EP2697844A1 - Batterie lithium-ion à tension élevée - Google Patents

Batterie lithium-ion à tension élevée

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Publication number
EP2697844A1
EP2697844A1 EP12714968.0A EP12714968A EP2697844A1 EP 2697844 A1 EP2697844 A1 EP 2697844A1 EP 12714968 A EP12714968 A EP 12714968A EP 2697844 A1 EP2697844 A1 EP 2697844A1
Authority
EP
European Patent Office
Prior art keywords
lithium
carbonate
battery according
separator
ion
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Withdrawn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
EP12714968.0A
Other languages
German (de)
English (en)
Inventor
Joerg Kaiser
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.)
Li Tec Battery GmbH
Original Assignee
Li Tec Battery 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 Li Tec Battery GmbH filed Critical Li Tec Battery GmbH
Publication of EP2697844A1 publication Critical patent/EP2697844A1/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Withdrawn legal-status Critical Current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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/42—Acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—Polyamide resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426—Fluorocarbon polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/454—Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/494—Tensile strength
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a secondary battery, in particular a lithium-ion battery, which has good stability even at high voltage output.
  • Secondary batteries can be used as a driving force for mobile information devices because of their high energy density and high capacity.
  • such batteries are used in tools, electric automobiles and hybrid-powered automobiles.
  • the batteries should have high voltage, high capacity, and long life, with high safety and reliability.
  • lithium metal phosphates with olivine structure As the cathode material in lithium-ion batteries, since these materials may have a high redox potential compared to lithium metal.
  • lithium manganese phosphate is a value of 4.1 V
  • lithium cobalt phosphate a value of 5 V known.
  • the object of the present invention is to provide a secondary battery, in particular a lithium-ion secondary battery, in which the separator used remains as stable as possible even at high voltages.
  • the and other object (s) is / are achieved by a lithium-ion battery, which comprises
  • a positive electrode comprising at least one olivine-structured lithium transition metal phosphate, wherein the transition metal is selected from manganese, cobalt, nickel, or a mixture of two or three of these elements;
  • separator which separates the positive and negative electrodes and is permeable to lithium ions; wherein the separator comprises a nonwoven web of non-woven, non-electrically conductive polymer fibers which is coated on one or both sides with an ion-conducting inorganic material;
  • lithium-ion battery and “lithium-ion secondary battery” are used interchangeably.
  • the terms also include the terms
  • Lithium battery lithium ion battery
  • lithium ion cell lithium ion cell
  • a lithium-ion battery generally consists of a series or
  • Lithium-ion battery is used as a collective term for the abovementioned terms used in the prior art.
  • positive electrode means the electrode that is capable of accepting electrons when the battery is connected to a consumer, such as an electric motor. So it represents the cathode.
  • negative electrode means the electrode that is capable of delivering electrons when in use. This electrode thus represents the anode.
  • a cathode material which comprises a lithium transition metal with olivine structure.
  • Preferred lithium transition metal phosphates are lithium manganese phosphate, lithium cobalt phosphate and lithium nickel phosphate.
  • lithium manganese phosphate and lithium cobalt phosphate are known in the art and can be prepared by known methods, for example by sintering mixtures containing the corresponding oxides as starting compounds or containing, as starting compounds, compounds which form the corresponding oxides during sintering.
  • the positive electrode may also contain mixtures of two or more of said substances.
  • the positive electrode contains the lithium transition metal phosphate, preferably in the form of nanoparticles.
  • the nanoparticles can take any shape, that is, they can be coarse-spherical or elongated.
  • the lithium transition metal phosphate has a particle size measured as a D95 value of less than 15 pm. Preferably, the particle size is less than 10 pm.
  • the lithium transition metal phosphate has a particle size measured as D95 value between 0.005 pm to 10 pm. In a further embodiment, the lithium transition metal phosphate has a particle size measured as a D95 value of less than 10 pm, wherein the D50 value is 4 pm ⁇ 2 pm and the D10 value is less than 1.5 pm.
  • the lithium transition metal phosphate contains carbon to increase the conductivity.
  • Such compounds can be prepared by known methods, for example by coating with carbon compounds such as acrylic acid or ethylene glycol. It is then pyrolyzed, for example at a temperature of 2500 ° C.
  • the negative electrode may be fabricated from a variety of materials known for use in a prior art lithium-ion battery. In principle, all materials that are capable of forming lithium intercalation compounds can be used.
  • the negative electrode may contain lithium metal or lithium in the form of an alloy, either in the form of a foil, a grid or in Form of particles held together by a suitable binder.
  • lithium metal oxides such as lithium titanium oxide are also possible.
  • Suitable negative electrode materials also include graphite, synthetic graphite, carbon black, mesocarbon, doped carbon, fullerenes.
  • Niobium pentoxide, tin alloys, titanium dioxide, tin dioxide, silicon can also be used as the electrode material for the negative electrode.
  • the materials used for the positive as well as for the negative electrode are preferably held together by a binder holding these materials on the electrode.
  • a binder holding these materials on the electrode.
  • polymeric binders can be used.
  • the binder for example, polyvinylidene fluoride, polyethylene oxide, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylate, ethylene (propylene-diene monomer) copolymer (EPDM), and mixtures and copolymers thereof may be used.
  • the separator used for the battery must be permeable to lithium ions to ensure ion transport of lithium ions between the positive and negative electrodes.
  • the separator for electrons must be insulating.
  • the separator comprises a nonwoven web of non-woven polymer fibers which are not electrically conductive. Such nonwovens are produced in particular by spinning processes with subsequent solidification.
  • the term “fleece” is used synonymously with terms such as “nonwoven fabrics", “knits” or “felt”. Instead of the term “unwoven” the term “not woven” is used.
  • the polymer fibers are selected from the group of polymers consisting of polyacrylonitrile, polyolefin, polyester, polyimide, polyetherimide, polysulfone, polyamide, polyether.
  • Suitable polyolefins are, for example, polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride.
  • Preferred polyesters are, for example, polyethylene terephthalates.
  • the nonwoven contained in the separator is preferably coated on one or both sides with an ion-conducting inorganic material.
  • coating also implies that the ion-conducting inorganic material may be located not only on one side or both sides of the web, but also within the web.
  • the ionically conductive inorganic material is ion conducting in a temperature range of -40 ° C to 200 ° C, i. ion-conducting for lithium ions.
  • the material used for the coating is at least one compound from the group of oxides, phosphates, sulfates, titanates, silicates, aluminosilicates at least one of zirconium, aluminum, silicon or lithium.
  • the ion-conducting material comprises or consists of alumina or zirconia or alumina and zirconia.
  • a separator is used in the battery according to the invention, which consists of an at least partially permeable carrier, which is not or only poorly electron-conducting.
  • This support is coated on at least one side with an inorganic material.
  • the organic material is in the form of polymer fibers, preferably polymer fibers of polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • the nonwoven is coated with an inorganic ion-conducting material, which is preferably ion-conducting in a temperature range of from -40.degree. C. to 200.degree.
  • the inorganic ion-conducting material preferably comprises at least one compound from the group of oxides, phosphates, sulfates, titanates, silicates, aluminosilicates with at least one of the elements zirconium, aluminum, lithium, particularly preferably zirconium oxide.
  • the inorganic ion-conducting material preferably has particles with a maximum diameter of less than 100 nm.
  • Such a separator is sold, for example, under the trade name "Separation®” by Evonik AG in Germany. Methods for producing such separators are known from the prior art, for example from EP 1 017 476 B1, WO 2004/021477 and WO 2004/021499.
  • shut-down temperature which is typically around 120 ° C.
  • break-down temperature is exceeded at approx. 150 to 180 ° C. From this temperature it comes in conventional separators to melt the separator, which contracts.
  • a pressure relief valve a rupture disk
  • separator used in the battery according to the invention comprising a nonwoven made of non-woven polymer fibers and the inorganic coating, it can only come to shutdown (shutdown), when melted by the high temperature, the polymer structure of the carrier material and penetrates into the pores of the inorganic material and this thereby closing.
  • shutdown the polymer structure of the carrier material and penetrates into the pores of the inorganic material and this thereby closing.
  • break-down there is no such break-down (collapse) as the inorganic particles ensure that complete melting of the separator can not occur. This ensures that there are no operating states in which a large-area short-circuit can occur.
  • separators can be produced that can meet the requirements for separators in high-performance batteries, especially lithium high-performance batteries.
  • the resulting separators are free or virtually free of closed pores, in which the electrolyte can not penetrate.
  • the separators used for the invention also have the advantage that the anions of the conductive salt partly adhere to the inorganic surfaces of the separator material, which leads to an improvement in the dissociation and thus to a better ion conductivity in the high-current range.
  • Another not inconsiderable advantage of the separator is the very good wettability. Due to the hydrophilic ceramic coating, wetting with electrolytes takes place very rapidly, which likewise leads to improved conductivity.
  • the separator used for the battery according to the invention comprising a flexible nonwoven fabric with a porous inorganic coating on and in this nonwoven, wherein the material of the nonwoven fabric is selected from unwoven, non-electrically conductive polymer fibers, is also characterized in that the nonwoven fabric has a thickness of less than 30 ⁇ m, a porosity of more than 50%, preferably of 50 to 97%, and a pore radius distribution in which at least 50% of the pores have a pore radius of 75 to 150 ⁇ m.
  • the separator particularly preferably comprises a nonwoven which has a thickness of 5 to 30 ⁇ m, preferably a thickness of 10 to 20 ⁇ m. Also particularly important is a homogeneous distribution of pore radii in the web as indicated above. An even more homogeneous distribution of pore radii in the nonwoven leads in conjunction with optimally matched oxide particles of a certain size to one optimized porosity of the separator.
  • the thickness of the substrate has a great influence on the properties of the separator, since on the one hand the flexibility but also the sheet resistance of the electrolyte-impregnated separator depends on the thickness of the substrate. Due to the small thickness, a particularly low electrical resistance of the separator is achieved in the application with an electrolyte.
  • the separator itself has a very high electrical resistance, since it itself must have insulating properties. In addition, thinner separators allow increased packing density in a battery pack so that one can store a larger amount of energy in the same volume.
  • the web has a porosity of 60 to 90%, more preferably from 70 to 90%.
  • the porosity is defined as the volume of the web (100%) minus the volume of the fibers of the web, ie the proportion of the volume of the web that is not filled by material.
  • the volume of the fleece can be calculated from the dimensions of the fleece.
  • the volume of the fibers results from the measured weight of the fleece considered and the density of the polymer fibers.
  • the large porosity of the substrate also allows a higher porosity of the separator, which is why a higher uptake of electrolytes with the separator can be achieved.
  • this has as polymer fibers for the nonwoven preferably non-electrically conductive fibers of polymers as defined above, which are preferably selected from polyacrylonitrile (PAN), polyester, such as.
  • PET polyethylene terephthalate
  • PO polyolefin
  • PP polypropylene
  • PE polyethylene
  • the polymer fibers of the nonwovens preferably have a diameter of from 0.1 to 10 ⁇ m, more preferably from 1 to 4 ⁇ m.
  • Particularly preferred flexible nonwovens have a basis weight of less than 20 g / m 2 , preferably from 5 to 10 g / m 2 .
  • the nonwoven is flexible and has a thickness of less than 30 ⁇ .
  • the separator has a porous, electrically insulating, ceramic coating on and in the fleece.
  • the porous inorganic coating on and in the nonwoven preferably has oxide particles of the elements Li, Al, Si and / or Zr with an average particle size of 0.5 to 7 ⁇ m, preferably 1 to 5 ⁇ m and very particularly preferably 1 , 5 to 3 pm up.
  • the separator has a porous inorganic coating on and in the nonwoven, which has aluminum oxide particles.
  • these have an average particle size of 0.5 to 7 pm, preferably from 1 to 5 pm and most preferably from 1, 5 to 3 pm.
  • the alumina particles are bonded to an oxide of the elements Zr or Si.
  • more than 50% by weight, and more preferably more than 80% by weight, of all particles are preferably in the abovementioned limits of average particle size.
  • the maximum particle size is preferably 1/3 to 1/5 and particularly preferably less than or equal to 1/10 of the thickness of the nonwoven used.
  • the separator preferably has a porosity of from 30 to 80%, preferably from 40 to 75% and particularly preferably from 45 to 70%.
  • the porosity refers to the achievable, ie open pores.
  • the porosity can be determined by the known method of mercury porosimetry or can be calculated from the volume and density of the starting materials used, if it is assumed that only open pores available.
  • the separators used for the battery according to the invention are also distinguished by the fact that they can have a tensile strength of at least 1 N / cm, preferably of at least 3 N / cm and very particularly preferably of 3 to 10 N / cm.
  • the separators can preferably be bent without damage to any radius down to 100 mm, preferably down to 50 mm and most preferably down to 1 mm.
  • the high tensile strength and the good bendability of the separator have the advantage that changes in the geometries of the electrodes occurring during the charging and discharging of a battery can be through the separator without being damaged.
  • the flexibility also has the advantage that commercially standardized winding cells can be produced with this separator. In these cells, the electrode / separator layers are spirally wound together in a standardized size and contacted.
  • the separator it is possible to design the separator to have the shape of a concave or convex sponge or pad, or the shape of wires or a felt. This embodiment is well suited to compensate for volume changes in the battery. Corresponding preparation methods are known to the person skilled in the art.
  • the polymer fleece used in the separator comprises a further polymer.
  • this polymer is arranged between the separator and the negative electrode and / or the separator and the positive electrode, preferably in the form of a polymer layer.
  • the separator is coated with this polymer on one or both sides.
  • Said polymer may be in the form of a porous membrane, ie as a film, or in the form of a nonwoven, preferably in the form of a nonwoven web of nonwoven polymer fibers.
  • These polymers are preferably selected from the group consisting of polyester, polyolefin, polyacrylonitrile, polycarbonate, polysulfone, polyethersulfone, polyvinylidene fluoride, polystyrene, polyetherimide.
  • the further polymer is a polyolefin.
  • Preferred polyolefins are polyethylene and polypropylene.
  • the separator is preferably coated with one or more layers of the further polymer, preferably of the polyolefin, which is preferably likewise present as a nonwoven, that is to say as nonwoven polymer fibers.
  • a non-woven of polyethylene terephthalate is used in the separator, which is coated with one or more layers of the further polymer, preferably of the polyolefin, which is preferably also present as a nonwoven, that is, as nonwoven polymer fibers.
  • separator of the above-described type of separation which is coated with one or more layers of the further polymer, preferably of the polyolefin, which is preferably likewise present as a nonwoven, that is to say as nonwoven polymer fibers.
  • the coating with the further polymer can be achieved by gluing, lamination, by a chemical reaction, by welding or by a mechanical connection.
  • Such polymer composites and processes for their preparation are known from EP 1 852 926.
  • the fiber diameters of the polyethylene terephthalate fleece are preferably larger than the fiber diameters of the further polymer fleece, preferably the polyolefin fleece, with which the separator is coated on one or both sides.
  • the nonwoven made of polyethylene terephthalate then has a higher pore diameter than the nonwoven, which is made of the other polymer.
  • the nonwovens usable in the separator are made of nanofibers of the polymers used, whereby nonwovens are formed which have a high porosity with formation of small pore diameters.
  • the use of a polyolefin in addition to the polyethylene terephthalate ensures increased safety of the electrochemical cell, since in unwanted or excessive heating of the cell, the pores of the polyolefin contract and the charge transport through the separator is reduced or terminated. Should the temperature of the electrochemical cell increase to such an extent that the polyolefin begins to melt, the polyethylene terephthalate effectively counteracts the melting together of the separator and thus an uncontrolled destruction of the electrochemical cell.
  • This combination is for use as a driving force for mobile Information devices, for tools, electric cars and hybrid cars.
  • Suitable electrolytes for the battery according to the invention are known from the prior art.
  • the electrolytes preferably comprise a liquid and a conducting salt.
  • the liquid is a solvent for the conducting salt.
  • the electrolyte is present as an electrolyte solution.
  • Suitable solvents are preferably inert.
  • Suitable solvents include, for example, solvents such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, butyl methyl carbonate, ethyl propyl carbonate, dipropyl carbonate, cyclopentanones, sulfolanes, dimethylsulfoxide, 3-methyl-1,3-oxazolidine-2-one, Butyrolactone, 1, 2-diethoxymethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, methyl acetate, ethyl acetate, nitromethane, 1, 3-propanesultone.
  • solvents such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, butyl methyl
  • ionic liquids may also be used.
  • Ionic liquids are known in the art. They contain only ions. Examples of useful cations which may in particular be alkylated are imidazolium, pyridinium, pyrrolidinium, guanidinium, uronium, thiuronium, piperidinium, morpholinium, sulfonium, ammonium and phosphonium cations. Examples of useful anions are halide, tetrafluoroborate, trifluoroacetate, triflate, hexafluorophosphate, phosphinate and tosylate anions.
  • Suitable ionic liquids are: N-methyl-N-propyl-piperidinium bis (trifluoromethylsulfonyl) imide, N-methyl-N-butyl-pyrrolidinium bis (trifluoromethyl-sulfonyl) imide, N-butyl-N-trimethyl-ammonium - bis (trifluoromethylsulfonyl) imide, triethylsulfonium bis (trifluoromethylsulfonyl) imide,
  • Preferred conductive salts are lithium salts which have inert anions and which are non-toxic.
  • Suitable lithium salts are, for example, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium bis (trifluoromethylsulfonylimide), lithium trifluoromethanesulfonate, lithium tris (trifluoromethylsulfonyl) methide, lithium tetrafluoroborate, lithium perchlorate, lithium tetrachloroaluminate, lithium chloride, lithium bisoxalatoborate, lithium difluoroxalatoborate, and mixtures of two or more of these salts ,
  • the preparation of the lithium-ion battery according to the invention may preferably be carried out by precipitating the lithium transition metal phosphate as a powder on the electrode and compacting it into a thin film, optionally with the use of a binder, to produce the positive electrode.
  • the other electrode may be laminated on the first electrode, the separator being laminated in the form of a foil beforehand on the negative or the positive electrode. It is also possible to simultaneously process the positive electrode, the separator and the negative electrode under mutual lamination.
  • the positive electrode of the battery according to the invention comprises lithium manganese phosphate or lithium cobalt phosphate as the lithium transition metal phosphate.
  • the lithium manganese phosphate or lithium cobalt phosphate is carbon coated.
  • the separator comprises a nonwoven web of nonwoven polyethylene terephthalate fibers which is coated on both sides with an ion-conducting inorganic material which comprises aluminum oxide.
  • the nonaqueous electrolyte comprises a liquid selected from: ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, butyl methyl carbonate, ethyl propyl carbonate, dipropyl carbonate, an ionic liquid, and mixtures of two or more of these liquids.
  • the lithium salt is LiPF 6 .
  • the battery according to the invention a high energy density and capacity can be made available at high voltage, wherein the battery has good stability even at high voltage output. Therefore, it can be preferably used for supplying power to mobile information devices, tools, electric automobiles and hybrid automobiles.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
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  • Physics & Mathematics (AREA)
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Abstract

L'invention concerne une batterie lithium-ion qui comprend : (i) une électrode positive renfermant au moins un phosphate de lithium et de métal de transition de structure olivine, le métal de transition étant choisi parmi le manganèse, le cobalt, le nickel ou un mélange de deux ou trois de ces éléments; (ii) une électrode négative; (iii) un séparateur qui isole l'électrode positive de l'électrode négative et qui est perméable aux ions lithium, ledit séparateur comprenant un nontissé qui est constitué de fibres polymères non tissées, non électroconductrices, et dont l'une ou les deux faces sont enduites d'une matière inorganique conductrice d'ions; (iv) un électrolyte non aqueux.
EP12714968.0A 2011-04-14 2012-04-05 Batterie lithium-ion à tension élevée Withdrawn EP2697844A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011017105A DE102011017105A1 (de) 2011-04-14 2011-04-14 Lithium-Ionen-Batterie mit hoher Spannung
PCT/EP2012/001535 WO2012139742A1 (fr) 2011-04-14 2012-04-05 Batterie lithium-ion à tension élevée

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EP2697844A1 true EP2697844A1 (fr) 2014-02-19

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US (1) US20140127536A1 (fr)
EP (1) EP2697844A1 (fr)
JP (1) JP2014514712A (fr)
KR (1) KR20140034779A (fr)
CN (1) CN103534836A (fr)
DE (1) DE102011017105A1 (fr)
WO (1) WO2012139742A1 (fr)

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US11050284B2 (en) * 2015-05-11 2021-06-29 Eaglepicher Technologies, Llc Electrolyte, a battery including the same, and methods of reducing electrolyte flammability
CN106920910A (zh) * 2015-12-27 2017-07-04 深圳市沃特玛电池有限公司 一种锂电池
JP6369818B2 (ja) * 2016-10-14 2018-08-08 Ａｔｔａｃｃａｔｏ合同会社 骨格形成剤を用いた電極
JP2018101639A (ja) * 2018-03-12 2018-06-28 Ａｔｔａｃｃａｔｏ合同会社 セパレータ
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JP6678358B2 (ja) * 2018-03-12 2020-04-08 Ａｔｔａｃｃａｔｏ合同会社 骨格形成剤、これを用いた電極及び電極の製造方法
JP6635616B2 (ja) * 2018-10-10 2020-01-29 Ａｔｔａｃｃａｔｏ合同会社 非水電解質二次電池用の正極及びこれを用いた電池
JP2021193693A (ja) * 2019-09-06 2021-12-23 Ａｔｔａｃｃａｔｏ合同会社 骨格形成剤、これを用いた電極及び電極の製造方法
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WO2012139742A1 (fr) 2012-10-18
CN103534836A (zh) 2014-01-22
US20140127536A1 (en) 2014-05-08
DE102011017105A1 (de) 2012-10-18
KR20140034779A (ko) 2014-03-20
JP2014514712A (ja) 2014-06-19

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