WO2013045567A1 - Cellule électrochimique - Google Patents

Cellule électrochimique Download PDF

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Publication number
WO2013045567A1
WO2013045567A1 PCT/EP2012/069115 EP2012069115W WO2013045567A1 WO 2013045567 A1 WO2013045567 A1 WO 2013045567A1 EP 2012069115 W EP2012069115 W EP 2012069115W WO 2013045567 A1 WO2013045567 A1 WO 2013045567A1
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Prior art keywords
lithium
electrochemical cell
group
electrode
carbonate
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PCT/EP2012/069115
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German (de)
English (en)
Inventor
Martin Winter
Stefano Passerini
Simon LUX
Peter Bieker
Tobias PLACKE
Hinrich-Wilhelm MEYER
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Westfälische Wilhelms-Universität Münster
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Publication of WO2013045567A1 publication Critical patent/WO2013045567A1/fr

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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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • 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
    • 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 an electrochemical cell, in particular a secondary
  • Lithium-ion technology is currently the leading technology in the field of rechargeable battery storage systems, especially for applications in portable electronics.
  • Lithium-ion batteries include two electrodes separated by a separator. The charge transport is via an electrolyte containing a lithium salt dissolved in a nonaqueous organic solvent. In lithium-ion batteries, lithium ions are reversibly stored or removed from the electrode active materials. When charging a lithium-ion battery Li + - ions are transported from the cathode to the anode and the discharge process, the Li + ions change back from the anode to the cathode.
  • lithium-ion batteries have various disadvantages.
  • metal oxides of mixtures of nickel and cobalt are often used in lithium-ion batteries as electrode material, whereby the production costs are greatly increased by the use of nickel and especially by cobalt.
  • the heavy metals nickel and cobalt have a high toxicity.
  • An alternative to conventional lithium-ion batteries form the so-called dual graphite systems, which are based on a storage of lithium in a graphite anode and an incorporation of anions in a graphite cathode.
  • the graphite electrodes are also separated in dual graphite systems by a separator and the charge transport via an electrolyte containing a lithium salt.
  • Lithium salt and its concentration dependent Another disadvantage of dual graphite systems is that they have a high capacity loss during the first cycle.
  • the present invention was therefore based on the object to provide an electrochemical cell which overcomes at least one of the aforementioned disadvantages of the prior art.
  • the present invention was based on the object of providing an electrochemical cell which operates within the thermodynamic stability window of organic electrolytes. This object is achieved by an electrochemical cell, in particular a secondary electrochemical cell, comprising a lithium ion reversibly receiving and donating electrode, anions reversibly receiving and donating electrode and a
  • An electrolyte comprising a lithium salt and a solvent, wherein the lithium ion reversibly receiving and donating electrode comprises lithium titanate as lithium ion reversibly receiving and donating electrode material.
  • Another object of the invention relates to the use of lithium titanate as lithium ion reversibly receiving and donating electrode material in an electrochemical cell, in particular a secondary electrochemical cell comprising a lithium ions reversibly receiving and donating electrode and anions reversibly receiving and donating electrode.
  • an electrochemical cell based on the dual-ion insertion principle comprising a lithium cation reversibly receiving and donating lithium titanate electrode, at relatively low concentrations of the lithium salt of 1 M, even at low temperatures, a good conductivity and thus have good capacity ,
  • the, in particular secondary, electrochemical cell can operate reversibly within the thermodynamic stability window of the organic electrolyte with good capacity.
  • electrochemical cell high efficiency of the charge / discharge after the first
  • the electrochemical cell can provide increased security.
  • the especially secondary electrochemical cell has a good fast charging and in particular discharging capability.
  • the electrochemical cell has the further advantage of being able to be operated even at low temperatures, for example in a temperature range from -40 ° C. to + 55 ° C. This is particularly advantageous for use in portable electronics.
  • the particular secondary electrochemical cell with lithium titanate electrode has a long service life. In particular, this system is less toxic than nickel and cobalt-containing lithium ion systems and therefore more environmentally friendly. The environmental friendliness of this cell, which manages without cobalt and nickel-containing compounds, is a major advantage over current lithium-ion batteries.
  • lithium titanate means spinels of the formula Li x Ti y 0 4 , where 0.8 ⁇ x ⁇ 1.4 and 1.6 ⁇ y ⁇ 2.2.
  • Lithium titanate is Li ⁇ isO ⁇ .
  • the electrodes of the electrochemical cell can reversibly absorb and release lithium ions or anions.
  • the term “reversibly take up and release” is understood to mean that the active materials of the electrodes can reversibly store and disperse lithium cations or anions, intercalate and deintercalate, or take up and release by compound formation or alloy formation.
  • the term reversibly "intercalate and deintercalate” is understood to mean that a graphite or a carbon-based electrode can absorb and release lithium cations or anions.
  • the electrodes are usually composite electrodes, which may contain binders and additives in addition to the materials reversibly receiving and donating or intercalating and deintercalating the respective ions. These electrode materials are mostly on a metal foil or a carbon-based current collector foil, which acts as a current conductor, applied.
  • the lithium ion reversibly receiving and donating electrode comprises lithium titanate in the range of> 50 wt% to ⁇ 98 wt%, preferably in the range of> 75 wt% to ⁇ 95 wt%, preferably in the range from> 80 wt .-% to ⁇ 95 wt .-%, based on the total weight of the electrode.
  • cells having a lithium ion reversibly receiving and donating electrode comprising lithium titanate in such a range can have a particularly good rapid charging and discharging capability.
  • the lithium ion reversibly receiving and donating electrode comprises lithium titanate particles having a size or average
  • Diameter in the range of> 0.1 nm to ⁇ 10 ⁇ preferably in the range of> 0.5 nm to ⁇ 5 ⁇ , more preferably in the range of> 1 nm to ⁇ 800 nm, most preferably in the range of> 100 nm up to ⁇ 500 nm.
  • Typical further constituents of an electrode are, in addition to the lithium ion reversibly receiving and donating electrode or active material additives and binders.
  • the total weight of the lithium titanate electrode therefore includes the lithium ion reversibly receiving and donating electrode material lithium titanate, and further additives and / or binders.
  • Suitable binders are, for example, polytetrafluoroethylene (PTFE), polyvinylidene difluoride-hexafluoropropylene copolymer (PVDF-HFP), styrene-butadiene elastomer (SBR),
  • PTFE polytetrafluoroethylene
  • PVDF-HFP polyvinylidene difluoride-hexafluoropropylene copolymer
  • SBR styrene-butadiene elastomer
  • Carboxymethylcelluloses in particular sodium carboxymethylcellulose (Na-CMC), or polyvinylidene difluoride (PVDF).
  • Suitable additives are in particular Conductivity additives such as metal particles, for example copper particles, in particular metal particles with a size in the nanometer range, as well as conductive carbon materials, in particular carbon blacks, carbon fibers, graphites, carbon nanotubes or mixtures thereof.
  • Suitable carbon blacks are, for example, the finely divided industrial carbon blacks known by the name carbon black.
  • the positive electrode, the cathode, the electrochemical cell can reversibly absorb and release anions.
  • the positive electrode preferably comprises one
  • Carbon or metal compounds in particular alkali, alkaline earth or
  • Transition metal compounds such as oxides, halides, phosphates, chalcogenides such as sulfides and selenides, silicates, aluminates or hydroxides. These compounds, in particular aluminates and hydroxides, are often layered compounds which can incorporate anions between the layers.
  • the anion is reversibly receiving and donating electrode material selected from the group comprising
  • Carbon, graphite, graphene, or carbon nanotubes are Carbon, graphite, graphene, or carbon nanotubes.
  • fluorinated carbons of the formula (CF x ) n where x is in the range of 0.01 to 1.24 and n is in the range of 1 to 1000,
  • Carbon oxides of the formula (CO y ) m which are solid at room temperature and where y is in the range of 0.01 to 1 and m is in the range of 1 to 100,
  • Telluride M z Te y of transition metals M selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Cd, Ta, Ni, Cu, Zn, Zr, Nb, Mo, Sn and / or AI where y in the range from 1 to 10 and z ranges from 1 to 3,
  • complex halides of metals selected from the group comprising Na, Mg, Al, Si, P, S, K, Ca, Ti, Zn, Cu, Ni, Co, Fe, Mn, Cr, V, Zr, Nb, Mo and / or Sn, anion-introducing metal oxides of the transition metals, preferably selected from the group comprising W, Mo, Cr, V and / or Ti,
  • M is a metal cation selected from the group of alkaline earth metals and alkali metals, preferably Li, Na, Mg, Ca, and / or K, particularly preferably Li and Ca and particularly preferably Ca, and m is in the range from 0 to 8,
  • D is at least one bivalent metal cation from the group comprising Mg, Ca,
  • Mn, Fe, Co, Ni, Cu and / or Zn, and d is in the range of 0 to 8,
  • T is a unit amount of at least one trivalent metal cation selected from the group comprising Al, Ga, Fe and / or Cr, and
  • transition metal chalcogenides Preference is given to sulfides, selenides and tellurides of the formulas M z S y , M z Se y and M z Te y of transition metals M selected from the group comprising Ti, V, Cr, Mn, Fe, Co, Cd, Ta, Ni, Cu , Zn, Zr, Nb, Mo, Sn and / or Al, wherein y is in the range of 1 to 10 and z is in the range of 1 to 3.
  • Preferred transition metals M are selected from the group comprising Ti, V, Cr, Ni and / or Mo.
  • Sulfides such as TiS 2 and NiS are particularly advantageous. Also useful are selenides such as TiSe 2 .
  • complex halides of metals selected from the group consisting of Na, Mg, Al, Si, P, S, K, Ca, Ti, Zn, Cu, Ni, Co, Fe, Mn, Cr, V, Zr, Nb , Mo and / or Sn.
  • complex halides is to be understood as meaning compounds in which the halides are present as complex ligands
  • the complex halides are insoluble in the electrolyte and are solid at room temperature (20 ⁇ 2 ° C.)
  • usable complex halides are selected from the group comprising chiolith (Na 5 Al 3 Fi 4 ), usovite (Ba 2 CaMgAl 2 Fi 4 ) and / or cryptophalite ((NH 4 ) 2 SiF 6 )
  • Metal oxides of the transition metals preferably of transition metals selected from the group comprising W, Mo, Cr, V and / or Ti. Particularly preferred are metal oxides
  • Also useful compounds are in particular layered metal silicates of the formula Me n [(Si x O y ) 4x_2y ], wherein Me is selected from the group consisting of Fe, Li, Ni, Ti, Na, K, Ba, Ca, Mg, Mn, Co, Al, Sn, Ag, Au, Cu and / or Sb, 1 ⁇ n ⁇ 12 and 1 ⁇ x ⁇ 65 and 1 ⁇ y ⁇ 130.
  • Me is selected from the group consisting of Fe, Li, Ni, Ti, Na, K, Ba, Ca, Mg, Mn, Co, Al, Sn, Ag, Au, Cu and / or Sb, 1 ⁇ n ⁇ 12 and 1 ⁇ x ⁇ 65 and 1 ⁇ y ⁇ 130.
  • Me is selected from the group consisting of Fe, Li, Ni, Ti, Na, K, Ba, Ca, Mg, Mn, Co, Al, Sn, Ag, Au, Cu and / or Sb, 1 ⁇ n ⁇ 12 and 1 ⁇ x ⁇
  • Preferred metals Me are selected from the group comprising Li, Na, Ca, Ba and / or Fe, in particular Li, Na and Fe are preferred.
  • Metal silicates selected from the group comprising Li 2 FeSiO 4 , Li 2 CoSiO 4 , Li 2 MnSiO 4 and / or NaFeSi 4 are particularly advantageously usable.
  • layered metal aluminates of the formula (MeAl (OH) x ) where Me is selected from the group consisting of Fe, Li, Ni, Ti, Na, K, Ba, Ca, Mg, Mn, Co, Al, Sn, Ag, Au, Cu and / or Sb and 2 ⁇ x ⁇ 7. Preference is given to NaAl (OH) 4 and KAl (OH) 4 .
  • layered metal hydroxides corresponding essentially to the general formula M m DdT (OH) (3 + m + d ) , where M is a metal cation selected from the group of alkaline earth metals and alkali metals, and m is in the range from 0 to 8 D is at least one divalent metal cation selected from the group consisting of Mg, Ca, Mn, Fe, Co, Ni, Cu and / or Zn, and d is in the range of 0 to 8, T is a unit amount of at least one trivalent metal cation selected from the group comprising Al, Ga, Fe and / or Cr, and (3 + m + d) corresponds to the number of OH groups that substantially satisfy the valence requirements of M, D and T, where m + d is not equal to zero ,
  • metal hydroxides are also referred to as “mixed” metal hydroxides due to the various metal cations M, D and T.
  • the term “substantially” has in the context of the present invention with respect to the general formula M m DdT (OH) (3 + m + d ) the meaning that the sum of the valences of the electropositive and electronegative elements equalize.
  • metal hydroxides of alkaline earth metals and alkali metals selected from the group comprising Li, Na, Mg, Ca and / or K, more preferably lithium and / or Calcium, and more preferably calcium.
  • a further preferred metal hydroxide is [MgdAl (OH) 3+ d] where d is between 0.5 and 4.
  • the anions are carbon-based reversibly receiving and donating electrode material.
  • the term "carbon-based” is to be understood as meaning a carbonaceous material such as graphite, pitch or tar, pitch coal, coke, synthetic graphite, carbon black, lamellar graphite, or mixtures thereof.
  • Further preferably usable carbon compounds are fluorinated carbons of the formula (CF x ) n where x is in the range of 0.01 to 1.24 and n is in the range of 1 to 1000, and carbon oxides of the formula (CO y ) m , which at room temperature and y is in the range of 0.01 to 1 and m is in the range of 1 to 100.
  • An example of such carbon oxides are temperature- and oxygen-treated graphites.
  • the anions are carbon-based reversibly receiving and donating electrode material.
  • Carbon based electrode material is also referred to as intercalation.
  • carbon-based is to be understood as meaning a carbonaceous material such as graphite, pitch or tar, pitch coal, coke, synthetic graphite, carbon black, lamellar graphite, or mixtures thereof.
  • the anions are reversibly receiving and donating electrode material formed of a material selected from the group consisting of carbon, graphite, graphene or carbon nanotubes.
  • Carbon and graphite show particularly good intercalating and deintercalating
  • the anions which comprise the electrolyte, in particular the anions of the lithium salt are.
  • the anions from the electrolyte may intercalate between the layer lattice planes of the graphite and / or deposit or intercalate with graphite layers of disordered carbons.
  • Carbon materials are particularly well suited if they have a partial graphitic structure. But even porous carbon-rich material can intercalate reversible anions within its crystal lattice.
  • the intercalating carbons or graphites preferably intercalate the anions without their solvation sheath.
  • carbon fibers such as carbon black, activated carbon, amorphous carbon, carbon fibers, graphites, graphene,
  • Graphite oxides as well as carbon nanotubes, carbon manure foam, amorphous carbon or mixtures thereof.
  • Carbon particles can be amorphous, crystalline or partially crystalline, so-called soft or hard carbons.
  • amorphous carbon are, for example, Ketjenblack,
  • Acetylene black or carbon black Preference is given to using crystalline
  • Carbon modifications such as graphite, carbon nanotubes, so-called carbon nanotubes, as well as fullerenes or mixtures thereof.
  • VGCF carbon vapor grown carbon fibers.
  • temperature-treated carbons such as graphene oxides.
  • Temperature treated carbons are preferably solid at room temperature.
  • Graphene, graphite and / or partially graphitized carbons are preferred.
  • Graphite and partially graphitized carbons can be particularly good anions between the
  • Useful graphite or carbon particles preferably have a middle one
  • Diameter in the range of> 2 nm to ⁇ 50 ⁇ preferably in the range of> 10 nm to ⁇ 30 ⁇ , more preferably in the range of> 30 nm to ⁇ 30 ⁇ , on.
  • Carbon material is particularly useful in powder form.
  • powdered carbon and graphite can be well processed with a binder into a composite electrode.
  • the anion is reversibly intercalating and deintercalating
  • Electrode material carbon-based the anions comprise reversibly intercalating and deintercalating electrode carbon and / or graphite in the range of> 70 wt .-% to ⁇ 100 wt .-%, preferably in the range of> 80 wt .-% to ⁇ 98 wt .-%, preferably in the range of> 90 wt .-% to ⁇ 97 wt .-%, based on the total weight of the electrode.
  • the proportion of> 70% by weight of the electrode formed in a dual intercalation cell of the carbon and / or graphite anion intercalation compound makes a significant difference to conventional lithium ion battery cathodes containing carbon and graphite as an additive contained only in small amounts of about 10% by weight.
  • the electrochemical cell furthermore has in particular a separator.
  • the separator separates the electrodes from each other.
  • the separator is disposed between the electrodes.
  • the particularly secondary electrochemical cell preferably comprises a lithium ion reversibly receiving and donating electrode, an anion reversibly receiving and donating electrode, a separator and an electrolyte comprising a lithium salt and a solvent.
  • the separator is permeable to the ions of the electrolyte.
  • Suitable materials for the separator are for example microporous plastics, for example poly-ethylene-tetrafluoroethylene, nonwovens made of glass fibers or polyethylene. Preference is given to microporous films, for example porous ethylene-tetrafluoroethylene film or nonwovens. Particularly suitable are nonwovens of glass fibers, in particular nonwoven glass fiber nonwoven.
  • the separator may further be a gel polymer separator.
  • a gel polymer separator can be prepared, for example, by admixing a polymer, in particular selected from the group consisting of polypropylene, polytetrafluoroethylene and / or polyvinylidene difluorides, preferably polyethylene oxides, into the electrolyte.
  • a liquid electrolyte is usually substantially one in one
  • Suitable lithium salts are in preferred embodiments selected from the group consisting of LiF, LiCl, LiBr, LiI, LiNO 3 , LiSO 4 , LiPF 6 , LiAsF 6 , LiC 10 4 , LiSbF 6 , LiPtCk, Li (CF 3 ) SO 3 (LiTf), LiC (SO 2 CF 3 ) 3 , LiPF 3 (CF 3 ) 3 (LiF AP), LiPF 4 (C 2 O 4 ) (LiTFOB), LiBF 4 , LiB (C 2 O 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 ) (LiF AB), Li 2 Bi 2 Fi 2 (LiDFB) , LiN (SO 2 F) 2 (LiFSI), LiN (SO 2 CF 3 ) 2 (LiTFSI)
  • LiN (S0 2 C 2 F 5 ) 2 LiBETI
  • Preferred lithium salts are selected from the group comprising LiPF 6 , Li (SO 2 F) 2 (LiFSI), LiN (SO 2 CF 3 ) 2 (LiTFSI) and / or LiB (C 2 O 4 ) 2 (LiBOB).
  • LiN (S0 2 F) 2 (LiFSI), LiN (S0 2 CF 3 ) 2 (LiTFSI), and LiB (C 2 0 4 ) 2 (LiBOB) can lead to improved electrochemical cell performance and performance
  • the anion of the lithium salt does not decompose to a potential of at least 3.5 V, preferably at least 4 V, preferably 5 V, relative to the potential of lithium.
  • the anion of the lithium salt preferably does not decompose in a potential range of> 4.55 V to ⁇ 5.6 V, preferably not a potential range of> 5.1 V to ⁇ 5.6 V, compared to the potential of lithium.
  • the electrochemical cell according to the invention which is based on the dual-ion insertion principle, is preferably operated at high cell voltages of at least 3.5 V, preferably at least 4 V, preferably 5 V, compared to the potential of lithium.
  • the inventive electrochemical cell is operated at a cell voltage in the range of> 3 V to ⁇ 4 V, preferably in the range of> 3.5 V to ⁇ 4 V, against lithium titanium oxide.
  • the anion is selected from the group comprising F ⁇ , Cl ⁇ , Br ⁇ , ⁇ , N0 3 ⁇ , SO, " PF 6 -, BF, " B (C 2 0 4 ) 2 " (BOB), BF 2 ( C 2 O 4 ) “ (DFOB), B (C 2 O 4 ) (C 3 O 4 ) " (MOB),
  • the anion is selected from the group consisting of PF 6 " , N (SO 2 F) 2 " (FSI), N ( S0 2 CF 3 ) 2 " (TFSI) and / or B (C 2 0 4 ) 2 " (BOB).
  • the lithium salt is dissolved in the solvent.
  • the concentration of the lithium salt in the electrolyte is in the range of> 0.5 M to ⁇ 19 M, preferably in the range of> 0.65 M to ⁇ 12 M, more preferably in the range of> 1 M to ⁇ 5 M.
  • lithium titanate as the anode material reduces the risk that the salts and / or solvents will decompose and lead to an exothermic decomposition of the cell. This reduces the security risk in the operation of the cell.
  • lower salt concentrations reduce the cost of manufacturing the cell.
  • the electrolyte is a substantially anhydrous, organic
  • the solvent is an organic solvent.
  • Suitable organic solvents are, for example, selected from the group comprising aliphatic hydrocarbons, in particular pentane, aromatic hydrocarbons, in particular toluene, alkenes, in particular hexene, Alkynes, in particular heptin, halogenated hydrocarbons, in particular chloroform or fluoromethane, alcohols, in particular ethanol, glycols, in particular ethylene glycol and diethylene glycol, ethers, in particular diethyl ether and tetrahydrofuran, esters, in particular ethyl acetate, carbonates, in particular diethyl carbonate, lactones, in particular gamma-butyrolactone and gamma-valerolactone, acetates, in particular sodium acetate, Sulfones, in particular sulfolane, sulfoxides, in particular dimethyl sulfoxide, amides, in
  • Preferred organic solvents are selected from the group comprising
  • Ethylene carbonate fluoroethylene carbonate, propylene carbonate, diethyl carbonate,
  • Mixture thereof preferably from the group comprising ethylene carbonate, diethyl carbonate, dimethyl carbonate and / or mixtures thereof.
  • Solvent more preferably with diethyl carbonate or dimethyl carbonate.
  • the solvent is a mixture of ethylene carbonate and dimethyl carbonate.
  • Particularly preferred as the solvent is a mixture of ethylene carbonate and dimethyl carbonate in equal parts by weight.
  • Another object of the invention relates to the use of lithium titanate as lithium ion reversibly receiving and donating electrode material in an electrochemical cell, in particular a secondary electrochemical cell, comprising a lithium ion reversibly receiving and donating electrode and anions reversibly receiving and donating electrode and an electrolyte comprising a lithium salt and a solvent.
  • the electrochemical cell is particularly suitable for a lithium-based
  • Lithium-based energy stores are preferably selected from the group comprising lithium batteries, lithium-ion batteries, lithium-ion accumulators, lithium-polymer batteries and / or lithium-ion capacitors, in particular lithium-ion batteries or lithium ions
  • FIG. 1 shows the discharge capacity and efficiency of the electrochemical cell against
  • Figure 2 shows the current / voltage curve of the electrochemical cell versus time.
  • Arkema®, France dissolved in N-methyl-2-pyrrolidone (Acros Organics, 99.5%, Extra Dry) as a solvent.
  • the mixture was homogenized at 8000 rpm for 1.5 hours using a T25 digital Ultra-Turrax stirrer and a S 25 N-18 G dispersing tool (both IKA® , Staufen, Germany).
  • the mixture was then applied using a doctor blade on an aluminum foil of a thickness of 20 ⁇ (99.88% pure, Evonik-Degussa ® ) as a current collector with a layer thickness of 175 ⁇ .
  • the electrode was dried at 80 ° C for 12 hours.
  • an electrode having a diameter of 12 mm was punched and dried for 24 hours at 120 ° C under vacuum.
  • the surface loading was> 3 mg / cm 2 .
  • the surface load was determined by weighing the pure aluminum foil and the punched electrodes.
  • a round electrode with a diameter of 12 mm, or an area of 1.13 cm 2 punched out and for 24 hours at 120 ° C under Vacuum dried.
  • the surface loading was 1.5 mg / cm 2 .
  • the surface load was determined by weighing the pure aluminum foil and the punched electrodes.
  • the separator used was a glass fiber separator from Whatman (Whatman GF / D, GE Healthcare®, Great Britain).
  • the electrolyte was a mixture of
  • Ethylene carbonate and dimethyl carbonate in equal parts by weight (1: 1). Both solvents were purchased in a "battery grade” grade frommonte®, Yamaguchi, Japan Lithium hexafluorophosphate LiPF 6 (Übe®,
  • Electrochemical investigation of the electrochemical cell with lithium titanate anode The electrochemical examination of the electrochemical cell prepared according to Example 1 was carried out in a cell made of a modified gas valve of the company
  • the potentiostat / galvanostat used was a Maccor 4000 series instrument or a BaSyTec MDS battery test system.
  • the electrodes used in the measuring cell were round with a diameter of 12 mm, respectively an area of 1.13 cm 2 .
  • the assembly of the cell was carried out in a glove box filled with an inert gas atmosphere of argon and an oxygen and water content of less than 1 ppm.
  • a galvanostatic current was then applied, which corresponded to a specific current density of 50 mA / g with respect to the active material of the graphite electrode.
  • the cell was charged to a final charge voltage of 3.3V and then discharged to 1.8 V with the same galvanostatic current, wherein the data in V respectively refer to the cell voltage between the graphite and the lithium titanate electrode.
  • This charge / discharge process is one cycle and has been repeated 20 times at 20 ⁇ 2 ° C.
  • FIG. 1 shows the discharge capacity and the efficiency of the charging / discharging process of the electrochemical cell as a function of the number of cycles applied on the x-axis.
  • the left y-axis shows the value of the discharge capacity, represented as a black circle
  • the right y-axis the efficiency of the charge / discharge, shown as
  • Graphite anode operates below the thermodynamic stability window of the electrolyte.
  • Figure 2 shows the current / voltage curve of the cell versus that on the x-axis
  • FIG. 2 shows the first 10 charging / discharging operations.
  • the shape of the potential shows that the ion storage in a limited
  • Lithium titanate anodes are worked in a Potentialarbeits Symposium in which the organic electrolyte is thermodynamically stable, but the total cell voltage was still above 3 volts. Furthermore, there was no formation of a passivation layer on the anode. Furthermore, high charging and discharging currents could be realized.

Abstract

L'invention concerne une cellule électrochimique comprenant une électrode acceptant et donnant de manière réversible des ions de lithium, une électrode acceptant et donnant de manière réversible des anions ainsi qu'un électrolyte comprenant un sel de lithium et un solvant. L'électrode acceptant et donnant de manière réversible des ions de lithium renferme du titane de lithium en tant que matière de l'électrode acceptant et donnant de manière réversible des ions de lithium.
PCT/EP2012/069115 2011-09-30 2012-09-27 Cellule électrochimique WO2013045567A1 (fr)

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DE102020108397B3 (de) 2020-03-26 2021-07-15 Westfälische Wilhelms-Universität Münster Elektrochemische Zelle mit Schwefel-Elektrode und reversiblem Dual-Ionen-Ladungstransfer

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DE102017219163A1 (de) * 2017-10-25 2019-04-25 Robert Bosch Gmbh Elektrochemische Zelle umfassend fluoriertes Graphen als Aktivmaterial

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EP2866283A1 (fr) * 2013-10-23 2015-04-29 Commissariat à l'Énergie Atomique et aux Énergies Alternatives Cellule électrochimique pour accumulateur au lithium et accumulateur au lithium comprenant une telle cellule électrochimique
US10090554B2 (en) 2014-12-18 2018-10-02 Ricoh Company, Ltd. Non-aqueous electrolyte storage element
DE102020108397B3 (de) 2020-03-26 2021-07-15 Westfälische Wilhelms-Universität Münster Elektrochemische Zelle mit Schwefel-Elektrode und reversiblem Dual-Ionen-Ladungstransfer
WO2021191347A1 (fr) 2020-03-26 2021-09-30 Westfälische Wilhelms-Universität Münster Cellule électrochimique comportant une électrode de soufre, et transfert réversible de charges d'ions doubles

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