EP4143903A1 - Pile électrochimique au lithium-ion secondaire - Google Patents

Pile électrochimique au lithium-ion secondaire

Info

Publication number
EP4143903A1
EP4143903A1 EP21721545.8A EP21721545A EP4143903A1 EP 4143903 A1 EP4143903 A1 EP 4143903A1 EP 21721545 A EP21721545 A EP 21721545A EP 4143903 A1 EP4143903 A1 EP 4143903A1
Authority
EP
European Patent Office
Prior art keywords
lithium
current collector
ion cell
negative electrode
electrode
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.)
Pending
Application number
EP21721545.8A
Other languages
German (de)
English (en)
Inventor
Edward Pytlik
David ENSLING
Ihor Chumak
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.)
VARTA Microbattery GmbH
Original Assignee
VARTA Microbattery 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 VARTA Microbattery GmbH filed Critical VARTA Microbattery GmbH
Publication of EP4143903A1 publication Critical patent/EP4143903A1/fr
Pending 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
    • H01M4/13—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/425—Structural combination with electronic components, e.g. electronic circuits integrated to the outside of the casing
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/109—Primary casings; Jackets or wrappings characterised by their shape or physical structure of button or coin shape
    • 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
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/538—Connection of several leads or tabs of wound or folded electrode stacks
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 a secondary electrochemical lithium-ion cell and a winding or stack formed from negative and positive electrodes for a secondary electrochemical lithium-ion cell and a method for producing such a winding or stack and a method for producing a secondary electrochemical Lithium-ion cell.
  • Electrochemical cells are able to convert stored chemical energy into electrical energy through a redox reaction.
  • the electrochemical cells typically include a positive and a negative electrode. In the event of a discharge, electrons are released at the negative electrode through an oxidation process. This results in a stream of electrons that can be tapped by an external consumer so that the electrochemical cell acts as an energy supplier. At the same time, an ion current corresponding to the electrode reaction occurs within the cell. This ion flow is made possible by an ion-conducting electrolyte.
  • the discharge is reversible, one speaks of a secondary cell, which means that it is possible to reverse the conversion of chemical energy into electrical energy that occurred during the discharge and thus to charge the cell.
  • the widespread lithium-ion cells are based on the use of lithium, which can migrate back and forth between the electrodes of the cell in ionic form.
  • the lithium-ion cells are characterized by a comparatively high energy density.
  • the negative electrode and the positive electrode of a lithium-ion cell are usually formed by so-called composite electrodes which, in addition to electrochemically active components, also include electrochemically inactive components.
  • electrochemically active components active materials
  • carbon-based particles such as graphitic carbon
  • non-graphitic carbon materials that are suitable for intercalation of lithium
  • metallic and semi-metallic materials that can be alloyed with lithium can also be used.
  • the elements tin, antimony and silicon are able to form intermetallic phases with lithium.
  • Lithium cobalt oxide (LiCo0 2 ), lithium manganese oxide (LiMn 2 0) or lithium iron phosphate (LiFeP0 4 ) or derivatives thereof can be used as active materials for the positive electrode.
  • the electrochemically active materials are usually contained in the electrodes in particle form.
  • the composite electrodes generally comprise a flat and / or strip-shaped current collector, for example a metallic foil, which is coated with the active material.
  • the current collector for the negative electrode can be formed from copper or nickel, for example, and the current collector for the positive electrode (cathode current collector) can be formed from aluminum, for example.
  • the electrodes can comprise an electrode binder (e.g. polyvinylidene fluoride (PVDF) or another polymer). This ensures the mechanical stability of the electrodes and often also the adhesion of the active material to the current collectors.
  • the electrodes can contain conductivity-improving additives and other additives.
  • lithium-ion cells are, for example, solutions of lithium salts such as lithium hexafluorophosphate (LiPF 6 ) in organic solvents (e.g. ethers and esters of carbonic acid).
  • LiPF 6 lithium hexafluorophosphate
  • organic solvents e.g. ethers and esters of carbonic acid
  • the composite electrodes are often processed into a stack or a roll, the negative electrode (s) and the positive electrode (s) being separated from one another by means of a separator within the stack or the roll.
  • current conductors can be provided which are connected to the current collectors, for example by welding. If necessary, the current collectors can also be contacted directly with a housing part of the lithium-ion cell.
  • a lithium-ion cell The function of a lithium-ion cell is based on the fact that sufficient mobile lithium ions (mobile lithium) are available to compensate for the electrical current tapped by migration between the anode and the cathode or between the negative electrode and the positive electrode.
  • mobile lithium is to be understood as meaning that the lithium is available for storage and retrieval processes in the electrodes as part of the discharging and charging processes of the lithium-ion cell or can be activated for this purpose.
  • the discharging and charging processes of a lithium-ion cell it occurs in the course of the Time to lose mobile lithium. These losses occur as a result of various, generally unavoidable side reactions. Mobile lithium is already lost during the first charging and discharging cycle of a lithium-ion cell.
  • a cover layer is usually formed on the surface of the electrochemically active components on the negative electrode.
  • This top layer is called Solid Electrolyte Interphase (SEI) and usually consists primarily of electrolyte decomposition products and a certain amount of lithium that is firmly bound in this layer.
  • SEI Solid Electrolyte Interphase
  • the loss of mobile lithium associated with this process can be between 10% and 35%.
  • the losses in the subsequent charging and discharging cycles are significantly lower.
  • the ongoing loss of mobile lithium leads to a continuously progressive decrease in the capacity and performance of conventional lithium-ion cells.
  • EP 2 486 620 B1 describes a lithium-ion cell with improved aging behavior, the capacity of the negative electrode to absorb lithium being overdimensioned in relation to the positive electrode and at the same time in relation to the total mobile lithium. At the same time, the cell contains an amount of mobile lithium that exceeds the capacity of the positive electrode to absorb lithium.
  • EP 3 255 714 A1 discloses an electrochemical cell with a lithium depot, the lithium depot being provided in the cell in the form of a lithium alloy.
  • the lithium depot can for example be arranged between the electrodes and the housing of the cell.
  • EP 2372732 A1 describes a spiral wound winding with negative and positive electrodes for an electrochemical lithium-ion cell, a lithium ion source being provided within the winding, which is separated from the positive electrode and the negative electrode by means of a separator is that it does not come into contact with the electrodes.
  • the invention has the object of providing an improved lithium-ion cell in which losses of mobile lithium can be compensated in a particularly advantageous manner.
  • this improved lithium-ion cell aging processes of the cell are to be prevented or slowed down in order to achieve a particularly long service life for the cell.
  • This task is accomplished by a secondary lithium-ion electrochemical cell and a coil or stack for a secondary lithium-ion electrochemical cell, such as those made of the independent claims emerge, solved. Furthermore, this object is achieved by a method for producing such a roll or stack and by a method for producing an electrochemical lithium-ion cell according to the further independent claims. Preferred configurations of this lithium-ion cell or of the roll or stack and the manufacturing method emerge from the dependent claims.
  • the lithium-ion cell according to the invention is always characterized by the following features: a. It comprises at least one composite electrode as a negative electrode, the composite electrode comprising at least one anode current collector and at least one electrochemically active component that is able to store and remove lithium ions. b. It comprises at least one composite electrode as a positive electrode, the composite electrode comprising at least one cathode current collector and at least one electrochemically active component that is able to store and remove lithium ions.
  • the negative electrode and / or the positive electrode has or have at least one area in which the anode current collector and / or the cathode current collector is at least partially free of the electrochemically active component, this area being designed as a lithium reserve.
  • the negative electrode and / or the positive electrode thus comprise a current collector with at least one area which is covered by an electrochemically active component and at least one further area which is free of this component and which is designed as a lithium reserve.
  • the area formed as a lithium reserve is preferably completely free of the electrochemically active component.
  • the area is preferably also free of the mentioned electrode binder and / or the mentioned conductivity-improving additives.
  • a lithium reserve means that this area of the negative electrode and / or the positive electrode has metallic lithium and / or a lithium-containing material applied to it.
  • the lithium stored in this area is used in the course the operating time of the lithium-ion cell according to the invention as a depot for lithium, which can be released as mobile lithium in ionic form and is available for the charging and discharging cycles of the lithium-ion cell after its release. This can significantly improve the service life of the lithium-ion cell, since aging processes based on a loss of mobile lithium can be compensated for by the lithium reserve.
  • the metallic lithium or the lithium-containing material of the lithium reserve differ materially from the electrochemically active component, which usually also contains lithium, possibly in ionic form (see below).
  • the lithium depot therefore preferably does not include any lithium-containing alloy or compound that is part of the electrochemically active component.
  • the arrangement of the lithium reserve directly on the current collectors has particular advantages, especially with regard to the optimal use of the geometry of the lithium-ion cell.
  • the space within the lithium-ion cell can be optimally used without the lithium reserve requiring additional space within the lithium-ion cell. Ion cell would take.
  • the area for the lithium reserve can be selected in such a way that geometric collisions with other elements of the lithium-ion cell do not occur.
  • the arrangement of the lithium depot described in EP 2372 732 A1 can increase the risk of electrical short circuits as a result of the lithium depot coming into contact with the edges of oppositely polarized electrodes.
  • the formation of the lithium depot according to the present invention can already take place during the manufacture of the electrodes. This means that no separate steps for training and placing the depot are required at a later point in time.
  • the anode current collector and the cathode current collector of the negative or positive electrode (s) are preferably flat metal substrates, for example made of metal foils or a metal foam or a metal mesh or a metal grid or a metallized fleece. Copper or nickel, for example, or other electrically conductive materials are suitable as the metal for the anode current collector. For example, aluminum or other electrically conductive materials are suitable as metal for the cathode current collector. Materials known to the person skilled in the art can be used as electrochemically active components for the negative electrode and the positive electrode. For the negative electrode, carbon-based particles such as graphitic carbon or non-graphitic carbon materials capable of intercalating lithium, preferably also in particle form, can be used for the negative electrode.
  • metallic and semi-metallic materials that can be alloyed with lithium can also be used, for example using the elements tin, antimony and silicon, which are able to form intermetallic phases with lithium. These materials are also preferably used in particle form.
  • lithium metal oxide compounds and lithium metal phosphate compounds such as LiCo0 2 and LiFeP0 can be used as electrochemically active components.
  • lithium nickel manganese cobalt oxide with the empirical formula LiNi x Mn y CO z 0 2 (where x + y + z is typically 1), lithium manganese spinel (LMO) with the empirical formula LiMn 2 0 4 , or lithium nickel cobalt aluminum oxide (NCA) with the empirical formula LiNi x Co y Al z 0 2 (where x + y + z is typically 1).
  • lithium nickel manganese cobalt aluminum oxide NMCA
  • lithium nickel manganese cobalt aluminum oxide with the empirical formula Lii . n (Nio .4 oMn 0.39 Coo .i6 Alo . o 5 ) o .89 0 2 or Lii + x M-0 compounds and / or mixtures of the materials mentioned can be used.
  • the particulate electrochemically active components are preferably embedded in a matrix made of the aforementioned electrode binder, adjacent particles in the matrix preferably being in direct contact with one another.
  • structured current collectors are used as anode and / or cathode current collectors, for example perforated or otherwise provided with openings, metal foils or metal meshes or metal grids or metallic or metallized fleeces or open-pored metal foams.
  • the cell according to the invention particularly preferably comprises, for the purpose of optimized distribution of lithium ions in the cell, as an anode current collector, a strip-shaped metal foil with a thickness in the range from 4 ⁇ m to 30 ⁇ m and with a first and a second longitudinal edge and two end pieces and
  • a cathode current collector a band-shaped metal foil with a thickness in the range from 4 ⁇ m to 30 ⁇ m and with a first and a second longitudinal edge and two end pieces
  • the anode current collector having a band-shaped main area that is loaded with a layer of negative electrode material, as well as a free edge strip that extends along the first longitudinal edge and which is not loaded with the electrode material
  • the cathode current collector has a band-shaped main area which is loaded with a layer of positive electrode material, and a free edge strip which extends along the first longitudinal edge and which is not loaded with the electrode material.
  • Both the anode current collector and the cathode current collector preferably each have the band-shaped main area and the free edge strip. It is preferred that the band-shaped main area of the anode current collector and / or the band-shaped main area of the cathode current collector, particularly preferably the band-shaped main area of the anode current collector and the band-shaped main area of the cathode current collector, have a plurality of openings.
  • the large number of openings results in a reduced volume and also a reduced weight of the current collector or collectors. This makes it possible to bring more active material into the cell and in this way to drastically increase the energy density of the cell. Energy density increases in the double-digit percentage range can be achieved in this way.
  • the cell according to the invention is characterized by at least one of the immediately following features a. and b. marked: a.
  • the openings in the main area are round or angular holes, in particular punched or drilled holes.
  • the main area of the anode current collector and / or the cathode current collector is perforated, in particular by means of round hole or slotted hole perforation.
  • the perforations are made in the ribbon-shaped main area by means of a laser.
  • the geometry of the openings is not essential to the invention. It is important that the mass of the current collector is reduced as a result of the introduction of the openings and that there is more space for active material, since the openings can be filled with the active material.
  • the openings should preferably not be more than twice the thickness of the layer of the electrode material on the respective current collector.
  • the cell according to the invention is characterized by the immediately following feature a. marked: a.
  • the openings in the current collector, in particular in the main area, have diameters in the range from 1 ⁇ m to 3000 ⁇ m.
  • the cell according to the invention is particularly preferably further characterized by at least one of the immediately following features a. and b. from: a.
  • the anode current collector and / or the cathode current collector have a lower weight per unit area at least in a section of the main area than in the associated free edge strip.
  • the anode current collector and / or the cathode current collector have no or fewer openings per unit area in the free edge strip than in the main area.
  • the free edge strips of the anode and cathode current collectors delimit the main area towards the first longitudinal edges.
  • the anode and cathode current collectors preferably include free edge strips along their two longitudinal edges.
  • the openings characterize the main area. In other words, the boundary between the main area and the free edge strip or strips corresponds to a transition between areas with and without openings.
  • the perforations are preferably distributed essentially uniformly over the main area or areas.
  • the cell according to the invention is characterized by at least one of the immediately following features a. to c. from: a.
  • the weight per unit area of the anode current collector and / or the cathode current collector is reduced by 5% to 80% in the main area compared to the weight per unit area of the respective current collector in the free edge strip.
  • the current collector has a hole area in the range from 5% to 80%.
  • the current collector has a tensile strength of 20 N / mm 2 to 250 N / mm 2 in the main area.
  • the hole area which is often referred to as the free cross-section, can be determined in accordance with ISO 7806-1983.
  • the tensile strength of the current collector or collectors in the main area is reduced compared to current collectors without the openings. It can be determined in accordance with DIN EN ISO 527 Part 3.
  • anode current collector and the cathode current collector are designed to be identical or similar with regard to the openings. The achievable in each case
  • the secondary electrochemical lithium-ion cell expediently also comprises a housing which preferably encloses the electrodes in a gas- and / or liquid-tight manner.
  • the cell comprises an electrical conductor for electrical contacting of the negative electrode and / or an electrical conductor for electrical contacting of the positive electrode in order to enable electrical contacting of the electrodes.
  • One end of these electrical conductors can be connected to the anode or the Cathode current collector be welded. Another end can be welded to a housing part or led out of the housing through a pole bushing.
  • direct contacting of the electrodes with the housing or with parts of the housing can also be provided. This is particularly preferred and will be dealt with separately.
  • the lithium-ion cell expediently comprises at least one separator for separating the positive and negative electrodes in a manner known per se.
  • the cell comprises at least one electrolyte which is customary per se, in particular based on at least one lithium salt such as lithium hexafluorophosphate, which is dissolved in an organic solvent (for example in a mixture of organic carbonates).
  • an organic solvent for example in a mixture of organic carbonates.
  • the lithium-ion cell according to the invention is characterized by at least one of the immediately following features a. to c. from: a.
  • the negative electrode designed as a composite electrode and the positive electrode designed as a composite electrode are each band-shaped.
  • the negative electrode and the positive electrode are separated from each other by a separator.
  • the negative electrode and the positive electrode are part of a coil.
  • the negative electrode and the positive electrode together with the separator form a composite which is processed into a roll, in particular a spiral-shaped roll.
  • a coil is preferably cylindrical and has two terminal, preferably flat end faces. The provision of the electrodes in the form of such a coil allows a particularly advantageous arrangement of the electrodes in cylindrical housings.
  • the lithium-ion cell according to the invention is characterized by at least one of the immediately following features a. and b. from: a.
  • the area is located at a longitudinal end of the band-shaped negative electrode and / or the band-shaped positive electrode.
  • the area with the lithium reserve forms an outer side of the winding and / or delimits a cavity in the center of the winding.
  • the outer side of the coil can for example be formed by the negative electrode.
  • the area with the lithium reserve can take up part of this outer side or the entire outer side of the coil.
  • the area of the lithium reserve is preferably only applied to the outer side of the anode current collector and not to the inner side of the anode current collector, so that the inner side of the electrode of the outer winding is usually coated with the electrochemically active component.
  • the area with the lithium reserve can be located in the core of the winding. In particular, these positions of the area for the lithium reserve are particularly advantageous, since these areas are generally unused and to this extent the utilization of these areas for a lithium reserve is particularly advantageous and economical.
  • the lithium-ion cell according to the invention is characterized by at least one of the immediately following features a. to c. from: a.
  • the negative electrode designed as a composite electrode and the positive electrode designed as a composite electrode are part of a stack in which they are arranged one above the other.
  • the negative electrode and the positive electrode are separated from each other by a separator.
  • the area designed as a lithium reserve is located at an edge of the band-shaped negative electrode and / or the band-shaped positive electrode.
  • This form of arrangement of negative electrode (s) and positive electrode (s) can also be used to advantage for different geometries of a lithium-ion cell, with this arrangement of the electrodes in particular lithium-ion cells with prismatic Housings can be manufactured.
  • the lithium-ion cell according to the invention is characterized by at least one of the immediately following features a. or b. from: a. the anode current collector and the cathode current collector each have two flat sides separated by a circumferential edge and are coated on both sides with the electrochemically active components, b. the area designed as a lithium reserve is located on only one flat side of the anode current collector and / or the cathode current collector.
  • both the anode current collector and the cathode current collector have the two flat sides which are each coated with the respective electrochemically active components.
  • the area with the lithium reserve is preferably located on only one of the flat sides of the anode current collector and / or the cathode current collector.
  • the lithium-ion cell according to the invention is characterized by at least one of the immediately following features a. or b. from: a. the lithium-ion cell comprises a housing which encloses the negative electrode and the positive electrode, b. the area of the negative electrode or the positive electrode designed as a lithium reserve faces the housing of the lithium-ion cell.
  • the edge regions of the electrode arrangement are used in order to carry out a coating with lithium-containing material instead of a coating with the electrochemically active components.
  • only the negative electrode is used to form the lithium reserve.
  • only the negative electrode has the at least one area in which the anode current collector is at least partially free of the electrochemically active component and this area is designed as a lithium reserve.
  • the lithium-ion cell according to the invention is characterized by at least one of the immediately following features a. until h. from: a.
  • the lithium reserve comprises electrochemically active lithium, which is arranged in the area formed as a lithium reserve on the anode current collector and / or the cathode current collector.
  • the lithium reserve comprises activatable lithium, which is arranged in the area formed as a lithium reserve on the anode current collector and / or the cathode current collector.
  • the lithium reserve comprises at least one lithium-containing compound, in particular a lithium-containing alloy, which is arranged in the area formed as a lithium reserve on the anode current collector and / or the cathode current collector.
  • the lithium reserve is formed by a lithium foil which is arranged in the area formed as a lithium reserve on the anode current collector and / or the cathode current collector.
  • the lithium reserve is formed by a lithium strip which is arranged in the area formed as a lithium reserve on the anode current collector and / or the cathode current collector.
  • the lithium reserve is formed by vapor-deposited lithium or lithium-containing material, which is arranged in the area formed as a lithium reserve on the anode current collector and / or the cathode current collector.
  • the lithium reserve is formed by encapsulated lithium particles which are arranged in the area formed as a lithium reserve on the anode current collector and / or the cathode current collector.
  • the lithium reserve is formed by a coating which is arranged in the area formed as a lithium reserve on the anode current collector and / or the cathode current collector.
  • the lithium or the lithium-containing materials can be applied, for example, in the form of a paste or some other coating to the corresponding area of the positive electrode and / or in particular the negative electrode.
  • encapsulated lithium particles such as SLMP (Stabilized Lithium Metal Powder, FMC Corporation, USA) can be used for this purpose.
  • the lithium can, for example, be electrochemically deposited, vapor-deposited or pressed on.
  • the lithium reserve can be activated by cycling.
  • the energy storage element according to the invention can be a button cell.
  • Button cells are cylindrical and have a height that is less than their diameter is. They are suitable for supplying small electronic devices such as watches, hearing aids and wireless headphones with electrical energy.
  • the energy storage element according to the invention is preferably a cylindrical button cell with a circular top, which is flat in at least a central sub-area, and a circular bottom, which is flat in at least a central sub-area, and an annular jacket in between.
  • the shortest distance between a point on the flat area or part of the top and a point on the area or part of the bottom is preferably in the range from 4 mm to 15 mm.
  • the maximum distance between two points on the jacket of the button cell is preferably in the range from 5 mm to 25 mm. The stipulation here is that the maximum distance between the two points on the shell side is greater than the distance between the two points on the top and bottom.
  • the nominal capacity of the energy storage element according to the invention is generally up to 1500 mAh.
  • the nominal capacity is preferably in the range from 100 mAh to 1000 mAh, particularly preferably in the range from 100 to 800 mAh.
  • the energy storage element according to the invention can also be a cylindrical round cell.
  • Cylindrical round cells have a height that is greater than their diameter. They are suitable for supplying modern metering, security and automotive applications such as electricity, water, gas meters, heating cost meters, medical pipettes, sensors and alarm systems, house alarm systems, sensors and sensor networks, backup batteries for theft protection systems in automotive engineering with electrical energy.
  • the height of the round cells is preferably in the range from 15 mm to 150 mm.
  • the diameter of the cylindrical round cells is preferably in the range from 10 mm to 50 mm. Within these ranges, form factors of, for example, 18 x 65 (diameter times height in mm) or 21 x 70 (diameter times height in mm) are particularly preferred. Cylindrical round cells with these form factors are particularly suitable for powering electrical drives for motor vehicles and tools.
  • the nominal capacity of the energy storage element according to the invention is generally up to 6000 mAh.
  • the cell has in one embodiment as a lithium Ion cell preferably has a nominal capacity in the range from 2000 mAh to 5000 mAh, particularly preferably in the range from 3000 to 4500 mAh.
  • the lithium-ion cell according to the invention is designed in such a way that the electrodes are designed in the form of a coil according to the so-called contact plate design, as described in particular in WO 2017/215900 A1. Reference is hereby made in full to WO 2017/215900 A1.
  • the lithium-ion cell according to the invention is characterized in that the positive and negative electrodes are offset from one another within the composite of electrodes and separator present as a coil, so that a longitudinal edge of the anode current collector consists of one of the end faces and a longitudinal edge of the cathode current collector emerges from the other of the end faces,
  • the lithium-ion cell according to the invention has a metallic contact plate which rests on one of the longitudinal edges so that a line-like contact zone results, and the contact plate is connected to the longitudinal edge along this line-like contact zone by welding.
  • the overhang of the current collectors resulting from the staggered arrangement can be used by preferring them over theirs by means of an appropriate current conductor full length contacted.
  • the aforementioned contact plate is used as a current conductor. This can very significantly reduce the internal resistance within the cell according to the invention. The arrangement described can therefore intercept the occurrence of large currents very well. With minimized internal resistance, thermal losses are reduced at high currents. In addition, the dissipation of thermal energy via the poles is promoted.
  • the contact plate can in turn be connected to a pole of the cell according to the invention, for example a housing pole.
  • the contact plate can be connected to the longitudinal edge.
  • the contact plate can be connected to the longitudinal edge along the linear contact zone via at least one weld seam.
  • the longitudinal edge can comprise one or more sections which are each continuously connected to the contact plate over their entire length via a weld seam.
  • the section (s) continuously connected to the contact plate over its entire length can extend over at least 25%, preferably over at least 50%, particularly preferably over at least 75%, of the total length of the longitudinal edge.
  • the longitudinal edge can be continuously welded to the contact plate over its entire length.
  • the cell according to the invention has at least one of the following features:
  • the contact plate is a metal plate with a thickness in the range from 200 ⁇ m to 1000 ⁇ m, preferably 400-500 ⁇ m.
  • the contact plate is made of aluminum, titanium, nickel, stainless steel or nickel-plated steel.
  • the contact plate can have at least one slot and / or at least one perforation. These serve to counteract any deformation of the plate when the welded connection is made.
  • the contact plate has the shape of a disk, in particular the shape of a circular or at least approximately circular disk. It then has an outer circular or at least approximately circular disc edge.
  • An approximately circular disk is to be understood here in particular as a disk which has the shape of a circle with at least one separated circle segment, preferably with two to four separated circle segments.
  • the cell according to the invention particularly preferably has a first contact plate, which rests on the longitudinal edge of the anode current collector, so that a line-like first contact zone with spiral geometry results, and a second contact plate, which rests on the longitudinal edge of the cathode current collector, so that a line-like second contact zone results Contact zone with spiral geometry results.
  • Both contact plates are preferably connected to one pole of the cell according to the invention, for example a housing pole.
  • the first contact plate and the anode current collector are both made of the same material. This is particularly preferably selected from the group with copper, nickel, titanium, nickel-plated steel and stainless steel.
  • the second contact plate and the cathode current collector are particularly preferably both made of the same material from the group comprising aluminum, titanium and stainless steel (e.g. of the 1.4404 type).
  • the invention further comprises a coil or stack for a secondary electrochemical lithium-ion cell.
  • the roll or stack has the following characteristics: a.
  • the winding or stack comprises at least one composite electrode as a negative electrode, the composite electrode comprising at least one anode current collector and at least one electrochemically active component that is able to store and remove lithium ions.
  • the coil or stack comprises at least one composite electrode as a positive electrode, the composite electrode comprising at least one cathode current collector and at least one electrochemically active component that is able to store and remove lithium ions.
  • the negative electrode and the positive electrode are separated from each other by a separator;
  • the negative electrode and / or the positive electrode have at least one area in which the anode current collector and / or the cathode current collector is at least partially free of the electrochemically active component and this area is designed as a lithium reserve.
  • the invention further comprises a method for producing the described coil or the described stack, which is provided for a secondary electrochemical lithium-ion cell.
  • This procedure consists of the following steps: a.
  • a composite electrode is provided as a negative electrode in that a strip-shaped and / or flat anode current collector is coated on both sides with at least one electrochemically active component that is able to store and remove lithium ions.
  • a composite electrode is provided as a positive electrode by coating a strip-shaped and / or flat cathode current collector with at least one electrochemically active component that is able to store and remove lithium ions on both sides.
  • At least one area is left out which is not coated with the respective electrochemical component.
  • a lithium-containing material is applied to the at least one recessed area in order to form a lithium reserve.
  • the negative and positive electrodes are processed into a roll or a stack with at least one separator.
  • the invention comprises a method for producing an electrochemical lithium-ion cell in the manner described above.
  • This procedure consists of the following steps: a. A roll or stack is provided as described above. b. The roll or stack is placed in a housing. c. The roll or stack is provided with at least one electrolyte, i. The negative electrode and the positive electrode are electrically contacted with the housing or with electrical conductors that can be guided through the housing, e. The case is closed.
  • the housing is in particular a housing that is customary for such cells, for example a housing for a cylindrical round cell or a button cell.
  • the method preferably includes electrical contacting of the negative and positive electrodes.
  • the electrical contact is made with the aid of separate electrical conductors.
  • it can also particularly in the case of the above described contact plate designs be provided that direct contact is made with the housing via the contact plates.
  • FIG. 1 shows a schematic view of a negative electrode and a positive electrode in a plan view according to a preferred embodiment of the invention
  • FIG. 2 shows a schematic view of a negative electrode and a positive electrode according to the preferred embodiment of the invention shown in FIG. 1 in cross section;
  • FIG 3 shows a schematic representation of an electrode arrangement arranged in a housing in the form of a coil (cross section) according to a preferred embodiment of the invention.
  • FIG. 4 shows a plan view of a current collector in an embodiment with openings
  • Fig. 5 is a sectional view of the current collector shown in Fig. 4,
  • FIG. 6 shows a plan view of a negative electrode which can be processed into a lithium-ion cell according to the invention
  • FIG. 7 is a sectional view of the negative electrode shown in FIG. 6;
  • FIG. 8 shows a plan view of a composite produced using the negative electrode shown in FIG. 7 and a positive electrode and two separators
  • FIG FIG. 9 is a sectional view of the composite shown in FIG. 8 from the
  • Electrodes and the separators are Electrodes and the separators.
  • FIGS. 1 and 2 schematically illustrate a negative electrode 10 and a positive electrode 20 in plan view (FIG. 1) and in cross section (FIG. 2).
  • the negative electrode 10 which is designed in the form of a strip, has at one end a region 11 which is designed as a lithium reserve.
  • Both the negative electrode 10 and the positive electrode 20 are designed as composite electrodes, an anode current collector 12 in the case of the negative electrode 10 and a cathode current collector 22 in the case of the positive electrode 20 being coated on both sides with an electrochemically active component 13 and 23, respectively .
  • the electrochemically active component 13 of the negative electrode 10 can be, for example, a mixture of silicon and graphite and an electrode binder.
  • the electrochemically active component 23 of the positive electrode 20 is, for example, a particulate lithium metal oxide compound in a binder matrix.
  • the region 11, which is designed as a lithium reserve, is located at one end of the strip-shaped electrode on one side of the anode current collector 12.
  • the lithium-containing material contained in area 11 can be, for example, a lithium foil or a lithium strip. In other exemplary embodiments, this can be vapor-deposited lithium or lithium substances in a paste or in another coating.
  • the lithium-containing material can be formed by encapsulated lithium particles which are applied to the anode current collector 12 in the form of a coating.
  • the anode current collector 12 and the cathode current collector 22 can be conventional electrically conductive foils, in particular metallic foils or foil strips. Copper or nickel are particularly suitable for the negative electrode. Aluminum is particularly suitable for the positive electrode.
  • the anode current collector and the cathode current collector are preferably in a structured form, for example perforated or as an open-pored foam.
  • FIG. 3 schematically illustrates the structure of a coil 100 formed from electrodes 10 and 20.
  • the coil 100 is constructed in a spiral shape, with a composite of negative electrode 10 and positive electrode 20, which are separated from one another by a separator 40, through Winding is built around a winding axis.
  • the electrodes 10 and 20 and the separator 40 are drawn at a distance from one another. In fact, they lie directly on top of one another and are connected to one another, for example, by lamination.
  • the outer turn is formed outwardly by the negative electrode 10, the outer side of the negative electrode 10 partially including a region 11 which is designed as a lithium reserve. In this area, the negative electrode 10 is not coated with an electrochemically active component, but instead has a lithium material applied to it.
  • the outer region of the negative electrode 10 does not face the positive electrode 20, but rather lies opposite the inside of the housing 30.
  • Figures 4 and 5 illustrate the design of a perforated current collector 110 that can be used in a cell according to the invention.
  • 4 is a section along S1.
  • the current collector 110 comprises a plurality of perforations 111, which are rectangular holes.
  • the area 110a is characterized by the openings 111, whereas in the area 110b there are no openings along the longitudinal edge 110e.
  • the current collector 110 therefore has a significantly lower weight per unit area in the area 110a than in the area 110b.
  • FIGS. 6 and 7 illustrate a negative electrode 120 which was manufactured with a negative electrode material 123 applied to both sides of the current collector 110 shown in FIGS. 4 and 5.
  • 7 is a section along S2.
  • the current collector 110 now has a band-shaped main region 122 which is loaded with a layer of the negative electrode material 123, as well as a free edge strip 121 which extends along the longitudinal edge 110e and which is not loaded with the electrode material 123.
  • the electrode material 123 also fills the openings 111.
  • FIGS. 8 and 9 illustrate an electrode-separator composite 104 that was fabricated using the negative electrode 120 illustrated in FIGS. 6 and 7.
  • it comprises the positive electrode 130 and the separators 118 and 119.
  • FIG. 9 is a section along S3.
  • the positive electrode 130 is based on the same current collector design as the negative electrode 120.
  • the current collectors 110 and 115 of the negative electrode 120 and the positive electrode 130 preferably differ only in the respective material selection.
  • the current collector 115 of the positive electrode 130 comprises a band-shaped main region 116 which is loaded with a layer of positive electrode material 125, as well as a free edge strip 117 which extends along the longitudinal edge 115e and which does not coincide with the Electrode material 125 is loaded.
  • the composite 104 can be converted into a coil such as can be contained in a cell according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

Pile électrochimique au lithium-ion secondaire comprenant au moins une électrode composite en tant qu'électrode négative (10), l'électrode composite comprenant au moins un collecteur de courant d'anode (12) et au moins un composant électrochimiquement actif qui permet aux ions lithium de se déplacer à l'intérieur et à l'extérieur. La pile au lithium-ion comprend en outre au moins une électrode composite en tant qu'électrode positive (20), l'électrode composite comprenant au moins un collecteur de courant de cathode (22) et au moins un composant électrochimiquement actif qui permet aux ions lithium de se déplacer à l'intérieur et à l'extérieur. En outre, l'électrode négative (10) et/ou l'électrode positive (20) présentent au moins une région (11), dans laquelle le collecteur de courant d'anode (12) et/ou le collecteur de courant de cathode (22) sont au moins partiellement exempts du composant électrochimiquement actif, et cette région (11) étant formée en tant que réserve de lithium.
EP21721545.8A 2020-04-29 2021-04-28 Pile électrochimique au lithium-ion secondaire Pending EP4143903A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20172155.2A EP3905388A1 (fr) 2020-04-29 2020-04-29 Élément électrochimique secondaire au lithium-ion
PCT/EP2021/061152 WO2021219732A1 (fr) 2020-04-29 2021-04-28 Pile électrochimique au lithium-ion secondaire

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JP4893495B2 (ja) * 1995-03-06 2012-03-07 宇部興産株式会社 非水二次電池
KR19980702606A (ko) * 1995-03-06 1998-08-05 무네유키 가코우 비수성 이차전지
DE19528049A1 (de) * 1995-07-31 1997-02-06 Varta Batterie Lithium-Ionen-Zelle
JP2000243452A (ja) * 1999-02-23 2000-09-08 Toyota Central Res & Dev Lab Inc リチウムイオン二次電池
US7846571B2 (en) * 2006-06-28 2010-12-07 Robert Bosch Gmbh Lithium reservoir system and method for rechargeable lithium ion batteries
JP2008159314A (ja) * 2006-12-21 2008-07-10 Fdk Corp リチウムイオン吸蔵・放出型有機電解質蓄電池
US9496584B2 (en) 2008-12-26 2016-11-15 Jm Energy Corporation Wound-type accumulator having simplified arrangement of a lithium ion source
DE102010044008A1 (de) 2010-11-16 2012-05-16 Varta Micro Innovation Gmbh Lithium-Ionen-Zelle mit verbessertem Alterungsverhalten
US9812701B2 (en) * 2014-06-30 2017-11-07 Samsung Sdi Co., Ltd. Rechargeable lithium battery
EP3255714B1 (fr) 2016-06-07 2019-07-31 VARTA Microbattery GmbH Cellules electrochimiques a depot de lithium, procede de preparation de telles cellules et batterie les comprenant
EP3258519A1 (fr) 2016-06-16 2017-12-20 VARTA Microbattery GmbH Cellule electrochimique a resistance interne optimisee
US11171388B2 (en) * 2018-06-12 2021-11-09 Global Graphene Group, Inc. Method of improving fast-chargeability of a lithium battery
CN109004234A (zh) * 2018-07-24 2018-12-14 安普瑞斯（无锡）有限公司 一种锂离子二次电池

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US20230207789A1 (en) 2023-06-29
EP3905388A1 (fr) 2021-11-03
JP2023523740A (ja) 2023-06-07
KR20220163479A (ko) 2022-12-09
CN115428187A (zh) 2022-12-02

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