EP2656418A1 - Électrodes pour batteries au lithium - Google Patents

Électrodes pour batteries au lithium

Info

Publication number
EP2656418A1
EP2656418A1 EP11824260.1A EP11824260A EP2656418A1 EP 2656418 A1 EP2656418 A1 EP 2656418A1 EP 11824260 A EP11824260 A EP 11824260A EP 2656418 A1 EP2656418 A1 EP 2656418A1
Authority
EP
European Patent Office
Prior art keywords
cellulose
cathode
lithium
binder
anode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11824260.1A
Other languages
German (de)
English (en)
Inventor
Martin Winter
Sangsik JEONG
Stefano Passerini
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Volkswagen AG
Albemarle Germany GmbH
Litarion GmbH
Original Assignee
Volkswagen AG
Rockwood Lithium GmbH
Evonik Litarion GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Volkswagen AG, Rockwood Lithium GmbH, Evonik Litarion GmbH filed Critical Volkswagen AG
Publication of EP2656418A1 publication Critical patent/EP2656418A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J101/00—Adhesives based on cellulose, modified cellulose, or cellulose derivatives
    • C09J101/02—Cellulose; Modified cellulose
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to improving the environmental friendliness of battery electrodes and lithium batteries using the same, an environmentally friendly manufacturing method for producing battery cathodes and anodes, and batteries containing one or more of these components.
  • the present invention relates in particular to electrodes for lithium batteries containing cellulose, preferably natural cellulose, and / or cellulose derivatives which are soluble in ionic liquids, to processes for producing these electrodes and to their use.
  • Lithium batteries include, but are not limited to, active cathode materials, anode active materials, and separators.
  • Active cathode materials for lithium batteries may be composed of lithium-containing transition metal oxides such as LiCoO 2 , LiMnO 2 , LiNiO 2 and binary or ternary compounds (LiCo ( ixy) NixMn y O 2 ), chalcogen compounds such as MoS 2 , and metal phosphates such as for example LiFeP0 4 . Since these compounds have a layered crystal structure, lithium ions can be reversibly intercalated / deintercalated into these structures. For this reason, these compounds are often used as active cathode materials for lithium batteries.
  • the active anode material may be metallic lithium, however, then acicular lithium dendrites may grow on the surface of the lithium. This can happen because the lithium is repeatedly released and re-deposited during charging / discharging of a battery. As a result, the acicular dendrites can adversely affect the discharge / charge efficiency and possibly even cause internal shorts by contact with the cathode.
  • a material that reversibly intercalates and deintercalates lithium ions can be used as the anode material.
  • This material may be a lithium alloy, a metal powder, a graphitic or carbonaceous material, metal oxides or metal sulfides.
  • a binder is necessary to bind powdery electrode materials to the electrical conductors and to form sheet-shaped electrodes.
  • lithium battery electrodes and separators have been manufactured Use of artificially produced polymers such as PE (polyethylene), PP (polypropylene), PEO (polyethylene oxide), PPO (polypropylene oxide), PTFE (polytetrafluoroethylene), PMMA (polymethyl methacrylate), PAN (polyacrylonitrile), PS (polystyrene), SBR (styrene-butadiene rubber) and many others, each alone or in mixtures of these substances.
  • PE polyethylene
  • PP polypropylene
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • PTFE polytetrafluoroethylene
  • PMMA polymethyl methacrylate
  • PAN polyacrylonitrile
  • PS polystyrene
  • SBR styrene-butadiene rubber
  • PVdF polyvinylidene difluoride, as such or as a copolymer
  • PVdF-HFP where HFP stands for hexafluoropropylene
  • NMP N-methyl-2-pyrrolidone
  • Japanese Patent Laid-Open Publication JP 05-074461 discloses a process for producing an aqueous slurry of active anode material using styrene-butadiene rubber (SBR) -based binder and a carboxymethyl cellulose (CMC) -based binder. In this case, water was used as the solvent.
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • Carboxymethyl cellulose or CMC a cellulose derivative having carboxymethyl groups (-CH 2 -COOH) attached to some of the hydroxyl groups of the cellulose backbone, is prepared by the alkali-catalyzed reaction of cellulose with chloroacetic acid.
  • this process is expensive and requires the use of toxic chemicals.
  • Cellulose is an environmentally friendly binder that requires no further chemical treatment (apart from the removal of the remains of its plant sources). Cellulose is the most common organic compound on earth. Approximately 33% of total plant matter is cellulose (up to 90% in cotton and 50% in wood). And it can be from almost any plant be won.
  • the object of the present invention is to avoid the disadvantages of the prior art.
  • more environmentally friendly binders for powdered anode and / or cathode materials and methods for producing anodes and cathodes with the aid of these binders are to be found.
  • cathodes or anodes in which the cathode or anode binder comprises or consists of cellulose, preferably natural cellulose, and / or cellulose derivatives which are soluble in ionic liquids, processes for their preparation and use of natural cellulose as a binder for the production of cathodes and anodes, in particular battery electrodes solved.
  • room temperature means a temperature of 20 ° C. Unless indicated otherwise, temperature data are in degrees Celsius (° C.).
  • compositions means physical and / or chemical mixtures or compounds of substances.
  • ionic liquid is understood as meaning exclusively liquids comprising cations and anions, which have low melting points of less than 100 ° C.
  • the ionic liquids have virtually no room temperature Vapor pressure.
  • the size and symmetry of the ions involved hinder the formation of a strong crystal lattice. Even low thermal energy is therefore sufficient to overcome the lattice energy and break up the solid crystal structure.
  • ionic liquids are understood in particular to mean those which are liquid at temperatures between -10 and 80.degree. C., in particular at room temperature.
  • natural cellulose in contrast to the present invention also usable fully synthetic cellulose, cellulose from various natural sources, especially cotton, flax, ramie, bamboo, straw, bacteria, wood, bagasse understood.
  • the present invention relates to an environmentally friendly manufacturing process for the production of cathodes and anodes, wherein cellulose is used as a binder, and lithium batteries containing all or some of these components.
  • the present invention is particularly directed to the use of natural cellulose as a binder for making battery electrodes.
  • the natural cellulose is dissolved in completely recyclable ionic liquids.
  • the ionic liquids are removed by a phase inversion process using water (or C 1 -C 5 alcohols) as cosolvents.
  • VOCs volatile organic compounds
  • the present invention accordingly provides cathodes and anodes, in which natural cellulose is used as binder, preferably containing battery electrodes and batteries, in particular lithium batteries all or some of these components.
  • the present invention accordingly also provides a process for the production of cathodes and anodes, in particular battery electrodes, in which
  • the cellulose-based electrode slurries are then applied to electron-resistant substrates, in particular power drainage films, or pasted into current conductor grid or foams,
  • the ionic liquids are removed by a phase inversion process using water (or natural alcohols) as co-solvents.
  • Completely recyclable in the context of the present invention means that the ionic liquids or the like by professional measures, such as filtration, distillation. separated from the other materials and at least 90 wt .-%, preferably at least 95 wt .-%, particularly preferably at least 98 wt .-% in a purity of at least 90%, preferably at least 95%, particularly preferably at least 98%, wherein the purity of the content of ionic liquid (s) in relation to other substances that are not ionic liquids, can be recovered.
  • professional measures such as filtration, distillation. separated from the other materials and at least 90 wt .-%, preferably at least 95 wt .-%, particularly preferably at least 98 wt .-% in a purity of at least 90%, preferably at least 95%, particularly preferably at least 98%, wherein the purity of the content of ionic liquid (s) in relation to other substances that are not ionic liquids, can be recovered.
  • the present invention furthermore relates to the use of natural cellulose as a binder for the production of cathodes and anodes, in particular battery electrodes.
  • battery cathodes and anodes employing natural cellulose as a binder function as well as battery cathodes and anodes made with conventional binders, although cellulose has multiple OH groups which are considered to be reactively unstable in the voltage range of a lithium battery.
  • the anodes and cathodes of the present invention can be used to make batteries, particularly lithium batteries, which have state-of-the-art characteristics, but additionally have the advantage of easier recyclability. Because the binder can be removed at the end of the life cycle of the battery by simple pyrolysis of the electrode. The pyrolysis of cellulose only results in the production of carbon dioxide and water, which are not harmful to the environment.
  • An embodiment of the present invention includes lithium battery cathodes and anodes containing cellulose as a binder. Furthermore, in a further embodiment, the present invention comprises a lithium battery containing one or both of the above lithium battery components.
  • the cellulosic binder used in the lithium battery components is prepared by dissolving in an ionic liquid (or in a mixture of ionic liquids or in a mixture of ionic liquid and water) and depositing by a phase inversion process the water (or alcohol) is used as co-solvent.
  • a lithium battery cathode is fabricated using cathode forming materials and cellulose.
  • a cathode plate according to the invention can be prepared by dissolving natural cellulose in an ionic liquid or a mixture of ionic liquids or a mixture of ionic liquid and water. After dissolution of the binder, the active cathode material and optionally a conductive material are added and the cathode slurry is obtained by stirring.
  • the slurry is then applied to a current collector foil, wherein the foil may be a metal foil, an electrically conductive plastic foil or a carbon-coated metal or electrically conductive plastic foil, preferably selected from the group consisting of an aluminum foil, a nickel foil, a titanium foil , a stainless steel foil, a carbon-coated aluminum foil, a carbon-coated nickel foil, a carbon-coated titanium foil, a carbon-coated stainless steel foil.
  • the slurry applied to the film is then subjected to a phase inversion process using water as a cosolvent to remove the ionic liquid from the cathode coating. Ionic liquids are very hydrophilic and when immersing the coated electrodes, the ionic liquid migrates into an aqueous phase.
  • C 1 -C 5 -alcohols can be used as co-solvents, preferably selected from the group consisting of methanol, ethanol, all isomers of propanol, all isomers of butanol, all isomers of Pentanols and mixtures thereof.
  • the phase inversion process consists of introducing the coated cathode into deionized water.
  • the coated electrode is immersed in an aqueous phase, wherein the ionic liquid migrates due to their high hydrophilicity in the water.
  • Phase inversion processes are well known and need not be detailed here, as can be found, for example, in Du Pasquier et al. , 2000, Solid State Ionics 135, 249-257 or DE 10 2008 041 477 A1 Application examples.
  • the ionic liquid can be completely recovered from the aqueous solution by subjecting the aqueous solution to filtration (to remove the solid particles that might have formed in the phase inversion process) and then evaporating the water, especially by using a rotary evaporator.
  • the coated cathode After removal of the ionic liquid, the coated cathode is dried to form a cathode plate.
  • the cathode-forming materials may include a cathode active material including, but not limited to, lithium iron phosphate (LiFePO 4 ) and a conductive material.
  • a cathode active material including, but not limited to, lithium iron phosphate (LiFePO 4 ) and a conductive material.
  • the conductive material it is possible to use all conductive materials normally known to the person skilled in the art, preferably based on conductive carbon black, graphite or metal, more preferably selected from the group consisting of graphite, nickel, aluminum, titanium and mixtures thereof.
  • the active cathode material may preferably be selected from the group consisting of
  • Lithiumcompositoxiden preferably of the formula Li w A x ByCzO v
  • the active cathode material is LiFeP0 4 .
  • Other cathode materials that can be used in a variant of the present invention are those commonly used in the art.
  • a lithium battery cathode current collector (cathode plate) may be constructed of any electronic conductor that is chemically unreactive in a battery.
  • the current collector may be made of stainless steel, Ni, Al, Ti or C.
  • the surface of the stainless steel may be C, Ni, Ti or Ag.
  • the cathodic current collector may be made of aluminum or an aluminum alloy, preferably of aluminum.
  • the amount of cellulose binder may be in the range of 0.1 to 40% by weight, preferably 1 to 35% by weight, more preferably 5 to 25% by weight, based on the total cathode composition.
  • the complete cathode composition may comprise the cathode active material, a conductive material, and the cellulosic binder.
  • a lithium battery anode is fabricated using anode forming materials and cellulose.
  • An anode plate can be made by dissolving natural cellulose in an ionic liquid or a mixture of ionic liquid and water.
  • the active anode material and optionally conductive material are added to produce the anode slurry by stirring.
  • the slurry is then applied to a film, wherein the film may be a metal foil, an electrically conductive plastic film or a carbon-coated metal or plastic film, preferably selected from the group consisting of a copper foil, a nickel foil, a stainless steel foil, a carbon-coated copper foil, a carbon-coated nickel foil, a carbon-coated stainless steel foil.
  • the applied slurry is then subjected to a phase inversion process using water as a cosolvent to remove the ionic liquid from the anode coating.
  • C 1 -C 5 -alcohols can be used as co-solvents, preferably selected from the group consisting of methanol, ethanol, all isomers of propanol, all isomers of butanol, all isomers of Pentanols and mixtures thereof.
  • the phase inversion process consists of introducing the coated anode into deionized water.
  • the coated electrode is immersed in an aqueous phase, wherein the ionic liquid migrates due to their high hydrophilicity in the water.
  • the ionic liquid can be completely recovered from the aqueous solution by filtration (to remove solid particles which might have formed during the phase inversion process) and evaporation of the water, particularly by a rotary evaporator. After removal of the ionic liquid, the coated anode can be dried to a To form an anode plate.
  • the anode forming materials may include an active anode material that may include, but is not limited to, a carbonaceous material and a conductive material.
  • conductive material it is possible to use all conductive materials normally known to the person skilled in the art, preferably based on conductive carbon black, graphite or metal powder or wisker, particularly preferably selected from the group consisting of graphite, nickel,
  • the active anode material is preferably selected from the group consisting of
  • carbonaceous material such as natural graphite, artificial graphite, coke, carbon fiber,
  • a lithium battery anode current collector according to the present invention may be made of any electrical conductor that is chemically unreactive in a battery.
  • the current collector may be made of stainless steel, Ni, Cu, Ti or C.
  • the surface of the stainless steel may be C, Ni, Ti or Ag.
  • the anodic current collector can be made of copper or of a copper alloy, in particular of copper.
  • the amount of cellulose binder may be in the range of 0.1 to 40% by weight, preferably 1 to 35% by weight, more preferably 5 to 25% by weight, based on the total anode composition.
  • the total anode composition may include the active anode material, a conductive material, and the cellulosic binder.
  • the solvent for the cellulose may be 1-ethyl-3-methylimidazolium acetate (also abbreviated in the context of the present invention as EMIAc), but is not limited thereto.
  • EMIAc 1-ethyl-3-methylimidazolium acetate
  • Other ionic liquids which can be used for this purpose are in particular ⁇ 2 ⁇ 2 " and all 1-alkyl-3-methylimidazolium acetate compounds.
  • Examples of compounds which can be used in a variant of the present invention can be found in DE 10 2005 017 715 A1, DE 10 2005 062 608 A1, DE 10 2006 042 892 A1, WO 2008/1 19770 A1.
  • the following describes a method of manufacturing a lithium battery according to the present invention.
  • the lithium salt used in the lithium battery of the present invention may be any lithium compound which dissolves in organic solvents to form lithium ions.
  • the lithium compound is preferably selected from the group consisting of lithium perchlorate (LiCIO 4 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluorophosphate (LiPF 6 ), Lithium trifluoromethanesulfonate (LiCF 3 S0 3 ), lithium bis (trifluoromethanesulfonyl) amide (LiN (CF 3 S0 2 ) 2) and mixtures thereof.
  • LiCIO 4 lithium perchlorate
  • LiBF 4 lithium tetrafluoroborate
  • LiPF 6 lithium hexafluorophosphate
  • LiPF 6 Lithium trifluoromethanesulfonate
  • LiN (CF 3 S0 2 ) 2 LiN (CF 3 S0 2 ) 2
  • the concentration of the lithium salt can be within the scope of the present invention in a range of 0.5 to 2 mol per liter move. If the concentration of the lithium salt moves outside this range, the ionic conductivity may be undesirably low.
  • An organic electrolytic solution containing such inorganic salts may function as a path through which lithium ions flow in a current flow direction.
  • the organic solvent for an electrolyte solution suitable in the context of the present invention can preferably be selected from the group consisting of polyglycol ethers, oxolanes, carbonates, 2-fluorobenzene,
  • the polyglycol may be selected from the group consisting of diethylene glycol dimethyl ether (CaiOChfeCHafeOCHa), diethylene glycol diethyl ether (C 2 H 5 (OCH 2 CH 2) 2 0C 2 H 5), triethyleneglycol dimethylether (CHaiOCHzCHzJaOCHa), triethylene glycol diethyl ether (C2 H5 (OCH2CH2) 30C 2 H5) and Mixtures thereof.
  • the dioxolanes may be selected from the group consisting of 1, 3-dioxolane, 4,5-diethyldioxolane, 4,5-dimethyldioxolane,
  • the carbonates may be selected from the group consisting of methylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, gamma-butyrolactone, propylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, vinylene carbonate, and mixtures thereof.
  • the organic solvent in a variant of the present invention may be a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC).
  • the amount of the solvent used may correspond to the amount used in a conventional lithium battery, preferably the concentration of the lithium salt is 0.5 to 2.0 mol / l of solvent.
  • the separator may in the context of the invention consist of any conventional separator, which is commonly used in lithium batteries. The separator is said to have less resistance against the migration of ions in the electrolyte and to have a high electrolyte-retaining capacity.
  • the separator may be selected from the group consisting of glass fibers, polyester, polyethylene, polypropylene, polytetrafluoroethylene, carboxymethyl cellulose, or a combination of these materials which may be in a woven or nonwoven form.
  • the separator may be constructed of a porous membrane of polyethylene and / or polypropylene, which is less reactive to organic solvent.
  • the separator may also be a polyelectrolyte which is applied in any manner to one or both electrodes before the battery is assembled.
  • the polyelectrolyte consists of a matrix-forming polymer resin that is normally used as a binder for an electrode plate.
  • the matrix-forming polymer resin may be composed of carboxymethyl cellulose, vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyethylene oxide, and any combination of these materials.
  • the matrix-forming polymer resin may further contain a filler to increase the mechanical strength of the polymer electrolyte.
  • the filler may preferably consist of silicon dioxide, kaolin or aluminum.
  • the matrix-forming polymer resin may contain a common plasticizer, if desired.
  • the electrodes (anodes, cathodes) usable according to the present invention can be used in conventional lithium batteries such as primary batteries, secondary batteries and sulfur batteries.
  • the electrodes according to the present invention can be used in arbitrarily shaped lithium batteries, e.g. As cylindrical, rectangular, disc-shaped or other designs, but is not limited thereto.
  • the present invention enables an environmentally friendly, inexpensive manufacturing process for the production of battery components (cathodes, anodes) using natural cellulose as a binder.
  • a lithium-ion secondary battery manufactured using these components exhibits excellent performance compared to a corresponding battery made using synthetic binders such as PVdF or CMC.
  • environmentally-damaging organic solvents and processes used in conventional lithium battery manufacturing are replaced by non-volatile, fully recoverable ionic liquids and environmentally friendly water.
  • a lithium battery produced by the present invention can be widely used as a power source for portable electronic devices such as cellular phones, PDAs and notebook computers, as well as electric vehicles.
  • the use of the lithium battery guarantees safety and a long life of the devices.
  • the sole binder for the known powdered electrode mixtures (consisting of the known active materials for cathodes and anodes, and conductivity enhancers and for attachment to known support materials), which are used in known cell designs with known separator materials and known electrolytes, consists of cellulose and / or cellulose derivatives , which are soluble only in ionic liquids, preferably cellulose, particularly preferably natural cellulose, which are dissolved in a known manner in an ionic liquid. With these solutions, an electrode paste is produced and applied to a carrier material applied.
  • FIG. 1 illustrates the process for producing the cellulose-based battery components as shown in Examples 1 and 2.
  • FIG. 2 illustrates the performance of a cellulose-based cathode produced as in Example 1 in a lithium metal cell.
  • the upper graph illustrates the capacity of the electrode during 20 cycles.
  • the lower graph illustrates the stress profile during a generic lithiation / delithiation cycle.
  • Figure 3 illustrates the performance of a cellulose-based anode prepared as described in Example 2 in a lithium metal cell.
  • the upper graph illustrates the capacity of the electrode during 20 cycles.
  • the lower graph illustrates the stress profile during a generic lithiation / delithiation cycle.
  • Figure 4 illustrates the performance of a lithium battery cell made with the components of Examples 1 and 2.
  • the upper graph illustrates the capacity of the battery during 20 cycles.
  • the lower graph illustrates the voltage profile during a generic charge / discharge cycle.
  • example 1 The following example relates to a method of producing a lithium battery cathode according to the present invention.
  • 0.04 g of cellulose were dissolved in 1.56 g of EMIAc (BASF).
  • 1.0 g of LiFePO 4 (Süd Chemie) and 0.107 g of conductive carbon (carbon black) Ketjen Black (AKZO Nobel) were added to the cellulose solution in EMIAc.
  • This mixture was stirred and a homogeneous slurry was formed.
  • This slurry was knife-coated on aluminum foil.
  • the applied slurry thickness was set to 0.05 mm and the application speed to 100 mm per second.
  • a coated area of 200 cm 2 was obtained.
  • the coated aluminum foil was placed in water and left there for 30 minutes to extract EMIAc. Thereafter, the aluminum foil was dried in air for 2 hours at 20 ° C and then at 60 ° C for 6 hours to obtain the cathode plate.
  • the aqueous solution was filtered and
  • the following example shows a method of producing a lithium battery anode according to the present invention.
  • Cellulose was used as a binder.
  • 0.05 g of cellulose was dissolved in 1.95 g of EMlAc.
  • 1.0 g of graphite SLP30 (TiMCAL) as the active anode material and 0.05 g of conductive carbon (conductive black) Super P (TIMCAL) were added to the cellulose solution in EMIAc. This mixture was stirred and a homogeneous slurry was formed.
  • This slurry was applied to a copper foil by means of a doctor blade.
  • the coated slurry thickness was set to 0.05 mm and the application speed to 100 mm per second. A coated area of 200 cm 2 was obtained.
  • the coated film was placed in water and held there for 30 minutes to extract the EMIAc. Thereafter, the film was dried in air for 2 hours at 20 ° C and for 6 hours at 60 ° C to obtain the anode plate. The aqueous solution was filtered, the water evaporated, and the EMIAc recovered completely.
  • Example 3 The following example shows a method of producing a lithium metal battery using the cellulose-based cathode according to the present invention.
  • a cathode disc (12 mm diameter, also called cathode plate) was cut out of the cathode foil, prepared as in Example 1.
  • a lithium metal anode was cut out of a commercial lithium foil (Chemetall).
  • a 12 mm non-woven glass fiber disk (Whatman) was used as a separator.
  • the separator was placed between the cathode plate and the anode plate (lithium).
  • the electrode assembly was inserted into a T-shaped battery case, then a nonaqueous electrolytic solution was injected, and then the package was sealed to obtain a lithium ion secondary battery.
  • the nonaqueous electrolytic solution consisted of a one molar solution of LiPF 6 dissolved in a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) in a ratio of 50:50 by weight.
  • the following example shows a method of producing a lithium ion battery using the battery components of the present invention obtained as described in Examples 1 and 2.
  • a cathode disk (12 mm diameter, also called cathode disk) was cut out of the cathode film as described in Example 1.
  • the anode plate was cut out of an anode foil as described in Example 2. Both electrodes were dried in an oven at 90 ° C for 10 hours.
  • a 12 mm non-woven glass fiber disk (Whatman) was used as a separator.
  • the separator was placed between the cathode plate and the anode plate.
  • the electrode assembly was inserted into a T-shaped battery case, whereupon a nonaqueous electrolytic solution was injected and then sealed to obtain a lithium ion secondary battery prototype.
  • the nonaqueous electrolytic solution consisted of a one molar Solution of LiPF 6 dissolved in a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) in a weight ratio of 50:50.

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  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Separators (AREA)

Abstract

L'invention concerne une cathode ou une anode, le liant de la cathode ou le liant de l'anode comportant ou étant constitué de cellulose et/ou de dérivés de cellulose solubles uniquement dans des liquides ioniques; leur procédé de production et l'utilisation de cellulose et/ou de dérivés de cellulose solubles, uniquement dans des liquides ioniques, en tant que liants pour la production de cathodes et d'anodes, notamment d'électrodes de batterie.
EP11824260.1A 2010-12-22 2011-12-20 Électrodes pour batteries au lithium Withdrawn EP2656418A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010061485A DE102010061485A1 (de) 2010-12-22 2010-12-22 Elektroden für Lithium-Batterien
PCT/EP2011/073312 WO2012084878A1 (fr) 2010-12-22 2011-12-20 Électrodes pour batteries au lithium

Publications (1)

Publication Number Publication Date
EP2656418A1 true EP2656418A1 (fr) 2013-10-30

Family

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EP11824260.1A Withdrawn EP2656418A1 (fr) 2010-12-22 2011-12-20 Électrodes pour batteries au lithium

Country Status (7)

Country Link
US (1) US20130327249A1 (fr)
EP (1) EP2656418A1 (fr)
JP (1) JP2014503967A (fr)
KR (1) KR20140040092A (fr)
CN (1) CN103534850A (fr)
DE (1) DE102010061485A1 (fr)
WO (1) WO2012084878A1 (fr)

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DE102013111853A1 (de) * 2013-10-28 2015-04-30 Rockwood Lithium GmbH Kohlenstoffbeschichtetes Lithiumsulfid
WO2017083822A1 (fr) * 2015-11-13 2017-05-18 Massachusetts Institute Of Technology Procédés et appareils de commande d'électrodéposition à l'aide de propriétés de charge de surface
US11251430B2 (en) 2018-03-05 2022-02-15 The Research Foundation For The State University Of New York ϵ-VOPO4 cathode for lithium ion batteries
US20190288272A1 (en) * 2018-03-17 2019-09-19 Jingzeng Zhang Method of making active electrode and ceramic separator in battery
KR20230044783A (ko) * 2021-09-27 2023-04-04 주식회사 엘지에너지솔루션 전극 코팅장치 및 이를 이용한 전극의 제조방법

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Also Published As

Publication number Publication date
DE102010061485A1 (de) 2012-06-28
US20130327249A1 (en) 2013-12-12
JP2014503967A (ja) 2014-02-13
CN103534850A (zh) 2014-01-22
KR20140040092A (ko) 2014-04-02
WO2012084878A1 (fr) 2012-06-28

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