiar to the person skilled in the art (liquid, gel, polymer and solid electrolytes).
• the conductive salt used is the lithium salts which are soluble or else can be introduced in such products and have weakly coordinating, oxidation-stable anions. These include, for example, LiPF 6 ,
• Lithium fluoroalkyl phosphates LiBF 4 , imide salts (eg LiN (SO 2 CF 3 ) 2 ), LiOSO 2 CF 3 , methide salts (eg LiC (SO 2 CF 3 ) 3 ), L1CIO4, lithium chelatoborates (eg LiBOB), lithium fluorochelato borates (eg L1C 2 O 4 BF 2 ), lithium chelatophosphates (eg LiTOP) and lithium fluorochelatophosphates (eg Li (C204) 2PF2).
• imide salts eg LiN (SO 2 CF 3 ) 2
• LiOSO 2 CF 3 methide salts
• methide salts eg LiC (SO 2 CF 3 ) 3
• L1CIO4 lithium chelatoborates
• lithium fluorochelato borates eg L1C 2 O 4 BF 2
• lithium chelatophosphates eg
• LiPF 6 LiF + PF 5 form reactive species (the Lewis acid PF 5 and / or derivatives thereof) which are capable of exothermic reaction with the aluminum-based hydride anodes of this invention even at relatively low temperature.
• the preparation of the discharged hydride anode material is carried out according to the prior art, for example by reaction of lithium aluminum hydride with
• the charged Al-containing hydride anode material of the present invention becomes
• a conductivity-improving additive is added to the mixture, and
• a particularly preferred, fine material is formed by reaction of
• the solvents used are preferably ethers, for example diethyl ether, dibutyl ether, methyl tert-butyl ether, tetrahydrofuran or methyltetrahydrofuran.
• this reaction also solvent-free in an autoclave at
• Lithium hydride / aluminum mixture consists of the reaction of U3AIH6 with lithium metal:
• This reaction is preferably carried out either under milling conditions or thermally in bulk (i.e., solvent-free) at temperatures above the melting point of lithium (180.5 ° C). If the lithium is used in excess, a mixture of elemental Li and Al or a Li / Al alloy is obtained.
• a galvanic element consisting of an aluminum-based hydride anode, a transition metal-containing cathode and an aprotic
• Hydride anode in the discharged state contains a bi- or ternary aluminum hydride of the formula (M 1 ) m (M 2 ) 3 -m AIH6 or consists thereof, wherein M and M 2 are independently an alkali metal element selected from Li, Na and K; m is a number between 1 and 3; n is a number 3;
• a galvanic element in which a partially or completely lithiated lithium insertion material is used as the cathode (positive mass);
• galvanic element in which as
• Lithium insertion material is a lithium metal oxide, a lithiated phosphate, a lithiated silicate or a mixed lithiated fluorometal used.
• the invention relates to: - A method for producing a lithium battery, wherein an anode containing a bi- or ternary metal aluminum hydride of the general formula (M) m (M 2 ) 3- ⁇ , wherein M 1 and M 2 is independently an alkali metal element selected from Li, Na and K; m is a number between 1 and 3; n is a number> 3 with a partially or completely lithiated lithium insertion material through a
• the lithium insertion material is a lithium metal oxide, a lithium phosphate, a lithium silicate or a lithiated
• Fluorometalloxid or a mixture of said substance groups represents.
• the invention also relates to:
• bi- or ternary aluminum hydride is LisAlHe
• a negative mass which contains or consists of lithium hydride and aluminum metal in the charged state
• a negative mass containing conductivity-improving additives such as graphite or Leitruß.
• the invention finally relates to: the preparation of a mixture of lithium hydride and aluminum metal by reaction of lithium aluminum hydride with lithium metal in a polar, aprotic solvent and
• Lithium metal either under grinding conditions or thermally at temperatures above 180.5 ° C.
• FIG. 2 1. Charge of L13AIH6 in the potential range 0.6-3 V
• Figure 3 2.-5. Charge-discharge cycle of L13AIH6 in the potential range 0.6 - 3 V
• FIG. 2 shows lithium incorporation at a potential of about 1 V.
• FIG. 3 demonstrates that lithium incorporation is reversible.
• the relatively low charge / discharge capacity is due to the non-optimized electrode preparation (the electronic contact between the particles is not sufficiently ensured).

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• Battery Electrode And Active Subsutance (AREA)
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• 2010
  • 2010-10-07 CN CN2010800453641A patent/CN102763248A/zh active Pending
  • 2010-10-07 DE DE102010047572A patent/DE102010047572A1/de not_active Withdrawn
  • 2010-10-07 US US13/497,880 patent/US9166227B2/en not_active Expired - Fee Related
  • 2010-10-07 WO PCT/EP2010/006132 patent/WO2011042185A1/de active Application Filing
  • 2010-10-07 JP JP2012532492A patent/JP6037832B2/ja not_active Expired - Fee Related
  • 2010-10-07 EP EP10773840A patent/EP2486616A1/de not_active Withdrawn

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