WO2015082711A1 - Alkali ion battery and method for producing the same - Google Patents

Alkali ion battery and method for producing the same Download PDF

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Publication number
WO2015082711A1
WO2015082711A1 PCT/EP2014/076787 EP2014076787W WO2015082711A1 WO 2015082711 A1 WO2015082711 A1 WO 2015082711A1 EP 2014076787 W EP2014076787 W EP 2014076787W WO 2015082711 A1 WO2015082711 A1 WO 2015082711A1
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cathode
battery
electrolyte
alkali ion
monomer
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PCT/EP2014/076787
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French (fr)
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Daniel CÍNTORA JUÁREZ
Shahzada Ahmad
Carlos Pérez Vicente
José Luis TIRADO COELLO
Samrana KAZIM
Manuel DOBLARÉ CASTELLANO
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Abengoa Research, S.L.
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Publication of WO2015082711A1 publication Critical patent/WO2015082711A1/en

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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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/0464—Electro organic synthesis
    • H01M4/0466—Electrochemical polymerisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • 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
    • H01M10/04—Construction or manufacture in general
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/049—Processes for forming or storing electrodes in the battery container
    • 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
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    • 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
    • H01M4/137—Electrodes based on electro-active 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
    • H01M4/13—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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
    • H—ELECTRICITY
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    • 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
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    • 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
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • 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

  • the present invention relates to alkali ion batteries, in particular lithium ion batteries, and methods for producing the same.
  • the invention further relates to methods for increasing capacity of alkali ion batteries and for methods of providing a polymer on the surface of cathode materials.
  • Lithium ion batteries are rechargeable batteries in which lithium ions move from the anode to the cathode during discharge and back when charging.
  • Lithium ion batteries generally use an intercalated lithium compound as the electrode material, compared to the metallic lithium used in non-rechargeable lithium batteries.
  • Lithium ion batteries are used in a wide range of applications, from small portable electronic devices to hybrid electric vehicles or electric vehicles. They can be used in many portable electronics. Lithium ion batteries play an important role in reducing atmospheric pollution by enabling the use of clean energy sources like solar, hydro and wind for transportation. Lithium ion batteries can thus be used as intermittent energy source and are carbon neutral.
  • the three main functional components of a lithium ion battery are the anode (negative), cathode (positive) and the electrolyte.
  • a separator for preventing the electrodes from getting in direct contact and electrical short circuit.
  • the separator is permeable to the lithium ions.
  • the active material of the anode of a conventional lithium ion battery is made of carbon (graphite), but the use of other anode materials shall not be excluded for the purpose of the present invention.
  • the positive electrode (cathode) generally contains lithium metal oxides or lithium metal anion or other materials as an active material.
  • the inside of a lithium ion battery is generally totally free of water.
  • the liquid electrolyte generally contains aprotic solvents such as organic carbonates and mixtures thereof.
  • the electrolyte generally contains non-coordinating anion salts of lithium, such as lithium hexafluorophosphate (L1PF5), lithium hexafluoroarsenate (L1ASF5), lithium perchlorate (L1CIO4), lithium tetrafluoroborate (L1BF4) and lithium triflate (L1CF3SO3).
  • LiFePC ⁇ olivine structured LiFePC ⁇ has emerged as a promising active cathode material for the next generation of lithium ion batteries. LiFePC ⁇ is relatively inexpensive and environmentally benign. Further, higher stability of this material is provided by the strong covalent P-0 bond.
  • LiFePC ⁇ and other active cathode materials suffer from disadvantages, such as low ionic and/or electronic conductivities. Furthermore, in the area of lithium ion batteries, it is always an objective of increasing maximum energy capacity of the device so as to store more energy.
  • a further objective with respect to lithium ion batteries is to avoid “memory effect", which is a gradual loss of maximum energy capacity if a battery is repeatedly recharged after being only partially discharged.
  • memory effect is a gradual loss of maximum energy capacity if a battery is repeatedly recharged after being only partially discharged.
  • One of the objectives of the invention is to provide rechargeable batteries that have low self- discharge effect. It is also an objective to increase lifetime of lithium ion batteries.
  • Yet another objective is to provide rechargeable batteries that produce regular, constant discharge current.
  • a significant improvement of low electronic conductivity of complex metal oxide powder and more specifically metal phosphate was achieved with the use of an organic carbon precursor that is pyrolysed onto the cathode material or its precursor to improve the electrical field at the level of cathode particles.
  • Organic carbon precursor that is pyrolysed onto the cathode material or its precursor to improve the electrical field at the level of cathode particles.
  • Coatings are usually formed by mixing an organic precursor with preformed Li metal oxide before heat treatment at 500-700°C in an inert or reducing atmosphere.
  • the decomposition of the organic constituent leads, in addition to the formation of carbon, to the formation of volatile organic compounds (VOCs), carbon monoxide (CO) and carbon dioxide (CO2), which poses environmental problems.
  • VOCs volatile organic compounds
  • CO carbon monoxide
  • CO2 carbon dioxide
  • conducting polymers can have a positive or synergistic effect in the performance of LiFeP04 and other active cathode materials.
  • Several means have been used to make polymer/ LiFeP04 composites, including electropolymerization from a suspension of LiFeP04 particles, polymerization using a chemical oxidant in the presence of the particle or formation of a colloidal suspension of the polymer immediately before the introduction of the LiFeP04 particles.
  • N.D. Trinh et al, J power sources, 221 (2013) 284-289 disclose a method of producing freestanding poly(3,4-ethylene dioxythiophene) (PEDOT)-LiFeP04 composite films by dynamic two phase interline electropolymerization.
  • EDOT (3,4-ethylene dioxythiophene) monomers present in the organic solvent polymerized at the interface occupied by the particles and thus formed a disk-shaped, PEDOT-LiFeP04 composite.
  • the resulting films were washed and dried and used as cathode in a lithium ion battery.
  • US 2012/0136136 discloses a method of synthesizing an organic electronically conductive polymer in presence of partially delithiated alkali metal phosphate.
  • Particulate, delithiated LiFeP04 for example of formula Li j . x FeP04, wherein 0 ⁇ x ⁇ l, was produced from nanosized LiFePC ⁇ or from LiFePC ⁇ microparticles by chemical delithiation.
  • the delithiated, particulate Li j . x FeP04, and a Li salt (Fluorad) were added to an alcohol solvent together with EDOT monomers. Chemical polymerization was conducted by heating at 50°C. In this manner, a powder was obtained, which, after washing and drying, could be used for preparing composite cathodes for Li ion batteries.
  • D. Lepage et al disclose a two-step process for producing a PEDOT-LiFePC ⁇ composite that can be used for lithium ion batteries.
  • LiFePC ⁇ is at least partially delithiated.
  • EDOT is polymerized by reinsertion of lithium into Li j . x FeP04.
  • EDOT is oxidized by the insertion of lithium (added as a salt to the alcohol solvent) into the delithiated Li j . x FeP04.
  • the composite powders obtained are used to form a cathode. It is also an objective of the present invention to provide still simpler and more efficient processes for obtaining cathode materials for lithium ion batteries.
  • the present invention addresses the problems depicted above.
  • the present inventors provided a new method for producing composite cathodes and cathode materials for lithium ion batteries.
  • the present invention provides methods for producing cathodes or lithium based cathode materials, such as, for example, lithium metal oxide or lithium metal anion material, and an organic polymer. In several aspects, the present invention provides methods for producing lithium ion batteries.
  • the present invention provides methods for producing composite cathodes and/or composite cathode materials.
  • the present invention provides a method for producing an alkali ion battery, the method comprising the steps of assembling a lithium-containing cathode, an anode, a separator material and an electrolyte so as to form an alkali ion battery, wherein said electrolyte comprises an aprotic and/or non-aqueous solvent, lithium salts and polymerizable monomers.
  • the present invention provides a method for producing a polymer-cathode composite for an alkali ion battery, the method comprising the steps of: providing an electrochemical device comprising a Li-containing working electrode, a counter electrode and an electrolyte; adding an monomer to said electrode and/or electrolyte; and, enabling polymerization of said monomer by oxidizing said monomer in said electrochemical device.
  • the present invention provides a method for producing an alkali ion battery, the method comprising the steps of: providing a partially or totally assembled alkali ion battery comprising a cathode, an anode and an electrolyte, wherein said cathode comprises a material selected from non-delithiated and partially or totally delithiated cathode materials; and, adding monomers to said electrolyte of said partially or totally assembled alkali ion battery.
  • the present invention provides a method for producing an alkali ion battery, the method comprising the steps of assembling a lithium-containing cathode, an anode, a separator material and an electrolyte so as to form an alkali ion battery, wherein electrolyte comprises an aprotic and/or non-aqueous solvent, Li-ions and unsaturated monomers.
  • the present invention provides a method for producing an alkali ion battery, the method comprising the steps of: adding an unsaturated monomer to an electrolyte of a pre- assembled or disassembled lithium ion battery comprising, besides said electrolyte, a cathode and an anode electrically connected by said electrolyte; producing said alkali ion battery by sealing the pre-assembled or disassembled lithium ion battery comprising said monomer in said electrolyte.
  • the invention provides a method for producing an alkali ion battery, the method comprising the steps of: providing an alkali ion battery, comprising a lithium-containing cathode, an anode and an electrolyte; delithiating said cathode by charging said battery; partially and/or totally disassembling said battery; reassembling a battery using said deliathiated cathode while adding a monomer to said delithiated cathode and/or to the electrolyte; and, enabling polymerization of said monomer by oxidizing said monomer in said reassembled battery.
  • the invention provides a method for producing a polymer-cathode composite for a lithium ion battery, the method comprising the steps of: providing an electrochemical device comprising a lithium-containing working electrode material, a counter electrode and an electrolyte; adding a monomer to said electrolyte; and, enabling polymerization of said monomer by oxidizing said monomer in said electrochemical device.
  • the present invention provides alkali ion batteries.
  • the invention provides an alkali ion battery and/or a lithium ion battery obtainable by the methods and/or processes of the invention.
  • the invention provides a secondary alkali ion battery comprising a lithium- containing cathode, an anode, a separator material and an aprotic and/or non-aqueous electrolyte, wherein said electrolyte comprises lithium salts and monomers.
  • the invention provides a consumer end product and/or an application comprising the battery of the invention. Further aspects and preferred embodiments of the invention are defined herein below and in the appended claims. Further features and advantages of the invention will become apparent to the skilled person from the description of the preferred embodiments given below. Brief Description of the Drawings
  • Figure 1 shows discharge profiles at C/10 discharge rate of lithium ion batteries without polymer (squares) and with polymer coating in accordance with various embodiments of the invention (circles, triangles and inversed triangles).
  • the batteries according to embodiments of the invention deliver higher capacities.
  • the discharge profiles show voltage during discharge and capacity, the latter shown per weight unit of cathode material LiFePC ⁇ , allowing comparison of different treatments.
  • Figure 2 shows discharge profiles for the same devices as Fig. 1, but at higher rate i.e. with a 2C discharge rate. As expected, the capacities are lower compared to slower discharge rate shown in Fig. 1, but devices in accordance with embodiments of the invention still have substantially increased capacity compared to devices using a conventional cathode.
  • Figure 3 shows the capacity of lithium ion batteries of different embodiments of the invention in dependence of discharge rates and number of charge-discharge cycles.
  • the battery with a cathode coated with poly(propylenedioxythiophene) [PProDOT] exhibits the best performance in terms of capacity retention at different discharge rates and capacity recovery after more than 50 cycles.
  • devices of preferred embodiments of the invention (triangles) outperform the standard bare cathode material (squares).
  • Figure 4 shows capacity of different lithium ion batteries including embodiments of the invention as a function of discharge rate.
  • the batteries of preferred embodiments have not only higher capacities, but further suffer less capacity loss at faster discharge rates.
  • battery reliability is increased. In particular, capacity fading on cycling rate decreases.
  • Figure 5 shows charge and discharge polarization in volt in dependence of the C rate. All samples with conducting polymer in accordance with embodiments of the invention (triangles, circle) show lower charge/discharge polarization than the standard sample (squares). The sample device with the cathode coated with PEDOT exhibits less polarization than the cathode coated with PProDOT. Detailed Description of the Preferred Embodiments
  • a first surprising finding is that the polymer can be induced in cathode materials to form composite cathode material via in situ methods, in an assembled lithium ion battery comprising monomers of a conductive polymer in the electrolyte and/or on the cathode.
  • the polymer part of a composite cathode material can be provided once the cathode is already formed to its final form and/or shape as used in the battery.
  • the polymer part of the composite cathode is formed directly on the self-contained scaffold formed in a deposition process, for example, such as casting.
  • the polymer is formed on micro- or nanoparticles of the active cathode material, such as lithium metal oxide or lithium metal anion, for example, and the cathode is shaped from the resulting composite powder.
  • the composite cathode film is formed by polymerization in presence of lithium metal oxide or lithium metal anion micro- or nano particles.
  • a self- contained and/or macroscopic cathode is formed from particulate lithium-containing active cathode material, such as lithium metal oxide and/or lithium metal anion, and the polymer part is provided in a subsequent step, for example in situ within an assembled lithium ion battery or in specific electrochemical device.
  • particulate lithium-containing active cathode material such as lithium metal oxide and/or lithium metal anion
  • the present invention encompasses methods for producing an alkali ion battery, methods for producing composite cathodes and methods for producing a polymer layer on an active cathode and/or active cathode material.
  • the expression "alkali ion battery” encompasses a lithium ion battery.
  • the alkali ion battery is a lithium ion battery.
  • the battery of the invention is a rechargeable and/or secondary battery.
  • the methods of the invention may comprise the step of assembling a lithium-containing cathode, an anode, and an electrolyte so as to form an alkali ion battery.
  • a separator material is also provided between the electrodes.
  • the cathode is preferably substantially free of a polymer, in particular of a conductive polymer coating, as the polymer may preferably be formed in a subsequent step.
  • Substantially free of polymer for the purpose of the present specification, preferably refers to ⁇ 5%, more preferably ⁇ 3%, even more preferably ⁇ 2%, ⁇ 1%, ⁇ 0.5%, ⁇ 0.2%, expressed per weight with respect to the active cathode material.
  • the cathode is totally free of polymer at this stage.
  • Preferred active cathode materials from which the cathode is formed are disclosed elsewhere in this specification.
  • the alkali ion battery obtained by the step of assembling the lithium-containing cathode, an anode, and an electrolyte is preferably a functional and/or operational alkali ion battery.
  • the battery is preferably chargeable and, following charging, useful as a source of electrical energy. Accordingly, an "assembled” or “totally assembled” alkali ion battery is a functional battery, which can be charged, or, if already charged, can be discharged while providing electrical energy.
  • a "partially assembled alkali ion battery", for the purpose of this specification, may not be functional, for example may not yet have been sealed.
  • said step of assembling said lithium-containing cathode, anode, separator material and electrolyte comprises the steps of: providing a partially or totally assembled alkali ion battery comprising a cathode, an anode and an electrolyte, wherein said cathode comprises a material selected from non-delithiated and partially or totally delithiated active cathode materials; and, adding polymerizable monomers to said electrode and/or electrolyte of said partially or totally assembled alkali ion battery.
  • the alkali ion battery is only partially assembled, it may be sealed following addition of said polymerizable monomers. In this way, a totally assembled alkali ion battery may be obtained following sealing the battery.
  • Preferred embodiments of polymerizable monomers will be disclosed elsewhere in this specification.
  • the methods of the invention may comprise a step of partially or totally disassembly for adding the monomers to the battery.
  • the electrolyte of the totally assembled battery may be removed and replaced with a new electrolyte comprising the monomers.
  • the electrolyte may be added in the form of an electrolyte-impregnated separator. Therefore, the separator may be replaced at the same time as and/or together with the electrolyte.
  • the step of assembling or reassembling said lithium containing cathode, anode, electrolyte, and, preferably, a separator comprises the step of sealing the battery and/or sealing the cathode, anode, electrolyte, and, if applicable, the separator, preferably in a common housing.
  • the housing contains electric contacts for charging and/or discharging the battery.
  • a functional alkali ion battery is generally sealed in a water tight manner and/or air-tight manner.
  • a functional alkali ion battery is substantially or totally free of water.
  • said step of assembling or reassembling said lithium battery containing cathode, anode, separator material and electrolyte comprises the steps of: adding a polymerizable monomer to an electrode (preferably to the cathode) and/or to the electrolyte of a pre-assembled or disassembled alkali ion battery comprising, besides said electrolyte, a cathode and an anode electrically connected by said electrolyte; producing said alkali ion battery by sealing the pre-assembled or disassembled alkali ion battery comprising said monomer in said electrolyte.
  • the cathode and an anode are electrically connected in that lithium ions are allowed to shuttle between them.
  • a previously assembled battery may be disassembled in accordance with the invention.
  • the lid or housing of the battery may be removed, and/or some or all of the main functional parts (cathode, anode, and electrolyte) may be completely disassembled, that is, separated from each other and/or from the housing.
  • the battery may be assembled again and/or reassembled, wherein the polymerizable monomer is added only to the newly assembled or pre-assembled battery.
  • the step of "reassembling" comprises using the cathode and optionally other components of the disassembled battery while assembling a battery anew.
  • the anode of the disassembled battery is reused as an anode in the newly assembled battery.
  • the electrolyte will generally be replaced as it may be lost during disassembly. Of course, if the electrolyte can be recovered, it may also be used when reassembling the battery and can thus be incorporated to the reassembled battery.
  • the pre-assembled and/or disassembled battery did preferably not yet contain the polymerizable monomers, as the monomers are preferably added during the second step, where the battery is produced (reassembled) by sealing the pre-assembled or disassembled alkali ion battery comprising said monomer in said electrolyte.
  • said pre-assembled or disassembled alkali ion battery comprises a cathode comprising an at least partially delithiated active cathode material as disclosed elsewhere in this specification.
  • the cathode of said pre-assembled or disassembled alkali ion battery is substantially or totally free of a conductive polymer.
  • the cathode of said pre-assembled or disassembled alkali ion battery comprises, consists essentially of or consists of said active cathode material, optionally supplemented with binders or other additives different from organic conductive polymers.
  • the invention provides a method for producing a polymer-cathode composite for an alkali ion battery, the method comprising the steps of: providing an electrochemical device comprising a lithium-containing working electrode, a counter electrode and an electrolyte; adding an monomer to said electrode and/or electrolyte; and, enabling polymerization of said monomer by oxidizing said monomer in said electrochemical device.
  • the electrochemical device may be a device that may not be a functioning, rechargeable alkali ion battery but has the purpose of preparing the composite cathode.
  • the composite cathode may be removed after polymerization from the electrochemical device and be used as a cathode in the fabrication of an alkali ion battery.
  • the lithium-containing working electrode may comprise or consist essentially of an active cathode material as defined elsewhere in this specification.
  • the active cathode material is preferably substantially or totally free of organic, conductive polymer.
  • said lithium-containing working electrode comprises a self-contained and/or macroscopic cathode.
  • this embodiment encompasses that the electrochemical device is an alkali ion battery or a partially assembled, disassembled or pre-assembled alkali ion battery.
  • polymerization of said monomer is enabled by applying an external charge to the electrochemical device before or after adding said unsaturated monomer and/or by providing a partially delithiated lithium-containing cathode material that is susceptible of oxidizing said monomer.
  • the method of the invention may comprise the step of charging the battery.
  • the external charge is applied until the battery is completely charged. Therefore, in an embodiment, the method may comprise the step of charging the battery completely. In other embodiments, the method comprises the step of charging the device partially and/or incompletely.
  • the method of the invention comprises the step of sealing the partially assembled alkali ion battery, the pre-assembled or disassembled alkali ion battery and/or the electrochemical device comprising the electrolyte with said monomer.
  • a sealed device is obtained, in which the cathode is preferably substantially or totally free of an organic conductive polymer at the surface of the cathode in this embodiment.
  • the present invention provides methods for producing alkali ion batteries, for producing composite cathode material and methods for polymerization.
  • the various methods of the invention may comprise the step of polymerization.
  • polymerization is not conducted as part of the invention, as it may take place only during the first charging cycle of the battery.
  • the first charging step of the battery may take place with the end consumer charging the battery for the first use, for example. In this case, polymerization taking place during charging conducted by the end consumer may not be encompassed by the present invention.
  • the first charging cycle may take place as part of the methods of the invention.
  • the first charging step may be conducted by the manufacturer of the alkali ion battery, the wholesale trader or by the retailer.
  • the method of the invention comprises the steps of: 1) applying a charge on an alkali ion battery so as to charge the battery at least partially so as to obtain a totally or partially charged battery; 2) disassembling at least partially said totally or partially charged battery so as to obtain an at least partially disassembled battery; 3) re-assembling said battery by using an electrolyte comprising an unsaturated monomer or adding the monomer to said at least partially disassembled battery.
  • said alkali ion battery in the first step preferably lacks the polymerizable monomers, so that, during the step of charging the battery at least partially, no polymerization is obtained.
  • the alkali ion battery and/or the electrochemical device generally comprises one or more electrolytes.
  • the electrolyte of the alkali ion battery is preferably a lithium salt in either a solid matrix (polymeric, vitreous or crystalline) or in a solution.
  • the electrolyte is a solution of the lithium salt
  • the solution may be impregnating a separator.
  • the liquid solvent for the electrolyte solution can be one or a mixture of several aprotic solvents, preferably polar aprotic solvents.
  • the solvent is selected from the group consisting of: linear or cyclic ethers, carbonates, esters, sulfamides, and nitriles, for example.
  • a liquid electrolyte comprising the lithium salt dissolved in a mixture of ethylene carbonate and diethyl carbonate is chosen.
  • Exemplary lithium salts that may be used in the electrolyte may be selected from lithium hexafluorophosphate (LiPFg), lithium hexafluoroarsenate (LiAsFg), lithium perchlorate
  • LiPFg is the preferred lithium salt for the purpose of this invention.
  • the electrolyte comprises an aprotic and/or non-aqueous solvent and one or more lithium salts.
  • the electrolyte is substantially free of water, preferably totally free of water.
  • the electrolyte contains polymerizable monomers.
  • the monomers are present in the battery already before the first charging cycle.
  • polymerizable monomers are added following charging the battery at least partially. In this latter case, the electrolyte used for charging the battery at the beginning may be free of polymerizable monomers.
  • Monomers are preferably added at a solution of > 0.005 M solution in the electrolyte.
  • monomers are present at > 0.01 M, more preferably > 0.015 M, even more preferably > 0.05 M and most preferably > 0.1 M, for example at 0.05 to 0.3 M in the electrolyte. These amounts apply before polymerization. In particular, these amounts correspond to the amounts of monomers added to the battery when assembling and/or reassembling the same.
  • the cathode or working electrode of the alkali ion battery and/or of the electrochemical device comprises a material suitable as cathode material for secondary alkali ion batteries.
  • This material may be referred to as an "active cathode material" in this specification.
  • Other components, such as binders, are not considered to be active cathode materials for the purpose of this specification.
  • the "composite cathode” or “composite cathode material” refer to the cathode or material, respectively, comprising the active cathode material and the conductive polymer.
  • active cathode materials comprise lithium metal oxide and/or lithium metal anion.
  • lithium metal anion refers to salts containing an oxyanion and other possible anions, such as disclosed elsewhere in this specification, for example.
  • the cathode comprises an active cathode material selected from lithium based cathode materials.
  • the cathode comprises an active cathode material selected from lithium-containing olivine- or spinel-structured solid materials suitable as cathode materials for alkali ion batteries.
  • the active cathode material comprises or consists essentially of a cathode material of formula (I) below. Accordingly, said cathode and/or said working electrode comprises a cathode material of formula (I) below:
  • A is Li, which can be accompanied by other non-transition metals
  • M is a first series transition metal or a combination of two, three or more different metals selected from first series transition metals and from Al, with the proviso that if M is a combination of different metals at least one metal is a first series transition metal;
  • u is 1 or if M is Mn may be 1 or 2;
  • O is an oxygen atom
  • p is 0, meaning that said oxygen O p is absent, or, if M is V (vanadium), p is 1;
  • X is selected from P, S, Mo, W and Si; r is 2, 3 or 4;
  • said active cathode material comprises or consists essentially of a material of any one of formulae (II) to (IV) below.
  • said cathode and/or said working electrode comprises a cathode material of any one of formulae (II) to
  • M is a first series transition metal or a combination of two, three or more different metals selected from first series transition metals and from Al, with the proviso that if M is a combination of different metals at least one metal is a first series transition metal;
  • Y is selected from (3 ⁇ 4, O3 and XO4;
  • XO4 is selected from PO4, SO4, M0O4, WO4, S1O4, and combinations of thereof;
  • N is Mn.
  • A is Li.
  • M u and M is a single metal atom or a combination of two or three metals of formula (1) and (2) below: Ml 1-n M2 n (1) Ml ,_ n _ m M 2n M3 m (2) wherein Ml, M2 and M3 are selected from first series transition metal and from Al, n being larger than 0 but smaller than 1 (0 ⁇ n ⁇ 1) and m being larger than 0 (formula 1) but smaller than 1 (0 ⁇ m ⁇ 1), with the proviso that n+m ⁇ 1.
  • n ⁇ 0.5 and n+m ⁇ 0.5 (if applicable), more preferably n ⁇ 0.4 and n+m ⁇ 0.4, even more preferably n ⁇ 0.3 and n+m ⁇ 0.3, and most preferably n ⁇ 0.2 and n+m ⁇ 0.2.
  • said active material comprises a material selected from the list below.
  • said cathode and/or working electrode preferably comprises a material selected from the group consisting of: L1VOPO4, LiCoC ⁇ , LiNiC ⁇ , LiNij_ n Co n 02, LiNij. n . m Co n Al m 0 2 , LiNi 1 . n . m Co n Mn m 0 2 , LiMn 2 0 4 , LiFeP0 4 and LiFe ⁇ M ⁇ P0 4 , LiCoP0 4 , Li 2 FeP 2 0 7 , Li 2 FeSi0 4 , and combinations thereof.
  • the active material is partially or totally delithiated before being exposed to polymerizable monomers.
  • Delithiation in accordance with the invention may be made, for example, by charging an alkali ion battery which lacks monomers in the electrolyte and/or on the surface of the cathode.
  • Such an alkali ion battery preferably also lacks the polymer component in contact with the cathode.
  • Li + ions migrate to the anode, thereby forming the partially or totally delithiated cathode.
  • the cathode is delithiated in situ, that is, in an assembled alkali ion battery.
  • delithiation may also be conducted chemically for example once the cathode has been shaped from the active material and possibly binders. Delithiation may also be performed before shaping the cathode. Delithiation may be also performed chemically on the active material particles, such as disclosed, for example, in US 2012/0136136.
  • the active material of the delithiated cathode may be described with formulae (I) to (IV) above, in which A or Li is replaced by A j . x , or Li j . x , wherein 0 ⁇ x ⁇ l, expressing the fact that some Li atoms have been removed from the active material.
  • formula (I) the delithiated version of this material would have formula (Id) below:
  • delithiated LiFePC ⁇ may be described with the formula Li j ⁇ FePC ⁇ .
  • shaping the cathode and/or “forming a cathode”, and various grammatical forms thereof, refer to the step of shaping the cathode material from generally particulate active cathode material.
  • the active cathode material is generally prepared first in the form of micro- and/or nanoparticles.
  • the cathode as such is then formed or shaped from the particulate material so as to achieve a macroscopic structure.
  • the macroscopic cathode structure is nano-porous and/or microporous, due to its preparation from particles.
  • the macroscopic cathode forms a matrix comprising interstitial spaces, which may get in contact with the electrolyte and/or which may be filled with the polymer.
  • the step of shaping or forming the cathode may be performed, for example, by a casting process.
  • the active particulate material is mixed with binders and possibly other additives having an impact on the performance of the cathode, such as dopants.
  • polymers are generally formed on the nano- and/or micro particles or the cathode is shaped in the course of polymerization.
  • the present invention encompasses in several embodiments that the cathode is shaped first, in the absence of a polymer, and that the polymer is formed once the cathode has been shaped or formed, in particular once the self-contained, generally rigid and/or structured scaffold of particulate active material has been formed.
  • the scaffold may be used as such as a cathode or may be subjected to cutting or other processing for obtaining its final dimensions.
  • the expressions “shaping the cathode” and/or “forming a cathode” generally refer to the process of transforming the particulate active material to obtain a macroscopically solid and consistent structure that can be used as a cathode as such or following cutting, for example, so as to achieve the exact geometric dimension.
  • the expression “cathode”, for the purpose of this specification, generally refers to the macroscopic cathode, whereas the expression “cathode material” generally refers to material from which the cathode is or can be made or which is contained in the macroscopic cathode.
  • the methods of the invention comprise a step of polymerization.
  • the methods may comprise the step of polymerizing monomers.
  • polymerization is oxidative polymerization.
  • polymerization is electropolymerization.
  • the method of the invention comprises the step of polymerizing said monomer in situ, inside a partially assembled and/or totally assembled alkali ion battery.
  • the method of the invention comprises the step of applying a charge on said alkali ion battery so as to induce polymerization of said monomer in said electrolyte.
  • a charge on a partially or totally assembled alkali ion battery, polymerization of the monomers contained in the electrolyte is induced.
  • said charge is applied as part of the first charging cycle. The charge is preferably applied until the battery is charged completely. In other embodiments, the battery is only partially and/or incompletely charged.
  • said monomer is polymerized on and/or in the matrix of said cathode and/or said working electrode.
  • said polymerization results in a polymer-cathode composite material and/or a composite polymer-working electrode.
  • the polymer-cathode composite material formed during polymerization is obtained by oxidative polymerization, for example electropolymerization.
  • polymerization results in the formation of a polymer- cathode composite.
  • the polymer-cathode composite is formed following addition of said monomers, particularly by polymerization of said monomers.
  • the composite-cathode is formed once polymerization has been initiated, for example by applying an external charge.
  • the step of polymerization generally refers to the polymerization of monomers.
  • the monomers are preferably added to the electrolyte of an alkali ion battery or of an electrochemical device in general.
  • the monomers may also be added to the cathode, for example by dropping solvent containing the monomers only on the cathode.
  • the monomers may be contained in and/or added to an electrolyte and/or on the cathode of an assembled alkali ion battery, in which the cathode is not partially nor totally delithiated.
  • polymerization may be initiated, for example, by applying a voltage on the alkali ion battery, for example by charging the battery.
  • the monomers may be added to a partially or totally delithiated cathode.
  • the cathode may be delithiated as discussed elsewhere in this specification.
  • the monomers may be added to the electrolyte and/or drop casted on the cathode of a partially assembled alkali ion battery.
  • the monomers are molecules that are susceptible of being polymerized.
  • the monomers are susceptible of being polymerized by oxidative polymerization, for example by electropolymerization.
  • the monomers are organic molecules.
  • the monomers are unsaturated molecules.
  • the monomers are cyclic compounds.
  • the monomers are aromatic compounds.
  • the monomers comprise one or more heterocycles.
  • the monomers are unsaturated aromatic or aliphatic organic molecules comprising from 2 to 20 carbons and from 0 to 15 heteroatoms, the hereoatoms being selected from O, S, N, and halogen.
  • the monomers are unsaturated aromatic or aliphatic organic molecules comprising from 3 to 15 carbons and from 0 to 10 heteroatoms, even more preferably 3 to 10 carbons and 0 to 5 heteroatoms, and most preferably 4 to 7 carbons and 0 to 3 heteroatoms.
  • said monomer is a dioxythiophene-based monomer and/or comprises a dioxythiophene moiety.
  • the monomer is a monomer of formula (XX) below:
  • R 1 and R 2 are organic substituents comprising from 1 to 20 carbons and from 0 to 15 heteroatoms, wherein R 1 and R 2 may be fused to form a ring fused to the thiophene ring.
  • the monomer is a monomer selected from the monomers formulae (XXI) and (XXII) below:
  • R 3 -R 8 are independently selected from H and from organic substituents comprising from 1 to 15 carbons and from 0 to 10 heteroatoms.
  • R 3 -R 8 are independently selected from H and from CI to CIO aliphatic substituents. More preferably, R 3 -R 8 are independently selected from H and from CI to C5 aliphatic substituents. In an embodiment, R 3 -R 8 lack and/or are free of any heteroatom.
  • R 3 -R 8 are H.
  • said monomer selected from the monomers formulae (XXIII) and (XXIV) belo
  • said monomer is selected from the monomers of formulae (XXII) and (XXIV) above.
  • the monomers are identical, forming a homopolymer during polymerization.
  • the polymer of the composite cathode is thus preferably a homopolymer.
  • the polymer is an organic polymer.
  • the polymer is a conducting polymer, in particular an organic conducting polymer.
  • the alkali ion battery comprises a separator.
  • said partially or totally assembled alkali ion battery, said pre-assembled or disassembled alkali ion battery and/or said electrochemical device, as applicable comprises a separator extending between said cathode and said anode or between said working electrode and said counter electrode, as applicable.
  • the invention provides a secondary alkali ion battery comprising a lithium-containing cathode, an anode, a separator material and an aprotic and/or nonaqueous electrolyte.
  • said electrolyte comprises lithium salts.
  • said electrolyte comprises monomers, as defined herein, for example unsaturated monomers.
  • Alkali ion batteries of this type may yet be free of a conductive polymer on the cathode matrix.
  • the polymer may be formed in situ once a voltage is applied for charging the battery.
  • a polymer is formed from said monomers.
  • said electrolyte, said cathode and said anode are selected so that and/or interact such that, upon charging, a polymer is formed from said monomers.
  • the anode may be formed from any suitable anode material. Typically, graphite is used as anode material.
  • the alkali ion batteries of the invention may be used in a wide variety of applications. Accordingly, the present invention encompasses such applications comprising the battery of the invention. In some aspects, the invention encompasses small scape application, such as portable electric devices, portable computers, mobile phones, digital cameras, laptop computers, as well as large scale applications, like electrical vehicles (EVs) and hybrid electric vehicles (HEVs) comprising the batteries of the invention.
  • the alkali ion batteries of the invention may also be used as intermittent power supply.
  • Exemplary alkali ion batteries of the invention may be, for example, as disclosed in the examples, which are Swagelok-type cells, such as disclosed, for example, in B. Kang and G. Ceder, Nature, 458, 2009, 190-193 and in US 20100323244 Al.
  • EDOT poly(3 ,4-ethylenedioxythiophene) :poly(styrene sulfonate) dispersion (PEDOT:PSS), and tetraethylammonium tetrafluoroborate (TEABF 4 ) were used without any previous treatment.
  • PEDOT:PSS poly(styrene sulfonate) dispersion
  • TEABF 4 tetraethylammonium tetrafluoroborate
  • LiFeP0 4 LFP
  • carbon-coated LiFeP0 4 LFP/C
  • PVDF poly(vinylidene fluoride) additives whith N-methyl pirrolidone as dispersant.
  • the battery electrolyte consisted of 1 M LiPF 6 in ethylene carbonate:diethyl carbonate electrolyte (EC:DEC, 1: 1 volume ratio).
  • LFP and LFP/C standard electrodes were prepared by mixing the active material with carbon black and PVDF additives (85:8:7 wt. %) in N-methyl pyrrolidone to form slurry.
  • the slurry was sonicated, deposited over an aluminum disk (0.64 cm ) and dried at 80°C under vacuum for 12 h (B. Leon, C. Perez Vicente, J. L. Tirado, Ph. Biensan, and C. Tessier, Journal of The Electrochemical Society, 155 (3) A211-A216 (2008)).
  • the average amount of active material ranges from 3-5 mg cm " .
  • Batteries were assembled in two-electrode Swagelok-type cells, using the cathode as working electrode, 1 M LiPF 6 (EC:DEC, 1: 1 volume ratio) electrolyte with Whatman glass- paper as separator, and lithium metal foil as reference/counter electrode.
  • Blending method The blending method consisted in mixing the active material and a selected source of PEDOT in N-methyl pyrrolidone to form slurry (without carbon black and PVDF additives). The slurry was sonicated, deposited over an aluminum disk and dried at 80-100 °C under vacuum for 12 h.
  • the different PEDOT sources are: a) PEDOT was synthesized potentiostatically in a three-electrode cell with platinum wire as working electrode, a graphite rod as counter electrode and Ag/AgCl (3M KC1,
  • the two-phase reaction medium contained TEABF 4 (0.1 M) dissolved in water and EDOT (0.1 M) dissolved in dichloromethane.
  • EDOT 0.1 M
  • the electropolymerization of EDOT monomer takes place over platinum at the aqueous/organic interphase when an oxidation potential of 1.3 V was applied.
  • the obtained polymer was washed by dionized water followed by acetonitrile, and dried for 12 h under vacuum at 60 °C.
  • the weight ratio of LFP:PEDOT in the composite was 80:20 wt. %.
  • PEDOT polymerized by chemical reaction 80:20 wt. %.
  • PEDOT was synthesized by oxidative chemical polymerization of EDOT (0.7 mmol) using FeCl 3 H 2 0 (1.6 mmol) as oxidant in 15 mL of boiling acetonitrile for 30 minutes. The solid product was washed repeatedly with deionized water until negative reaction of chloride ion with AgN0 3 (0.1 M). The product was dried for 12h under vacuum at 60 °C. The weight ratio of LFP:PEDOT in the composite was 90: 10 wt. %. c) PEDOT/PSS dispersion. Due to high water content, the composite cathode incorporating this PEDOT source was dried at 100°C after its deposition over an aluminum disk. The weight ratio of LFP:PEDOT was 90: 10 wt.
  • PEDOTrPSS deposit This method consisted in depositing drops PEDOT:PSS dispersion over a standard LFP electrode to incorporate polymer (10% wt.) after evaporation of the solvents/dispersants by heating at 80-100°C under vacuum.
  • Electrodeposition Standard LFP and LFP/C cathodes were used as substrate for the electrodeposition/polymerization of EDOT.
  • the electrodeposition was carried out using a standard cathode as working electrode in a three electrode cell with an aluminum disk as counter electrode and Ag/AgCl (3M KCl, AgCl sat.) reference electrode.
  • the reaction medium consisted of a 0.1 M EDOT, 0.1 M TEABF 4 solution in acetonitrile.
  • the electropolymerization over the LFP or LFP/C electrode was performed potentiostatically at 1.3 V (Ag/AgCl) during 30 and 3 min., respectively.
  • EDOT polymerization was performed inside the lithium battery with stoichiometric (LiFePO 4 ) or partially delithiated cathodes (Lii_ x FePO 4 ). Details are described below: i) In situ polymerization with LiFePO.j. Method 1. The polymerization of EDOT monomer with the stoichiometric cathode was performed inside a battery with a standard LFP cathode.
  • EDOT monomer was added to the battery as a 0.15 M solution in the electrolyte (1 M LiPF 6 in EC:DEC, 1: 1 volume ratio). Polymerization of EDOT takes place during the first charging cycle at C/10 from the open circuit potential to 4.2 V (Li + /Li). ii) In situ polymerization with LiFePO_(. Method 2. EDOT monomer was mixed only with LFP active material (neither Carbon black nor PVDF were added) to form a slurry which was formed as a cathode as described above.

Abstract

The present invention relates to methods for producing an alkali ion battery and to a secondary alkali ion battery. In accordance with the method of the invention, an alkali ion battery is assembled, wherein said battery comprises an electrolyte comprising polymerizable monomers or a cathode on which polymerizable monomers can be added before bringing in contact with the electrolyte. When charging the battery, a polymer coating is formed on the cathode of the battery. In a preferred embodiment, the composite cathode comprising the polymer is formed in situ, that is, within the assembled alkali ion battery. The alkali batteries of the invention have higher capacities; suffer less capacity loss at faster discharge rates. Furthermore, the batteries of the invention have increased battery reliability in that capacity fading decreases and rate performance increases.

Description

Alkali Ion Battery and Method for Producing the Same
Technical Field The present invention relates to alkali ion batteries, in particular lithium ion batteries, and methods for producing the same. The invention further relates to methods for increasing capacity of alkali ion batteries and for methods of providing a polymer on the surface of cathode materials. Prior Art and the Problem Underlying the Invention
Lithium ion batteries are rechargeable batteries in which lithium ions move from the anode to the cathode during discharge and back when charging. Lithium ion batteries generally use an intercalated lithium compound as the electrode material, compared to the metallic lithium used in non-rechargeable lithium batteries.
Lithium ion batteries are used in a wide range of applications, from small portable electronic devices to hybrid electric vehicles or electric vehicles. They can be used in many portable electronics. Lithium ion batteries play an important role in reducing atmospheric pollution by enabling the use of clean energy sources like solar, hydro and wind for transportation. Lithium ion batteries can thus be used as intermittent energy source and are carbon neutral.
The three main functional components of a lithium ion battery are the anode (negative), cathode (positive) and the electrolyte. In case of a liquid electrolyte, there is also a separator for preventing the electrodes from getting in direct contact and electrical short circuit. The separator is permeable to the lithium ions. The active material of the anode of a conventional lithium ion battery is made of carbon (graphite), but the use of other anode materials shall not be excluded for the purpose of the present invention. The positive electrode (cathode) generally contains lithium metal oxides or lithium metal anion or other materials as an active material. The inside of a lithium ion battery is generally totally free of water. The liquid electrolyte generally contains aprotic solvents such as organic carbonates and mixtures thereof. The electrolyte generally contains non-coordinating anion salts of lithium, such as lithium hexafluorophosphate (L1PF5), lithium hexafluoroarsenate (L1ASF5), lithium perchlorate (L1CIO4), lithium tetrafluoroborate (L1BF4) and lithium triflate (L1CF3SO3). Among the components in the lithium ion batteries, cathode materials have attracted much attention in recent years. For example, olivine structured LiFePC^ has emerged as a promising active cathode material for the next generation of lithium ion batteries. LiFePC^ is relatively inexpensive and environmentally benign. Further, higher stability of this material is provided by the strong covalent P-0 bond.
However, LiFePC^ and other active cathode materials suffer from disadvantages, such as low ionic and/or electronic conductivities. Furthermore, in the area of lithium ion batteries, it is always an objective of increasing maximum energy capacity of the device so as to store more energy.
Further key factors to be improved are to increase the open circuit voltage, to reduce temperature sensitivity and to increase the maximum charging or discharging current.
A further objective with respect to lithium ion batteries is to avoid "memory effect", which is a gradual loss of maximum energy capacity if a battery is repeatedly recharged after being only partially discharged. In LiFePC^-based cells, there may be anomalies in the course of the discharge curves, which may be referred to as "memory effect".
One of the objectives of the invention is to provide rechargeable batteries that have low self- discharge effect. It is also an objective to increase lifetime of lithium ion batteries.
Yet another objective is to provide rechargeable batteries that produce regular, constant discharge current.
Several strategies have been adopted to overcome disadvantages of cathode materials, for example in LiFePC^ and other active cathode materials. For example, doping of the cathode materials with foreign metal ions has been proposed.
Reducing LiFePC^ particles to the nanoscale level was pointed out as one solution to the low electronic conductivity and limited Li+ diffusivity in the material.
A significant improvement of low electronic conductivity of complex metal oxide powder and more specifically metal phosphate was achieved with the use of an organic carbon precursor that is pyrolysed onto the cathode material or its precursor to improve the electrical field at the level of cathode particles. Today, the most common approach for improving LiFePC^ and other active cathode materials remains coating with carbon. Coatings are usually formed by mixing an organic precursor with preformed Li metal oxide before heat treatment at 500-700°C in an inert or reducing atmosphere. The decomposition of the organic constituent leads, in addition to the formation of carbon, to the formation of volatile organic compounds (VOCs), carbon monoxide (CO) and carbon dioxide (CO2), which poses environmental problems.
Furthermore, irregular coating of the cathode material can lead to poor connectivity of the particles and hence performance loss. It would therefore be an improvement if ambient temperature process can be found to coat Li metal oxide materials uniformly without the formation of VOCs, CO and C02.
Previously it has been shown that conducting polymers can have a positive or synergistic effect in the performance of LiFeP04 and other active cathode materials. Several means have been used to make polymer/ LiFeP04 composites, including electropolymerization from a suspension of LiFeP04 particles, polymerization using a chemical oxidant in the presence of the particle or formation of a colloidal suspension of the polymer immediately before the introduction of the LiFeP04 particles.
N.D. Trinh et al, J power sources, 221 (2013) 284-289 disclose a method of producing freestanding poly(3,4-ethylene dioxythiophene) (PEDOT)-LiFeP04 composite films by dynamic two phase interline electropolymerization. The polymer formed by electropolymerization at the interface of a water/dichloromethane mixture, which was covered by LiFeP04 particles that were added via the aqueous solution. EDOT (3,4-ethylene dioxythiophene) monomers present in the organic solvent polymerized at the interface occupied by the particles and thus formed a disk-shaped, PEDOT-LiFeP04 composite. The resulting films were washed and dried and used as cathode in a lithium ion battery.
US 2012/0136136 discloses a method of synthesizing an organic electronically conductive polymer in presence of partially delithiated alkali metal phosphate. Particulate, delithiated LiFeP04, for example of formula Lij.xFeP04, wherein 0<x<l, was produced from nanosized LiFePC^ or from LiFePC^ microparticles by chemical delithiation. In a next step, the delithiated, particulate Lij.xFeP04, and a Li salt (Fluorad) were added to an alcohol solvent together with EDOT monomers. Chemical polymerization was conducted by heating at 50°C. In this manner, a powder was obtained, which, after washing and drying, could be used for preparing composite cathodes for Li ion batteries.
Similarly, D. Lepage et al (Angew. Chem. Int. Ed. 2011, 50, 6884-6887) disclose a two-step process for producing a PEDOT-LiFePC^ composite that can be used for lithium ion batteries. In a first step, LiFePC^ is at least partially delithiated. In a second step, EDOT is polymerized by reinsertion of lithium into Lij.xFeP04. According to the authors, EDOT is oxidized by the insertion of lithium (added as a salt to the alcohol solvent) into the delithiated Lij.xFeP04. The composite powders obtained are used to form a cathode. It is also an objective of the present invention to provide still simpler and more efficient processes for obtaining cathode materials for lithium ion batteries.
It is also an objective to provide methods simpler and more efficient processes for producing composite polymer-lithium metal oxide or anion cathode materials.
It is a further objective to produce lithium ion batteries based on composite cathodes having improved characteristics.
The present invention addresses the problems depicted above.
Summary of the Invention
Remarkably, the present inventors provided a new method for producing composite cathodes and cathode materials for lithium ion batteries.
In several aspects, the present invention provides methods for producing cathodes or lithium based cathode materials, such as, for example, lithium metal oxide or lithium metal anion material, and an organic polymer. In several aspects, the present invention provides methods for producing lithium ion batteries.
In other aspects, the present invention provides methods for producing composite cathodes and/or composite cathode materials.
In an aspect, the present invention provides a method for producing an alkali ion battery, the method comprising the steps of assembling a lithium-containing cathode, an anode, a separator material and an electrolyte so as to form an alkali ion battery, wherein said electrolyte comprises an aprotic and/or non-aqueous solvent, lithium salts and polymerizable monomers.
In an aspect, the present invention provides a method for producing a polymer-cathode composite for an alkali ion battery, the method comprising the steps of: providing an electrochemical device comprising a Li-containing working electrode, a counter electrode and an electrolyte; adding an monomer to said electrode and/or electrolyte; and, enabling polymerization of said monomer by oxidizing said monomer in said electrochemical device.
In an aspect, the present invention provides a method for producing an alkali ion battery, the method comprising the steps of: providing a partially or totally assembled alkali ion battery comprising a cathode, an anode and an electrolyte, wherein said cathode comprises a material selected from non-delithiated and partially or totally delithiated cathode materials; and, adding monomers to said electrolyte of said partially or totally assembled alkali ion battery.
In an aspect, the present invention provides a method for producing an alkali ion battery, the method comprising the steps of assembling a lithium-containing cathode, an anode, a separator material and an electrolyte so as to form an alkali ion battery, wherein electrolyte comprises an aprotic and/or non-aqueous solvent, Li-ions and unsaturated monomers.
In an aspect, the present invention provides a method for producing an alkali ion battery, the method comprising the steps of: adding an unsaturated monomer to an electrolyte of a pre- assembled or disassembled lithium ion battery comprising, besides said electrolyte, a cathode and an anode electrically connected by said electrolyte; producing said alkali ion battery by sealing the pre-assembled or disassembled lithium ion battery comprising said monomer in said electrolyte.
In an aspect, the invention provides a method for producing an alkali ion battery, the method comprising the steps of: providing an alkali ion battery, comprising a lithium-containing cathode, an anode and an electrolyte; delithiating said cathode by charging said battery; partially and/or totally disassembling said battery; reassembling a battery using said deliathiated cathode while adding a monomer to said delithiated cathode and/or to the electrolyte; and, enabling polymerization of said monomer by oxidizing said monomer in said reassembled battery.
In an aspect, the invention provides a method for producing a polymer-cathode composite for a lithium ion battery, the method comprising the steps of: providing an electrochemical device comprising a lithium-containing working electrode material, a counter electrode and an electrolyte; adding a monomer to said electrolyte; and, enabling polymerization of said monomer by oxidizing said monomer in said electrochemical device.
In several aspects, the present invention provides alkali ion batteries. In an aspect, the invention provides an alkali ion battery and/or a lithium ion battery obtainable by the methods and/or processes of the invention.
In an aspect, the invention provides a secondary alkali ion battery comprising a lithium- containing cathode, an anode, a separator material and an aprotic and/or non-aqueous electrolyte, wherein said electrolyte comprises lithium salts and monomers.
In an aspect, the invention provides a consumer end product and/or an application comprising the battery of the invention. Further aspects and preferred embodiments of the invention are defined herein below and in the appended claims. Further features and advantages of the invention will become apparent to the skilled person from the description of the preferred embodiments given below. Brief Description of the Drawings
Figure 1 shows discharge profiles at C/10 discharge rate of lithium ion batteries without polymer (squares) and with polymer coating in accordance with various embodiments of the invention (circles, triangles and inversed triangles). The batteries according to embodiments of the invention deliver higher capacities. The discharge profiles show voltage during discharge and capacity, the latter shown per weight unit of cathode material LiFePC^, allowing comparison of different treatments. Figure 2 shows discharge profiles for the same devices as Fig. 1, but at higher rate i.e. with a 2C discharge rate. As expected, the capacities are lower compared to slower discharge rate shown in Fig. 1, but devices in accordance with embodiments of the invention still have substantially increased capacity compared to devices using a conventional cathode. Figure 3 shows the capacity of lithium ion batteries of different embodiments of the invention in dependence of discharge rates and number of charge-discharge cycles. The battery with a cathode coated with poly(propylenedioxythiophene) [PProDOT] exhibits the best performance in terms of capacity retention at different discharge rates and capacity recovery after more than 50 cycles. In particular at a discharge rate of 2C, devices of preferred embodiments of the invention (triangles) outperform the standard bare cathode material (squares).
Figure 4 shows capacity of different lithium ion batteries including embodiments of the invention as a function of discharge rate. The batteries of preferred embodiments have not only higher capacities, but further suffer less capacity loss at faster discharge rates. Furthermore, in embodiments of the invention, battery reliability is increased. In particular, capacity fading on cycling rate decreases.
Figure 5 shows charge and discharge polarization in volt in dependence of the C rate. All samples with conducting polymer in accordance with embodiments of the invention (triangles, circle) show lower charge/discharge polarization than the standard sample (squares). The sample device with the cathode coated with PEDOT exhibits less polarization than the cathode coated with PProDOT. Detailed Description of the Preferred Embodiments
The present invention is based on a revolutionary yet simple approach and gives unprecedented findings. Without wishing to be bound by theory, a first surprising finding is that the polymer can be induced in cathode materials to form composite cathode material via in situ methods, in an assembled lithium ion battery comprising monomers of a conductive polymer in the electrolyte and/or on the cathode.
Another finding is that the polymer part of a composite cathode material can be provided once the cathode is already formed to its final form and/or shape as used in the battery. For example, the polymer part of the composite cathode is formed directly on the self-contained scaffold formed in a deposition process, for example, such as casting. This differs from previously known techniques, where the polymer is formed on micro- or nanoparticles of the active cathode material, such as lithium metal oxide or lithium metal anion, for example, and the cathode is shaped from the resulting composite powder. Alternatively, the composite cathode film is formed by polymerization in presence of lithium metal oxide or lithium metal anion micro- or nano particles. In preferred embodiments of the present invention, a self- contained and/or macroscopic cathode is formed from particulate lithium-containing active cathode material, such as lithium metal oxide and/or lithium metal anion, and the polymer part is provided in a subsequent step, for example in situ within an assembled lithium ion battery or in specific electrochemical device.
Further and other surprising findings will become apparent from the detailed description below.
The present invention encompasses methods for producing an alkali ion battery, methods for producing composite cathodes and methods for producing a polymer layer on an active cathode and/or active cathode material. For the purpose of this specification, the expression "alkali ion battery" encompasses a lithium ion battery. In a preferred embodiment, the alkali ion battery is a lithium ion battery. Preferably, the battery of the invention is a rechargeable and/or secondary battery.
The methods of the invention may comprise the step of assembling a lithium-containing cathode, an anode, and an electrolyte so as to form an alkali ion battery. Preferably, a separator material is also provided between the electrodes. At this stage, the cathode is preferably substantially free of a polymer, in particular of a conductive polymer coating, as the polymer may preferably be formed in a subsequent step.
"Substantially free" of polymer, for the purpose of the present specification, preferably refers to < 5%, more preferably < 3%, even more preferably < 2%, < 1%, < 0.5%, < 0.2%, expressed per weight with respect to the active cathode material. Preferably, the cathode is totally free of polymer at this stage. Preferred active cathode materials from which the cathode is formed are disclosed elsewhere in this specification.
The alkali ion battery obtained by the step of assembling the lithium-containing cathode, an anode, and an electrolyte is preferably a functional and/or operational alkali ion battery. The battery is preferably chargeable and, following charging, useful as a source of electrical energy. Accordingly, an "assembled" or "totally assembled" alkali ion battery is a functional battery, which can be charged, or, if already charged, can be discharged while providing electrical energy. A "partially assembled alkali ion battery", for the purpose of this specification, may not be functional, for example may not yet have been sealed. In an embodiment, said step of assembling said lithium-containing cathode, anode, separator material and electrolyte comprises the steps of: providing a partially or totally assembled alkali ion battery comprising a cathode, an anode and an electrolyte, wherein said cathode comprises a material selected from non-delithiated and partially or totally delithiated active cathode materials; and, adding polymerizable monomers to said electrode and/or electrolyte of said partially or totally assembled alkali ion battery.
If the alkali ion battery is only partially assembled, it may be sealed following addition of said polymerizable monomers. In this way, a totally assembled alkali ion battery may be obtained following sealing the battery. Preferred embodiments of polymerizable monomers will be disclosed elsewhere in this specification.
If the alkali ion battery is already totally assembled, the methods of the invention may comprise a step of partially or totally disassembly for adding the monomers to the battery. For example, the electrolyte of the totally assembled battery may be removed and replaced with a new electrolyte comprising the monomers. The electrolyte may be added in the form of an electrolyte-impregnated separator. Therefore, the separator may be replaced at the same time as and/or together with the electrolyte. Preferably, the step of assembling or reassembling said lithium containing cathode, anode, electrolyte, and, preferably, a separator, comprises the step of sealing the battery and/or sealing the cathode, anode, electrolyte, and, if applicable, the separator, preferably in a common housing. Preferably, the housing contains electric contacts for charging and/or discharging the battery. A functional alkali ion battery is generally sealed in a water tight manner and/or air-tight manner. Furthermore, a functional alkali ion battery is substantially or totally free of water.
In an embodiment of the method of the invention, said step of assembling or reassembling said lithium battery containing cathode, anode, separator material and electrolyte comprises the steps of: adding a polymerizable monomer to an electrode (preferably to the cathode) and/or to the electrolyte of a pre-assembled or disassembled alkali ion battery comprising, besides said electrolyte, a cathode and an anode electrically connected by said electrolyte; producing said alkali ion battery by sealing the pre-assembled or disassembled alkali ion battery comprising said monomer in said electrolyte. The cathode and an anode are electrically connected in that lithium ions are allowed to shuttle between them.
In accordance with this embodiment, a previously assembled battery may be disassembled in accordance with the invention. For example, the lid or housing of the battery may be removed, and/or some or all of the main functional parts (cathode, anode, and electrolyte) may be completely disassembled, that is, separated from each other and/or from the housing. In a subsequent step, the battery may be assembled again and/or reassembled, wherein the polymerizable monomer is added only to the newly assembled or pre-assembled battery. The step of "reassembling" comprises using the cathode and optionally other components of the disassembled battery while assembling a battery anew. Preferably, the anode of the disassembled battery is reused as an anode in the newly assembled battery. The electrolyte will generally be replaced as it may be lost during disassembly. Of course, if the electrolyte can be recovered, it may also be used when reassembling the battery and can thus be incorporated to the reassembled battery. In the previous and other embodiments, the pre-assembled and/or disassembled battery did preferably not yet contain the polymerizable monomers, as the monomers are preferably added during the second step, where the battery is produced (reassembled) by sealing the pre-assembled or disassembled alkali ion battery comprising said monomer in said electrolyte.
Preferably, said pre-assembled or disassembled alkali ion battery comprises a cathode comprising an at least partially delithiated active cathode material as disclosed elsewhere in this specification. Preferably, the cathode of said pre-assembled or disassembled alkali ion battery is substantially or totally free of a conductive polymer. Preferably, the cathode of said pre-assembled or disassembled alkali ion battery comprises, consists essentially of or consists of said active cathode material, optionally supplemented with binders or other additives different from organic conductive polymers. In an embodiment, the invention provides a method for producing a polymer-cathode composite for an alkali ion battery, the method comprising the steps of: providing an electrochemical device comprising a lithium-containing working electrode, a counter electrode and an electrolyte; adding an monomer to said electrode and/or electrolyte; and, enabling polymerization of said monomer by oxidizing said monomer in said electrochemical device. In accordance with this embodiment, the electrochemical device may be a device that may not be a functioning, rechargeable alkali ion battery but has the purpose of preparing the composite cathode. The composite cathode may be removed after polymerization from the electrochemical device and be used as a cathode in the fabrication of an alkali ion battery. For example, the lithium-containing working electrode may comprise or consist essentially of an active cathode material as defined elsewhere in this specification. The active cathode material is preferably substantially or totally free of organic, conductive polymer. Preferably, said lithium-containing working electrode comprises a self-contained and/or macroscopic cathode. Alternatively, this embodiment encompasses that the electrochemical device is an alkali ion battery or a partially assembled, disassembled or pre-assembled alkali ion battery.
In an embodiment of the method for producing a polymer-cathode composite for an alkali ion battery, polymerization of said monomer is enabled by applying an external charge to the electrochemical device before or after adding said unsaturated monomer and/or by providing a partially delithiated lithium-containing cathode material that is susceptible of oxidizing said monomer. The method of the invention may comprise the step of charging the battery. In accordance with a preferred embodiment, the external charge is applied until the battery is completely charged. Therefore, in an embodiment, the method may comprise the step of charging the battery completely. In other embodiments, the method comprises the step of charging the device partially and/or incompletely.
In an embodiment, the method of the invention comprises the step of sealing the partially assembled alkali ion battery, the pre-assembled or disassembled alkali ion battery and/or the electrochemical device comprising the electrolyte with said monomer. In this manner, a sealed device is obtained, in which the cathode is preferably substantially or totally free of an organic conductive polymer at the surface of the cathode in this embodiment.
The present invention provides methods for producing alkali ion batteries, for producing composite cathode material and methods for polymerization. The various methods of the invention may comprise the step of polymerization. In some embodiments, polymerization is not conducted as part of the invention, as it may take place only during the first charging cycle of the battery. The first charging step of the battery may take place with the end consumer charging the battery for the first use, for example. In this case, polymerization taking place during charging conducted by the end consumer may not be encompassed by the present invention. Alternatively, the first charging cycle may take place as part of the methods of the invention. For example, the first charging step may be conducted by the manufacturer of the alkali ion battery, the wholesale trader or by the retailer. In an embodiment, the method of the invention comprises the steps of: 1) applying a charge on an alkali ion battery so as to charge the battery at least partially so as to obtain a totally or partially charged battery; 2) disassembling at least partially said totally or partially charged battery so as to obtain an at least partially disassembled battery; 3) re-assembling said battery by using an electrolyte comprising an unsaturated monomer or adding the monomer to said at least partially disassembled battery. In this embodiment, said alkali ion battery in the first step preferably lacks the polymerizable monomers, so that, during the step of charging the battery at least partially, no polymerization is obtained.
The alkali ion battery and/or the electrochemical device generally comprises one or more electrolytes. The electrolyte of the alkali ion battery is preferably a lithium salt in either a solid matrix (polymeric, vitreous or crystalline) or in a solution.
If the electrolyte is a solution of the lithium salt, the solution may be impregnating a separator.
The liquid solvent for the electrolyte solution can be one or a mixture of several aprotic solvents, preferably polar aprotic solvents. Preferably, the solvent is selected from the group consisting of: linear or cyclic ethers, carbonates, esters, sulfamides, and nitriles, for example.
According to a preferred embodiment of the present invention, a liquid electrolyte comprising the lithium salt dissolved in a mixture of ethylene carbonate and diethyl carbonate is chosen. Exemplary lithium salts that may be used in the electrolyte may be selected from lithium hexafluorophosphate (LiPFg), lithium hexafluoroarsenate (LiAsFg), lithium perchlorate
(L1CIO4), lithium tetrafluoroborate (L1BF4) and lithium triflate (L1CF3SO3), and combinations thereof, for example. LiPFg is the preferred lithium salt for the purpose of this invention.
In an embodiment, the electrolyte comprises an aprotic and/or non-aqueous solvent and one or more lithium salts.
Typically, the electrolyte is substantially free of water, preferably totally free of water.
In some embodiments, the electrolyte contains polymerizable monomers. Preferably, the monomers are present in the battery already before the first charging cycle. In other embodiments, polymerizable monomers are added following charging the battery at least partially. In this latter case, the electrolyte used for charging the battery at the beginning may be free of polymerizable monomers.
Monomers are preferably added at a solution of > 0.005 M solution in the electrolyte. Preferably, monomers are present at > 0.01 M, more preferably > 0.015 M, even more preferably > 0.05 M and most preferably > 0.1 M, for example at 0.05 to 0.3 M in the electrolyte. These amounts apply before polymerization. In particular, these amounts correspond to the amounts of monomers added to the battery when assembling and/or reassembling the same.
In an embodiment, the cathode or working electrode of the alkali ion battery and/or of the electrochemical device comprises a material suitable as cathode material for secondary alkali ion batteries. This material may be referred to as an "active cathode material" in this specification. Other components, such as binders, are not considered to be active cathode materials for the purpose of this specification. The "composite cathode" or "composite cathode material" refer to the cathode or material, respectively, comprising the active cathode material and the conductive polymer.
In an embodiment, active cathode materials comprise lithium metal oxide and/or lithium metal anion. For the purpose of the present specification, the expression "lithium metal anion" refers to salts containing an oxyanion and other possible anions, such as disclosed elsewhere in this specification, for example.
In an embodiment, the cathode comprises an active cathode material selected from lithium based cathode materials. Preferably, the cathode comprises an active cathode material selected from lithium-containing olivine- or spinel-structured solid materials suitable as cathode materials for alkali ion batteries.
According to an embodiment, the active cathode material comprises or consists essentially of a cathode material of formula (I) below. Accordingly, said cathode and/or said working electrode comprises a cathode material of formula (I) below:
A Mu Op Xq Or (I) wherein:
A is Li, which can be accompanied by other non-transition metals;
M is a first series transition metal or a combination of two, three or more different metals selected from first series transition metals and from Al, with the proviso that if M is a combination of different metals at least one metal is a first series transition metal;
u is 1 or if M is Mn may be 1 or 2;
O is an oxygen atom;
p is 0, meaning that said oxygen Op is absent, or, if M is V (vanadium), p is 1;
X is selected from P, S, Mo, W and Si; r is 2, 3 or 4;
q is 0, meaning that said X is absent, or 1; with the provisos that if r is 4, q is 1 or 0 and if r is 2 or 3, q is 0. According to a preferred embodiment, said active cathode material comprises or consists essentially of a material of any one of formulae (II) to (IV) below. Preferably, said cathode and/or said working electrode comprises a cathode material of any one of formulae (II) to
(IV) below:
A M Y (II) A M O X04 (III)
A N2 04 (IV) wherein A represents Li, which can be accompanied by other non-transition metals;
M is a first series transition metal or a combination of two, three or more different metals selected from first series transition metals and from Al, with the proviso that if M is a combination of different metals at least one metal is a first series transition metal;
Y is selected from (¾, O3 and XO4;
XO4 is selected from PO4, SO4, M0O4, WO4, S1O4, and combinations of thereof;
N is Mn. According to a preferred embodiment of the materials of formulae (I) to (IV), A is Li.
According to an embodiment of the materials of formulae (I), (II), and (III), Mu and M is a single metal atom or a combination of two or three metals of formula (1) and (2) below: Ml 1-n M2n (1) Ml ,_n_m M2n M3m (2) wherein Ml, M2 and M3 are selected from first series transition metal and from Al, n being larger than 0 but smaller than 1 (0 < n < 1) and m being larger than 0 (formula 1) but smaller than 1 (0 < m < 1), with the proviso that n+m <1. Preferably, n<0.5 and n+m<0.5 (if applicable), more preferably n<0.4 and n+m<0.4, even more preferably n<0.3 and n+m<0.3, and most preferably n<0.2 and n+m<0.2.
According to an embodiment, said active material comprises a material selected from the list below. Accordingly, said cathode and/or working electrode preferably comprises a material selected from the group consisting of: L1VOPO4, LiCoC^, LiNiC^, LiNij_nCon02, LiNij.n. mConAlm02, LiNi1.n.mConMnm02, LiMn204, LiFeP04 and LiFe^M^ P04 , LiCoP04, Li2FeP207, Li2FeSi04, and combinations thereof.
In some embodiments, the active material is partially or totally delithiated before being exposed to polymerizable monomers. Delithiation in accordance with the invention may be made, for example, by charging an alkali ion battery which lacks monomers in the electrolyte and/or on the surface of the cathode. Such an alkali ion battery preferably also lacks the polymer component in contact with the cathode. During charging, Li+ ions migrate to the anode, thereby forming the partially or totally delithiated cathode. In this case, the cathode is delithiated in situ, that is, in an assembled alkali ion battery. Alternatively, delithiation may also be conducted chemically for example once the cathode has been shaped from the active material and possibly binders. Delithiation may also be performed before shaping the cathode. Delithiation may be also performed chemically on the active material particles, such as disclosed, for example, in US 2012/0136136.
The active material of the delithiated cathode may be described with formulae (I) to (IV) above, in which A or Li is replaced by Aj.x, or Lij.x, wherein 0<x<l, expressing the fact that some Li atoms have been removed from the active material. For example, in case of formula (I), the delithiated version of this material would have formula (Id) below:
Aj.x Mu Op Xq Or (Id)
In case of the material of formula (II), the delithiated material would have formula (lid): Aj.x M Y (lid) In formulae (Id) and (lid), all letters are defined as above.
For example, delithiated LiFePC^ may be described with the formula Lij^FePC^.
The expressions "shaping the cathode" and/or "forming a cathode", and various grammatical forms thereof, refer to the step of shaping the cathode material from generally particulate active cathode material. The active cathode material is generally prepared first in the form of micro- and/or nanoparticles. The cathode as such is then formed or shaped from the particulate material so as to achieve a macroscopic structure. In many cases, the macroscopic cathode structure is nano-porous and/or microporous, due to its preparation from particles. Generally, the macroscopic cathode forms a matrix comprising interstitial spaces, which may get in contact with the electrolyte and/or which may be filled with the polymer. The step of shaping or forming the cathode may be performed, for example, by a casting process. Generally, the active particulate material is mixed with binders and possibly other additives having an impact on the performance of the cathode, such as dopants. In the prior art, polymers are generally formed on the nano- and/or micro particles or the cathode is shaped in the course of polymerization. In contrast thereto, the present invention encompasses in several embodiments that the cathode is shaped first, in the absence of a polymer, and that the polymer is formed once the cathode has been shaped or formed, in particular once the self-contained, generally rigid and/or structured scaffold of particulate active material has been formed. The scaffold may be used as such as a cathode or may be subjected to cutting or other processing for obtaining its final dimensions.
In accordance with the above, the expressions "shaping the cathode" and/or "forming a cathode" generally refer to the process of transforming the particulate active material to obtain a macroscopically solid and consistent structure that can be used as a cathode as such or following cutting, for example, so as to achieve the exact geometric dimension. The expression "cathode", for the purpose of this specification, generally refers to the macroscopic cathode, whereas the expression "cathode material" generally refers to material from which the cathode is or can be made or which is contained in the macroscopic cathode.
In some embodiment, the methods of the invention comprise a step of polymerization. In particular, the methods may comprise the step of polymerizing monomers. Preferably, polymerization is oxidative polymerization. According to a preferred embodiment, polymerization is electropolymerization.
In an embodiment, the method of the invention comprises the step of polymerizing said monomer in situ, inside a partially assembled and/or totally assembled alkali ion battery.
In an embodiment, the method of the invention comprises the step of applying a charge on said alkali ion battery so as to induce polymerization of said monomer in said electrolyte. Surprisingly, by applying a charge to a partially or totally assembled alkali ion battery, polymerization of the monomers contained in the electrolyte is induced. Preferably, said charge is applied as part of the first charging cycle. The charge is preferably applied until the battery is charged completely. In other embodiments, the battery is only partially and/or incompletely charged.
In an embodiment of the method of the invention, said monomer is polymerized on and/or in the matrix of said cathode and/or said working electrode.
In an embodiment, said polymerization results in a polymer-cathode composite material and/or a composite polymer-working electrode. In an embodiment, the polymer-cathode composite material formed during polymerization is obtained by oxidative polymerization, for example electropolymerization.
In accordance with the invention, polymerization results in the formation of a polymer- cathode composite. The polymer-cathode composite is formed following addition of said monomers, particularly by polymerization of said monomers. The composite-cathode is formed once polymerization has been initiated, for example by applying an external charge.
The step of polymerization generally refers to the polymerization of monomers. The monomers are preferably added to the electrolyte of an alkali ion battery or of an electrochemical device in general. The monomers may also be added to the cathode, for example by dropping solvent containing the monomers only on the cathode. Depending on the embodiment or aspect of the invention, the monomers may be contained in and/or added to an electrolyte and/or on the cathode of an assembled alkali ion battery, in which the cathode is not partially nor totally delithiated. In these embodiments, polymerization may be initiated, for example, by applying a voltage on the alkali ion battery, for example by charging the battery. In other embodiments, the monomers may be added to a partially or totally delithiated cathode. The cathode may be delithiated as discussed elsewhere in this specification.
The monomers may be added to the electrolyte and/or drop casted on the cathode of a partially assembled alkali ion battery.
According to an embodiment, the monomers are molecules that are susceptible of being polymerized. Preferably, the monomers are susceptible of being polymerized by oxidative polymerization, for example by electropolymerization. Preferably, the monomers are organic molecules. According to a preferred embodiment, the monomers are unsaturated molecules. According to an embodiment, the monomers are cyclic compounds. According to an embodiment, the monomers are aromatic compounds. Preferably, the monomers comprise one or more heterocycles. According to an embodiment, the monomers are unsaturated aromatic or aliphatic organic molecules comprising from 2 to 20 carbons and from 0 to 15 heteroatoms, the hereoatoms being selected from O, S, N, and halogen. More preferably, the monomers are unsaturated aromatic or aliphatic organic molecules comprising from 3 to 15 carbons and from 0 to 10 heteroatoms, even more preferably 3 to 10 carbons and 0 to 5 heteroatoms, and most preferably 4 to 7 carbons and 0 to 3 heteroatoms.
In an embodiment, said monomer is a dioxythiophene-based monomer and/or comprises a dioxythiophene moiety. According to an embodiment, the monomer is a monomer of formula (XX) below:
Figure imgf000021_0001
wherein R1 and R2 are organic substituents comprising from 1 to 20 carbons and from 0 to 15 heteroatoms, wherein R1 and R2 may be fused to form a ring fused to the thiophene ring.
According to an embodiment, the monomer is a monomer selected from the monomers formulae (XXI) and (XXII) below:
Figure imgf000021_0002
wherein R3-R8 are independently selected from H and from organic substituents comprising from 1 to 15 carbons and from 0 to 10 heteroatoms. Preferably, R3-R8 are independently selected from H and from CI to CIO aliphatic substituents. More preferably, R3-R8 are independently selected from H and from CI to C5 aliphatic substituents. In an embodiment, R3-R8 lack and/or are free of any heteroatom. Preferably, R3-R8 are H.
According to a preferred embodiment, said monomer selected from the monomers formulae (XXIII) and (XXIV) belo
Figure imgf000022_0001
According to an embodiment, said monomer is selected from the monomers of formulae (XXII) and (XXIV) above.
According to a preferred embodiment, the monomers are identical, forming a homopolymer during polymerization. The polymer of the composite cathode is thus preferably a homopolymer. Preferably, the polymer is an organic polymer. According to a preferred embodiment, the polymer is a conducting polymer, in particular an organic conducting polymer.
Accordingly, other monomers than those specifically disclosed herein may be used for the purpose of the present invention, as long as a conductive polymer is formed. In an embodiment, the alkali ion battery comprises a separator. In particular, said partially or totally assembled alkali ion battery, said pre-assembled or disassembled alkali ion battery and/or said electrochemical device, as applicable, comprises a separator extending between said cathode and said anode or between said working electrode and said counter electrode, as applicable.
In an embodiment, the invention provides a secondary alkali ion battery comprising a lithium-containing cathode, an anode, a separator material and an aprotic and/or nonaqueous electrolyte. Preferably, said electrolyte comprises lithium salts. Preferably, said electrolyte comprises monomers, as defined herein, for example unsaturated monomers. Alkali ion batteries of this type may yet be free of a conductive polymer on the cathode matrix. As described elsewhere in this specification, the polymer may be formed in situ once a voltage is applied for charging the battery. Preferably, upon charging, a polymer is formed from said monomers.
Preferably, in the alkali ion battery of the invention, which said electrolyte, said cathode and said anode are selected so that and/or interact such that, upon charging, a polymer is formed from said monomers.
The anode may be formed from any suitable anode material. Typically, graphite is used as anode material.
The alkali ion batteries of the invention may be used in a wide variety of applications. Accordingly, the present invention encompasses such applications comprising the battery of the invention. In some aspects, the invention encompasses small scape application, such as portable electric devices, portable computers, mobile phones, digital cameras, laptop computers, as well as large scale applications, like electrical vehicles (EVs) and hybrid electric vehicles (HEVs) comprising the batteries of the invention. The alkali ion batteries of the invention may also be used as intermittent power supply.
Exemplary alkali ion batteries of the invention may be, for example, as disclosed in the examples, which are Swagelok-type cells, such as disclosed, for example, in B. Kang and G. Ceder, Nature, 458, 2009, 190-193 and in US 20100323244 Al.
The present invention will now be illustrated by way of examples. These examples do not limit the scope of this invention, which is defined by the appended claims.
Examples:
1. Reagents
3 ,4-ethylenedioxythiopene (EDOT) , poly(3 ,4-ethylenedioxythiophene) :poly(styrene sulfonate) dispersion (PEDOT:PSS), and tetraethylammonium tetrafluoroborate (TEABF4 ) were used without any previous treatment.
Commercial LiFeP04 (LFP) and carbon-coated LiFeP04 (LFP/C) were used as standard active materials in combination with carbon black and poly(vinylidene fluoride) (PVDF) additives whith N-methyl pirrolidone as dispersant. The battery electrolyte consisted of 1 M LiPF6 in ethylene carbonate:diethyl carbonate electrolyte (EC:DEC, 1: 1 volume ratio).
2. Preparation of standard cathodes
LFP and LFP/C standard electrodes were prepared by mixing the active material with carbon black and PVDF additives (85:8:7 wt. %) in N-methyl pyrrolidone to form slurry. The slurry was sonicated, deposited over an aluminum disk (0.64 cm ) and dried at 80°C under vacuum for 12 h (B. Leon, C. Perez Vicente, J. L. Tirado, Ph. Biensan, and C. Tessier, Journal of The Electrochemical Society, 155 (3) A211-A216 (2008)). The average amount of active material ranges from 3-5 mg cm" .
3. Battery assembly and cycling tests
Batteries were assembled in two-electrode Swagelok-type cells, using the cathode as working electrode, 1 M LiPF6 (EC:DEC, 1: 1 volume ratio) electrolyte with Whatman glass- paper as separator, and lithium metal foil as reference/counter electrode. The cells were assembled in a glove box under controlled argon atmosphere (H20, 02 < 1 ppm). Galvanostatic cycling at different C-rates (C = 1 Li h"1 mol"1) was carried out at room temperature using an MPG station. 4. Preparation of PEDOT composites with LFP or LFP/C
The different methods used to incorporate a source of PEDOT to the standard LFP or LFP/C active materials are described below:
4.1. Blending method. The blending method consisted in mixing the active material and a selected source of PEDOT in N-methyl pyrrolidone to form slurry (without carbon black and PVDF additives). The slurry was sonicated, deposited over an aluminum disk and dried at 80-100 °C under vacuum for 12 h. The different PEDOT sources are: a) PEDOT was synthesized potentiostatically in a three-electrode cell with platinum wire as working electrode, a graphite rod as counter electrode and Ag/AgCl (3M KC1,
AgCl sat.) reference electrode. The two-phase reaction medium contained TEABF4 (0.1 M) dissolved in water and EDOT (0.1 M) dissolved in dichloromethane. The electropolymerization of EDOT monomer takes place over platinum at the aqueous/organic interphase when an oxidation potential of 1.3 V was applied. The obtained polymer was washed by dionized water followed by acetonitrile, and dried for 12 h under vacuum at 60 °C. The weight ratio of LFP:PEDOT in the composite was 80:20 wt. %. b) PEDOT polymerized by chemical reaction. PEDOT was synthesized by oxidative chemical polymerization of EDOT (0.7 mmol) using FeCl3 H20 (1.6 mmol) as oxidant in 15 mL of boiling acetonitrile for 30 minutes. The solid product was washed repeatedly with deionized water until negative reaction of chloride ion with AgN03 (0.1 M). The product was dried for 12h under vacuum at 60 °C. The weight ratio of LFP:PEDOT in the composite was 90: 10 wt. %. c) PEDOT/PSS dispersion. Due to high water content, the composite cathode incorporating this PEDOT source was dried at 100°C after its deposition over an aluminum disk. The weight ratio of LFP:PEDOT was 90: 10 wt.
Composite cathodes with this PEDOT source detach from the current collector during drying, neither for an LFP(90 wt.)+PEDOT(10 wt.) composite nor for an LFP(75 wt.)+PEDOT(10 wt.)+carbon black (8% wt.)+PVDF (7% wt.). Due to loss of contact to the current collector, no battery has been yet tested and no results are available for this material.
4.2. PEDOTrPSS deposit. This method consisted in depositing drops PEDOT:PSS dispersion over a standard LFP electrode to incorporate polymer (10% wt.) after evaporation of the solvents/dispersants by heating at 80-100°C under vacuum.
4.3. Electrodeposition. Standard LFP and LFP/C cathodes were used as substrate for the electrodeposition/polymerization of EDOT. The electrodeposition was carried out using a standard cathode as working electrode in a three electrode cell with an aluminum disk as counter electrode and Ag/AgCl (3M KCl, AgCl sat.) reference electrode. The reaction medium consisted of a 0.1 M EDOT, 0.1 M TEABF4 solution in acetonitrile. The electropolymerization over the LFP or LFP/C electrode was performed potentiostatically at 1.3 V (Ag/AgCl) during 30 and 3 min., respectively. After electropolymerization, the working electrode was washed with acetonitrile and dried at 80 °C under vacuum for 12 h. 4.4. In situ polymerization of EDOT. EDOT polymerization was performed inside the lithium battery with stoichiometric (LiFePO4) or partially delithiated cathodes (Lii_xFePO4). Details are described below: i) In situ polymerization with LiFePO.j. Method 1. The polymerization of EDOT monomer with the stoichiometric cathode was performed inside a battery with a standard LFP cathode. EDOT monomer was added to the battery as a 0.15 M solution in the electrolyte (1 M LiPF6 in EC:DEC, 1: 1 volume ratio). Polymerization of EDOT takes place during the first charging cycle at C/10 from the open circuit potential to 4.2 V (Li+/Li). ii) In situ polymerization with LiFePO_(. Method 2. EDOT monomer was mixed only with LFP active material (neither Carbon black nor PVDF were added) to form a slurry which was formed as a cathode as described above. Polymerization of EDOT in the LFP/EDOT composite takes place during the first charging cycle at C/10 until 4.2 V (Li+/Li), in the presence of 1 M LiPF6 (EC:DEC, 1: 1 volume ratio) electrolyte, and a lithium metal counter electrode. iii) In situ polymerization with Lii-xFePO4. For the polymerization of EDOT monomer with the delithiated cathode, a battery with a standard LFP cathode, 1 M LiPF6
(EC:DEC, 1: 1 volume ratio) electrolyte and a lithium metal counter electrode, was charged at C/10 until 4.2 V (Li+/Li). After the first charge, the battery was opened inside the glovebox and EDOT monomer was added as a 0.15 M solution to the electrolyte. The complete charging of the battery including complete polymerization was then performed at C/10 until 4.2 V (Li+/Li).
4.5. In situ polymerization of ProDOT. ProDOT polymerization was also performed inside the lithium battery with stoichiometric (LiFePO4) or partially delithiated cathodes (Lii_xFePO4). Details are described below: i) In situ polymerization with LiFePO.j. Method 1. Same as described above for EDOT polymerization. ii) In situ polymerization with LiFePO.j. Method 2. Same as described above for EDOT polymerization.
iii) In situ polymerization with Lii-xFePO_(. Same as described above for EDOT polymerization.

Claims

Claims
A method for producing an alkali ion battery, the method comprising the steps of assembling a lithium-containing cathode, an anode, a separator material and an electrolyte so as to form an alkali ion battery, wherein said electrolyte comprises an aprotic and/or non-aqueous solvent, lithium salts and a polymerizable monomers.
The method of claim 1, wherein said step of assembling said lithium-containing cathode, anode, separator material and electrolyte comprises the steps of:
- providing a partially or totally assembled alkali ion battery comprising a cathode, an anode and an electrolyte, wherein said cathode comprises a material selected from non-delithiated and partially or totally delithiated cathode materials;
- adding polymerizable monomers to said electrode and/or electrolyte of said partially or totally assembled alkali ion battery.
The method of claim 1 or 2, wherein said step of assembling said lithium-containing cathode, anode, separator material and electrolyte comprises the steps of:
- adding a polymerizable monomer to an electrode and/or electrolyte of a pre- assembled or disassembled alkali ion battery comprising, besides said electrolyte, a cathode and an anode electrically connected by said electrolyte;
- producing said alkali ion battery by sealing the pre-assembled or disassembled alkali ion battery comprising said monomer in said electrolyte.
A method for producing an alkali ion battery, the method comprising the steps of:
- providing an alkali ion battery, comprising a lithium-containing cathode, an anode and an electrolyte;
- partially or totally delithiating said cathode by charging said battery at least partially;
- partially and/or totally disassembling said battery;
- reassembling a battery using said deliathiated cathode while adding a monomer to said delithiated cathode and/or to the electrolyte; and,
- enabling polymerization of said monomer by oxidizing said monomer in said reassembled battery.
5. The method of any one of the preceding claims, wherein polymerization of said monomer is enabled by applying an external charge to the battery and/or to the reassembled battery.
5 6. The method of any one of the preceding claims, comprising the step of polymerizing said monomer by oxidative polymerization.
7. The method of any one of the preceding claims, comprising the step of polymerizing said monomer in situ, inside a partially assembled and/or totally assembled alkali ion
10 battery.
8. The method of any one of the preceding claims, further comprising the step of applying a charge on said alkali ion battery so as to induce polymerization of said monomer in said electrolyte.
15
9. The method of any one of the preceding claims, wherein said monomer is polymerized on and/or in the matrix of said cathode and/or said working electrode.
10. The method of any one of claims 6-9, wherein said polymerization results in a 20 polymer-cathode composite material and/or a composite polymer-working electrode.
11. The method of any one of the preceding claims, further comprising the step of sealing the partially assembled alkali ion battery, the pre-assembled or disassembled alkali ion battery and/or the electrochemical device comprising the electrolyte with
25 said monomer.
12. The method of any one of the preceding claims, further comprising the steps of:
applying a charge on said alkali ion battery so as to charge the battery at least partially so as to obtain a totally or partially charged battery;
30 - disassembling at least partially said totally or partially charged battery so as to obtain an at least partially disassembled battery;
- re-assembling said battery by using an electrolyte comprising an unsaturated monomer or adding the monomer to said at least partially disassembled battery.
35 13. The method of any one of the preceding claims, wherein said monomer is susceptible of being polymerized by oxidative polymerization. The method of any one of the preceding claims, wherein said monomer is susceptible of being oxidized in presence of said electrode and/or electrolyte, and wherein oxidized monomer is susceptible of initiating polymerization of the monomer.
The method of any one of the preceding claims, wherein said monomer is a monomer selected from the monomers of form :
Figure imgf000030_0001
wherein R3-R8 are independently selected from H and from organic substituents comprising from 1 to 15 carbons and from 0 to 10 heteroatoms.
The method of any one of the preceding claims, wherein said cathode or working electrode comprises a material selected from Li-containing layered, olivine or spinel- related solid materials suitable as cathode materials for alkali ion batteries.
The method of any one of the preceding claims, wherein said cathode and/or said working electrode comprises a cathode material of any one of formulae (II) to (IV) below:
A M Y (II) A M O X04 (III) A N2 04 (IV) wherein A represents Li, which can be accompanied by other non-transition metals; M is a first series transition metal or a combination of two, three or more different metals selected from first series transition metals and from Al, with the proviso that if M is a combination of different metals at least one metal is a first series transition metal
Y is selected from (¾, O3 and XO4;
XO4 is selected from PO4, SO4, M0O4, WO4, S1O4, and combinations thereof;
N is Mn; The method of any one of the preceding claim, wherein said cathode and/or working electrode material is selected from the group consisting of: L1VOPO4, LiCo02,
LiNi02, LiNi1.nCon02, LiNi1.n.mConAlm02, LiNi1.n.mConMnm02, LiMn204, LiFeP04 and LiFej.nMnnP04 , L1C0PO4, Li2FeP207, Li2FeSi04, and combinations thereof.
A secondary alkali ion battery comprising a Li-containing cathode, an anode, a separator material and an aprotic and/or non-aqueous electrolyte, wherein said electrolyte comprises lithium salts and unsaturated monomers.
20. The secondary alkali ion battery of claim 19, in which said electrolyte, said cathode and said anode are selected so that and/or interact such that, upon charging, a polymer is formed from said monomers.
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