EP2715859A1 - Cellule électrochimique - Google Patents

Cellule électrochimique

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Publication number
EP2715859A1
EP2715859A1 EP12721419.5A EP12721419A EP2715859A1 EP 2715859 A1 EP2715859 A1 EP 2715859A1 EP 12721419 A EP12721419 A EP 12721419A EP 2715859 A1 EP2715859 A1 EP 2715859A1
Authority
EP
European Patent Office
Prior art keywords
sei layer
protective device
electrochemical cell
stabilizing additive
lithium
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Withdrawn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
EP12721419.5A
Other languages
German (de)
English (en)
Inventor
Tim Schaefer
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 EP2715859A1 publication Critical patent/EP2715859A1/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Withdrawn legal-status Critical Current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
    • 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
    • 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
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 cell can preferably be used for driving a vehicle with an electric motor, preferably with hybrid drive or in "plug-in" operation.
  • electrochemical cells in particular lithium secondary batteries
  • mobile information devices such as, for example, mobile telephones, in tools or in electrically powered automobiles and in hybrid-powered automobiles.
  • electrochemical cells all the cells used, but especially those for propulsion of automobiles, have to meet the high requirements: as far as possible high electrical capacity and energy density, which remains stable over a high number of charging and discharging cycles, with the lowest possible weight.
  • electrochemical cells The longevity of electrochemical cells is often dependent on the aging of the electrodes. In the aging process, the electrochemical cells lose capacity and performance. This process takes place to a greater or lesser extent in most common electrochemical cells, depending on the circumstances of use (temperature, storage conditions, state of charge, etc.), but also the quality and processing of the materials during the electrochemical cell manufacturing process. For example, high-quality processing of pure materials can lead to long-lasting electrochemical cells that age only slightly over a longer period of time, thus losing less capacity and performance.
  • SEI layer An example of such a chemical reaction is the formation of the so-called SEI layer.
  • the solid electrolyte interface (SEI) layer is formed at the interface between the active material of the cathode and / or the anode and the nonaqueous electrolyte during the first charging and discharging cycles, and consists essentially of reaction products of electrolyte and active material , Such reaction products may be, for example, Li 2 O, LiF, polymeric compounds or (semi) carbonates such as Li 2 C0 3 .
  • the initial formation of the SEI layer results in an initial irreversible capacity loss of the electrochemical cell.
  • the formation of a stable SEI layer on the surface of the electrochemical active material is of vital importance for the longevity of the cell.
  • Some of the aforementioned reaction products, such as the (semi) carbonates, are metastable compounds which under certain conditions (eg, heat) can degrade to more stable products, such as LiF. This can lead to the formation of cracks within the SEI layer, as a result of which electrolyte can re-penetrate into the active material and further decompose it, which can lead to a further irreversible loss of capacity of the cell; the SEI layer is growing.
  • Overloading the cell can lead to the opposite process, namely the decomposition of the SEI layer.
  • the cell may experience a loss of capacity; the cell is aging.
  • the SEI layer plays not only a role in the aging of the cell but also in its safety by making lithium dendrite growth more difficult, if not impossible.
  • cracking within the SEI layer can cause lithium dendrites to grow through the cracks or pores, which can lead to cell shorting.
  • an electrochemical cell comprising at least one negative electrode, at least one positive electrode and at least one electrolyte, wherein the at least one negative electrode substantially comprises at least one carbon-containing electrochemical active material which is capable of producing a "solid electrolyte interface".
  • the electrochemical cell has at least one stabilizing additive which is capable of stabilizing the SEI layer
  • at least one protective device is provided which at least has a stabilizing additive and is preferably configured as a storage container, wherein the at least one stabilizing additive is at least partially released from the at least one protective device when, with regard to the SEI layer, at least a predetermined parameter is reached or exceeded or undershot.
  • An advantage of the electrochemical cell according to the invention is that the use of at least one protective device, which can interact with the SEI layer at least one stabilizing additive only when needed, and not before, for example, by unwanted chemical and / or physical processes during operation electrochemical cell is destroyed, and thus is not available or not in sufficient quantity when needed.
  • an electrochemical cell at least one protective device which has a first shape, and a second shape, wherein the at least one protective device changes from the first to the second shape if, with regard to the SEI layer, at least one predetermined parameter, in particular a temperature, pressure, pH Value, content of a chemical compound, in particular HF, H 2 0, C0 2 , capacity loss of the cell or voltage or combinations thereof, is reached, exceeded or undershot, and wherein the protective device releases said stabilizing additive in the second form
  • an electrochemical cell at least one protective device which at at least comprises a polymeric material.
  • an electrochemical cell has at least one protective device, which is designed as a storage container for the at least one stabilizing additive.
  • an electrochemical cell comprises at least one stabilizing additive selected from phenylene carbonate, vinylidene carbonate fluorine-containing or non-fluorine-containing lithium organoborates, lithium difluoro (oxalato) borate (LiDFOB) or lithium bis (oxalato) borate (LiBOB) and fluorine-containing or non-fluorine-containing lithium organophosphates, lithium tetrafluoro (oxalato) phosphate (LiTFOP), lithium tris (oxalato) phosphate (LiTOP), or kinetic and / or thermodynamically stable electrically insulating and / or ion-conducting compounds, kinetic and / or thermodynamically stable lithium salts, inorganic lithium salts, LiF, LiOH, Li 2 C0 3 and Li 2 0 or mixtures thereof
  • an electrochemical cell has at least one negative electrode comprising at least one carbonaceous electrochemical active material selected from amorphous graphite, crystalline graphite, carbonaceous materials or mixtures thereof.
  • an electrochemical cell has at least one positive electrode which at least partially comprises at least one electrochemical active material selected from: at least one compound LiMP0 4 , wherein M is at least one transition metal cation selected from manganese, iron, cobalt , Titanium or a combination of these elements; or at least one spinel-type lithium metal oxide or lithium metal mixed oxide, wherein the metal is selected from cobalt, manganese or nickel; or at least one lithium metal oxide or lithium metal mixed oxide in a type different from spinel type, wherein the metal is selected from cobalt, manganese or nickel; or mixtures thereof.
  • An SEI layer according to the present invention is preferably formed during the first charge and discharge cycles at least partially on the surface of the electrochemical active material, in particular the electrochemical active material of the negative electrode, which preferably comprises substantially carbonaceous electrochemically active material.
  • the formation of the SEI layer can be carried out by reaction of a lithium ion-containing electrolyte with the surface of the active material. It is but also possible that the formation of the SEI layer is effected by the reaction of an additive which influences the SEI layer formation, such as LiBOB. Preferably, up to 40%, preferably up to 70%, further preferably up to 100% of the surface area of the electrochemical active material, an SEI layer is formed.
  • the SEI layer has an average thickness of greater than 0 nm up to 20 nm, preferably up to 30 nm, preferably up to 40 nm, preferably up to 50 nm, more preferably up to 60 nm.
  • the SEI layer has an average thickness of 30 nm and more and 50 nm and less.
  • the SEI layer has electrically insulating and lithium ion conducting properties.
  • polymeric compounds such as polyolefins, or mixtures thereof.
  • stable SEI layer is to be understood as meaning that the average volume change, in particular the average thickness of the SEI layer, does not change or does not change significantly as the number of charging and discharging cycles increases, for example becomes thicker or thinner
  • a “stable” SEI layer preferably has no cracks or pores which cause the surface of the active material to be exposed to the electrolyte.
  • a stable SEI layer substantially kinetically and / or thermodynamically stable compounds, preferably LiF, LiOH, Li 2 CO 3 and Li 2 O or mixtures thereof.
  • one possible measurable parameter for a stable SEI layer may be a constant capacity of the cell.
  • stable SEI layer is to be understood as meaning that the average volume change, in particular the average thickness of the SEI layer, changes substantially as the number of charge and discharge cycles increases, for example has become thicker or thinner compared to the average
  • an unstable SEI layer may have cracks or pores causing the surface of the active material to expose to the electrolyte
  • An unstable SEI layer has at least partially metastable compounds, such as ROCO 2 Li or (CH 2 OCO 2 Li) 2 , which decompose to more stable compounds under certain conditions, such as at elevated temperatures, causing the aforementioned cracks or pores can arise Therefore, an unstable SEI layer does not resist, or does not sufficiently withstand, the ingrowth of lithium dendrites.
  • volume change is understood to mean the change in the extent of the SEI layer in all degrees of freedom.
  • the "instability" or “instability” of the SEI layer is defined by at least one predetermined parameter within the electrochemical cell which is reached or exceeded or undershot with respect to the SEI layer.
  • a predetermined parameter may preferably be selected from: specific temperature, specific temperature range, specific pressure, specific pressure range, certain pH, range of pH, a certain amount of volume change of the SEI layer, content of certain chemical compound (s), for example HF, H 2 O, C0 2 , specific capacity loss of the cell, certain voltage, voltage range or combinations it.
  • one possible measurable parameter for an unstable SEI layer may be an irreversible capacity loss of the cell.
  • stabilizing additive is to be understood essentially as meaning all additives known to the person skilled in the art which are capable of stabilizing the SEI layer and / or of being able to form a stable SEI layer itself
  • stabilizing additives are added to the electrolyte prior to or during manufacture of the electrochemical cell, so these additives are already present when the SEI layer is even formed during the first charging and discharging cycles.
  • the at least one stabilizing additive is preferably selected from phenylene carbonate, vinylidene carbonate, fluorine-containing or non-fluorine-containing lithium organoborates, for example lithium difluoro (oxalato) borate (LiDFOB) or lithium bis (oxalato) borate (LiBOB) and fluorine-containing or non-fluorine-containing Lithium organophosphates, for example lithium tetrafluoro (oxalato) phosphate (LiTFOP) or lithium tris (oxalato) phosphate (LiTOP), or mixtures thereof.
  • fluorine-containing or non-fluorine-containing lithium organoborates for example lithium difluoro (oxalato) borate (LiDFOB) or lithium bis (oxalato) borate (LiBOB)
  • fluorine-containing or non-fluorine-containing Lithium organophosphates for example lithium tetrafluoro (o
  • the at least one stabilizing additive is preferably selected from kinetic and / or thermodynamically stable electrically insulating and / or ion-conducting compounds, preferably kinetic and / or thermodynamically stable lithium salts inorganic lithium salts, preferably LiF, LiOH, Li 2 C0 3 and Li 2 0 or mixtures thereof.
  • stabilize SEI layer is to be understood that the at least one stabilizing additive interacts with the SEI layer, and thereby the SEI layer is at least partially, preferably completely stabilized, in particular restored to its original state.
  • the stabilization in particular the recovery of the SEI layer, preferably takes place by incorporation and / or addition of at least one stabilizing additive into defect sites of the SEI layer.
  • the at least one stabilizing additive preferably has electrically insulating and / or ion-conducting, in particular lithium-ion-conducting properties.
  • the at least one stabilizing additive is similar, preferably identical to at least one compound occurring in the SEI layer, preferably similar or identical to at least one thermodynamically and / or kinetically stable compound occurring in the SEI layer, preferably designed as at least an inorganic lithium salt, in particular LiF, Li 2 C0 3 or Li 2 0.
  • the advantage of using at least one stabilizing additive, which is essentially present in the electrochemical cell, or formed therein, is that such additives only a small, preferably no disturbing influence on the running in the electrochemical cell chemical and physical processes.
  • Protective device in the sense of the present invention is understood to mean at least one device which has the at least one stabilizing additive such that an interaction of the at least minimizes, preferably prevents, a stabilizing additive with the SEI layer at least as long as the SEI layer is or becomes unstable.
  • the design of the protective device as a storage for the at least one stabilizing additive.
  • this at least one protective device is that the at least one stabilizing additive can interact with the SEI layer only when necessary, and is not already destroyed, for example, by undesired chemical and / or physical processes during the operation of the electrochemical cell, and thus if necessary, not available or not available in sufficient quantity.
  • a need for an interaction between the at least one stabilizing additive and the SEI layer is preferably present when the SEI layer is or becomes unstable, preferably when a parameter predetermined with respect to the SEI layer is reached or exceeded or undershot.
  • Such a predetermined parameter in the sense of the present invention can preferably be selected from: specific temperature, specific temperature range, specific pressure, specific pressure range, specific pH, pH range, specific amount of volume change of the SEI layer, content of certain chemical Compound (s), for example, HF, H 2 O, C0 2 , specific capacity loss of the cell, particular voltage, voltage range, or combinations thereof.
  • the at least one protective device has a first shape or a second shape, wherein the first shape differs from the second shape in that the first shape minimizes, preferably prevents, the interaction of the at least one stabilizing additive with the SEI layer the second form the interaction of the allows at least one stabilizing additive with the SEI layer, preferably reinforced.
  • the at least one protection device is capable of changing from the first shape to the second shape under certain conditions, such as increasing the pH of the electrolyte solution, or elevated temperatures, or in the presence of certain compounds, such as HF or water.
  • certain compounds such as HF or water.
  • a similar mechanism is known, for example, from pharmaceutical research.
  • micelle capsules are formed in the interior of which a pharmaceutical active substance is located. The "loaded" micelle capsules are used for the targeted "delivery" of pharmaceutical active ingredient to target cells.
  • an active substance (comparable to the relevant stabilizing additive ) and / or release in response to certain physiological parameters can in principle be transferred to electrochemical cells.
  • the at least one protection device at least partially comprises at least one material which is capable of participating in the formation of the first shape and / or the second shape of the at least one protection device.
  • material is meant at least one compound or at least one compound mixture, for example, the material may be one or more polymers.
  • the material must be chosen so that it will not be damaged during normal operation of the electrochemical cell, so that the stabilizing additive is released.
  • the at least one material is at least partially capable of chemically and / or physically reacting under certain conditions, and thereby preferably involved in the first-to-second transformation process of the protection device and / or initiating the conversion process and / or the conversion process support.
  • the at least one protective device at least partially comprises at least one polymeric material.
  • the protective device at least partially comprises a material which melts from a certain temperature and / or changes its phase state, preferably at least one polymeric compound.
  • the at least one protective device at least partially comprises at least one material which is capable of at least one chemical reaction.
  • the material is capable of reacting with at least one "undesirable" compound which is formed when the SEI layer becomes unstable or participates in the instability of the SEI layer
  • "undesired” compounds are, for example, acids, especially protic acids, preferably HF , C0 2 , H 2 0 or mixtures thereof.
  • the advantage of using materials which are capable of reacting with at least one "undesirable” compound, which arises when the SEI layer becomes unstable or is involved in the instability of the SEI layer, is that said compounds are at least partially characterized by a chemical Reaction "consumed”, in particular degraded, and thus their harmful influence on the electrochemical cell is reduced, preferably prevented. Furthermore, it is advantageous that the at least one stabilizing additive is released in particular only in the presence of at least one corresponding "undesired” compound.
  • R 2 may be identical or different.
  • the compound is preferably capable of entering into a chemical reaction with water and / or acids, in particular protic acids HR, which are preferably present at least partially in dissociated form, in particular as H + and R " , in particular an ester cleavage, in particular with formation of the corresponding alcohol ROH and the corresponding acid RC0 2 H.
  • the protective device comprises at least partially polyester.
  • the at least one protective device at least partially comprises a material which has at least one ether bond (R OR 2 , Ri and R 2 may be identical or different) which is capable of reacting with water and / or acids, in particular protic acids, which are preferably present at least partially in dissociated form, in particular as H + and Rklare " to enter into a chemical reaction, in particular an ether cleavage, in particular with formation of the corresponding alcohol R 1 2 OH and Ri / 2-Rsaure-
  • the protective device comprises at least partially polyether on.
  • the at least one protective device at least partially comprises a material having at least one disulfide bond R 1 -SSR 2, while R ⁇ and R2 may be identical or different.
  • the compound is preferably capable of undergoing a chemical reaction, in particular under reductive conditions, in particular with cleavage of the disulfide bond, for example with thiol R 1 2 -SH.
  • the at least one protective device at least partially comprises a material which is at least partially capable of binding C0 2 . This can preferably be achieved by the presence of epoxide groups or of amine groups.
  • the at least one protective device is at least partially designed as a sheath.
  • the at least one protective device is at least partially formed as a release film.
  • the at least one protective device having the at least one stabilizing additive is preferably arranged inside the electrochemical cell.
  • the at least one protective device having the at least one stabilizing additive is at least partially disposed in the electrolyte. This is preferably done by adding the at least one protective device comprising the at least one stabilizing additive to the electrolyte, which is subsequently introduced into the electrochemical cell.
  • the at least one protective device comprising the at least one stabilizing additive is distributed substantially homogeneously within the electrochemical cell, preferably within the electrochemical active material of the negative electrode.
  • the at least one protective device having the at least one stabilizing additive has a maximum spread of a few micrometers, preferably of a few nanometers, preferably of less than 100 ⁇ m, more preferably of less than 75 m, further preferably of less than 50 m.
  • the at least one protective device having at least one stabilizing additive preferably does not close the pores of the separator or can clog.
  • the maximum intake of a protective device is limited to stabilizing additive.
  • the at least one protective device having the at least one stabilizing additive is arranged at least partially on at least one component, preferably the at least one sheath and / or the at least one negative electrode, of the electrochemical cell.
  • At least one first protective device having at least one stabilizing additive is arranged at least partially in the electrolyte and / or at least one second protective device has at least one stabilizing additive at least partially on at least one component, preferably the at least one coating and / or the at least one negative Electrode arranged.
  • the at least first protective device may be different from the at least second protective device, or at least have a stabilizing additive which is different from the stabilizing additive in the second protective device.
  • the at least first and the at least second protective devices can also be identical or the stabilizing additives present in the protective devices can be identical.
  • the at least one protective device having at least one stabilizing additive is at least partially net-like formed, wherein in the reticulated structure at least partially formed areas which are capable of having the at least one stabilizing additive, preferably by forming cavities.
  • Zeolites or similar matrix structures are particularly preferred as a protective device, furthermore also carbon nanotubes.
  • the at least one protective device having at least one stabilizing additive is at least partially connected to the SEI layer by chemical and / or physical interactions, such as electrostatic or covalent or non-covalent interactions, in particular so connected that the at least one protective device in the Essentially non-destructive from the surface of the SEI layer is separable.
  • this is preferably achieved by the following steps: providing an electrochemical cell and generating a stable SEI layer on the electrochemical active material of the negative electrode, for example by methods known in the art. This is followed by a step of disassembling the electrochemical cell to obtain the stable SEI layer located on the electrochemical active material of the negative electrode. Subsequently, the formation of a functionalization layer is performed by applying a functionalization step to the surface of the SEI layer which does not face the electrochemical active material of the negative electrode. Subsequent application of the protective device comprising the at least one stabilizing additive on the functionalized surface of the SEI layer. In one embodiment, the at least one protective device is designed as a storage container for at least one stabilizing additive.
  • the designed as a storage container protection device at least partially an enclosure which is capable of at least partially enclosing the at least one stabilizing additive such that the at least one stabilizing additive is capable of interacting with the SEI layer only after its at least partial release from the at least one protective device ,
  • the release of the at least one stabilizing additive is effected by at least partial destruction of the protective device.
  • the at least partial destruction of the envelope can in turn be carried out by performing mechanical work, such as tensile work and / or by chemical processes, such as degradation reactions, such as ester cleavage, disulfide cleavage or ether cleavage, and / or by physical processes, such as melting the cladding.
  • Battery monitoring device is capable of detecting an irreversible capacity loss of the electrochemical cell.
  • a transmission device such as a wire or a wire mesh.
  • the at least one protection device In response to the signal, which is preferably a thermal and / or electrical signal, sets the at least one protection device the at least one stabilizing additive at least partially free. This is preferably done by heating the at least one protective device, whereby it is at least partially destroyed, preferably by at least partial melting.
  • the electrochemical cell has at least one electrolyte.
  • the electrolyte used can be a nonaqueous electrolyte consisting of at least one organic solvent and at least one alkali metal-containing, preferably lithium ion-containing, inorganic or organic salt.
  • the organic solvent is selected from ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethyl methyl carbonate (EMC), methyl formate (MF), methyl acrylate (MA), methyl butyrate (MB ), Ethyl acetate (EA), 1, 2-dimethoxyethane, ⁇ -butyrolactone, tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,3-dioxane, sulfulane, ethylmethylsulfone (EMS), tetramethylenesulfone (TMS), butylsulfone (BS), ethylvinylsulfone (EVS), 1-fluoro-2- (methylsulf
  • the alkali ion-containing, preferably lithium-ion-containing salt has one or more counterions selected from AsF 6 " , PF 6 " , PF 3 (C 2 F 5 ) 3 " PF 3 (CF 3 ) 3 " BF 4 " BF 2 (CF 3 ) 2 -, BF 3 (CF 3 ) - [B (COOCOO) 2 r, [ ⁇ (0 6 ⁇ 5 ) 4 ⁇ .
  • the separator of the electrochemical cell is impregnated with the electrolyte.
  • the separator is impregnated with an electrolyte which is designed as an ionic liquid.
  • Ionic liquids are ionic compounds which are in a liquid state at room temperature.
  • Ionic liquids consist of anions and cations, with the size ratio between cations and anions chosen so that they do not dispose at room temperature in a crystal lattice, whereby a liquid at room temperature salt can be obtained, which is referred to as ionic liquid.
  • the ionic liquid typically has "large" organic cations, such as the ethylmethylimidazolium cation, and relatively "small” anions, such as the tetrafluoroborate anion.
  • the properties of the ionic liquid can also be influenced. For example, if a basic anion such as the cyanato anion OCN "is used, the ionic liquid is also more basic in nature.
  • ionic liquids which have cationic imidazole-containing derivatives, in particular the cation ethyl-methyl-imidazolium.
  • Preferred anions can be selected from the group AICU, Al 2 Cl 7, F, F x HF, N0 2 , N0 3 , BF 4 , AIF 4 , PF 6 , AsF 6 , SbF 6 , NbF 6 , TaF 6 , WF 7 , CH 3 C0 2, CF3CO 2, C 3 F 7 C0 2, CH 3 S0 3, CF 3 S0 3, C 4 F 9 S0 3, (CF 3 CO) (CF 3 S0 3) N, (CF 3 S0 2) 2 N, (CF 3 S0 2 ) (C 2 F 5 S0 2 ) N, (C 2 F 5 S0 2 ) 2 N, (CF 3 S0 2 ) 3 C, (CN) 2 N, (CN) 3 C, CF 3 BF 3 , C 2 F 5 BF 3 , C 3
  • the electrolyte may have adjuvants that are commonly used in electrolytes for lithium-ion batteries.
  • these radical scavengers such as biphenyl
  • flame retardant additives such as organic Phosphoric acid esters or hexamethylphosphoramide
  • acid scavengers such as amines.
  • the electrolyte preferably comprises additives preferably phenylene carbonate, fluorine-containing or non-fluorine-containing lithium organoborates, for example lithium difluoro (oxalato) borate (LiDFOB) or lithium bis (oxalato) borate (LiBOB) and fluorine-containing or non-fluorine-containing lithium organophosphates, for example lithium tetrafluoro (oxalato) phosphate (LiTFOP) or lithium tris (oxalato) phosphate (LiTOP), which may affect the formation of the SEI layer on the electrodes.
  • fluorine-containing or non-fluorine-containing lithium organoborates for example lithium difluoro (oxalato) borate (LiDFOB) or lithium bis (oxalato) borate (LiBOB)
  • fluorine-containing or non-fluorine-containing lithium organophosphates for example lithium tetrafluoro (ox
  • an electrochemical cell is any type of device for the electrical storage of energy to understand.
  • the term defines in particular electrochemical cells of the primary or secondary type, but also other forms of energy storage, such as capacitors.
  • an electrochemical cell is to be understood as a lithium-ion battery / cell.
  • the electrochemical cell has at least one positive electrode, at least one negative electrode and at least one separator which separates the positive from the negative electrode and which are at least partially surrounded by at least one sheath. electrodes
  • the term "negative electrode” means that the electrode emits electrons when connected to a consumer, such as an electric motor.
  • the negative electrode is the anode.
  • the negative electrode has at least one electrochemical active material which is suitable for incorporation and / or removal of redox components, in particular of lithium ions.
  • the electrochemical active material of the negative electrode is selected from amorphous graphite, crystalline graphite, carbonaceous materials, or mixtures thereof.
  • the negative electrode in addition to the electrochemical active material, also has at least one further additive, preferably an additive for increasing the conductivity, for example based on carbon, for example carbon black, and / or a redox-active additive which, if the electrochemical cell is overcharged, destroys the electrochemical active material reduced, preferably minimized, preferably prevented.
  • an additive for increasing the conductivity for example based on carbon, for example carbon black
  • a redox-active additive which, if the electrochemical cell is overcharged, destroys the electrochemical active material reduced, preferably minimized, preferably prevented.
  • the negative electrode has a metallic substrate.
  • this metallic substrate is at least partially coated with electrochemical active material.
  • the negative electrode comprises a binder capable of enhancing adhesion between electrochemical active material and a metallic substrate.
  • a binder comprises a polymer, preferably a fluorinated polymer, preferably polyvinylidene fluoride, which is sold under the tradenames Kynar® or Dyneon®.
  • the term "positive electrode” means that the electrode receives electrons when connected to a consumer, such as an electric motor.
  • the positive electrode is the cathode.
  • the positive electrode of the electrochemical cell preferably has at least one electrochemical active material which is suitable for incorporation and / or removal of redox components, in particular of lithium ions.
  • the electrochemical active material of the positive electrode is selected from at least one oxide, preferably a mixed oxide, which has one or more elements selected from nickel, manganese, cobalt, aluminum, phosphorus, iron or titanium.
  • the positive electrode comprises a compound having the formula LiMPO 4 wherein M is at least one transition metal cation, preferably a transition metal cation of the first series of transition metals of the Periodic Table of the Elements.
  • the at least one transition metal cation is preferably selected from the group consisting of manganese, iron, nickel, cobalt or titanium or a combination of these elements.
  • the compound preferably has an olivine structure, preferably parent olivine, with iron or cobalt being particularly preferred, preferably LiFePO 4 or LiCoPO 4 .
  • the compound may also have a structure different from the olivine structure.
  • the positive electrode comprises an oxide, preferably a transition metal oxide, or a transition metal mixed oxide, preferably of the spinel type, preferably a lithium manganate, preferably LiMn 2 O 4 , a lithium cobaltate, preferably LiCoO 2 , or a lithium Nickelate, preferably LiNiO 2 , or a mixture of two or three of these oxides.
  • the oxides can also be different from the spinel type.
  • the positive electrode may be in addition to the aforementioned transition metal oxides or exclusively a lithium Have transition metal mixed oxide containing manganese, cobalt and nickel, preferably a lithium-cobalt manganate, preferably LiCoMn0 4 , preferably a lithium-nickel manganate, preferably LiNi 0 .5Mn 1 , 5 O4, preferably a lithium-nickel-manganese-cobalt -Oxid, preferably Li io, 3 3 Mno, 33Coo , 3302, or a lithium-nickel-cobalt oxide, preferably LiNiCoO 2 , which may not be in the spinel type or in the spinel type.
  • a lithium-cobalt manganate preferably LiCoMn0 4
  • a lithium-nickel manganate preferably LiNi 0 .5Mn 1 , 5 O4
  • a lithium-nickel-manganese-cobalt -Oxid preferably Li i
  • the positive electrode in addition to the electrochemical active material, also has at least one further additive, preferably an additive for increasing the conductivity, for example based on carbon, for example carbon black, and / or a redox-active additive which, if the electrochemical cell is overcharged, destroys the electrochemical active material reduced, preferably minimized, preferably prevented.
  • an additive for increasing the conductivity for example based on carbon, for example carbon black
  • a redox-active additive which, if the electrochemical cell is overcharged, destroys the electrochemical active material reduced, preferably minimized, preferably prevented.
  • the positive electrode comprises a binder capable of enhancing adhesion between electrochemical active material and a metallic substrate.
  • a binder comprises a polymer, preferably a fluorinated polymer, preferably polyvinylidene fluoride, which is sold under the tradenames Kynar® or Dyneon®.
  • the positive electrode has a metallic substrate.
  • this metallic substrate is at least partially coated with electrochemical active material.
  • the term "metallic substrate” preferably refers to that component of an electrochemical cell known as “electrode carrier” and "collector.”
  • the metallic substrate is presently suitable for applying electrochemical active material and is substantially metallic in nature, preferably entirely metallic in nature.
  • at least one electrode has at least partially a metallic substrate.
  • this metallic substrate is at least partially designed as a film or as a network structure or as a fabric, preferably comprising a metal.
  • a metallic substrate comprises copper or a copper-containing alloy. In a further embodiment, a metallic substrate comprises aluminum. In one embodiment, the metallic substrate can be configured as a film, mesh structure or fabric, which preferably comprises at least partially plastics.
  • up to 30%, preferably up to 50%, preferably up to 70%, preferably up to 100%, of the total surface of a metallic substrate has at least one layer which has at least one electrochemical active material which is suitable for incorporation and / or removal of lithium ions suitable is.
  • a separator which separates the positive electrode from the negative electrode and is not or only poorly electron-conducting, and which consists of an at least partially permeable carrier.
  • the support is preferably coated on at least one side with an inorganic material.
  • at least partially permeable carrier is preferably an organic material is used, which is preferably designed as a non-woven fabric.
  • the organic material which preferably comprises a polymer, and more preferably one or more polymers selected from polyethylene terephthalate (PET), polyolefin or polyetherimide, is coated with an inorganic, preferably ion-conducting material, which is more preferably in a temperature range of -40 ° C is ionically conductive up to 200 ° C, and preferably at least one compound from the group of oxides, phosphates, silicates, titanates, sulfates, aluminosilicates having at least one of the elements zirconium, aluminum, lithium and particularly preferably zirconium oxide.
  • the inorganic, ion-conducting material of the separator preferably has particles with a size diameter below 100 nm, preferably from 0.5 to 7 ⁇ m, preferably from 1 to 5 ⁇ m, preferably from 1.5 to 3 ⁇ m.
  • the separator has a porous inorganic coating on and in the nonwoven, the aluminum oxide particles having an average particle size of from 0.5 to 7 ⁇ m, preferably from 1 to 5 ⁇ m, and very particularly preferably from 1.5 to 3 ⁇ which are bonded to an oxide of the elements Zr or Si.
  • the maximum particle size is preferably 1/3 to 1/5 and more preferably less than or equal to 1/10 of the thickness of the nonwoven fabric used.
  • Suitable polyolefins are preferably polyethylene, polypropylene or polymethylpentene. Particularly preferred is polypropylene.
  • polyamides, polyacrylonitriles, polycarbonates, polysulfones, polyethersulfones, polyvinylidene fluorides, polystyrenes as organic carrier material is also conceivable. It is also possible to use mixtures of the polymers.
  • a separator with PET as carrier material is commercially available under the name Separion®. It can be prepared by methods as disclosed in EP 1 017 476.
  • nonwoven web means that the polymers are in the form of nonwoven fibers (non-woven fabric).
  • Such fleeces are known from the prior art and / or can be prepared by the known methods, for example, by a spunbonding process or a meltblown process such as in DE 195 01 271 A1 referenced.
  • the separator preferably has a nonwoven which has an average thickness of 5 to 30 ⁇ m, preferably 10 to 20 ⁇ m.
  • the fleece is flexible.
  • the nonwoven fabric has a homogeneous pore radius distribution, preferably at least 50% of the pores have a pore radius of 75 to 100 pm.
  • the web has a porosity of 50%, preferably from 50 to 97%.
  • Porcity is defined as the volume of the web (100%) minus the volume of the fibers of the web (corresponds to the volume fraction of the web that is not filled by material.)
  • the volume of the web can be calculated from the dimensions of the web.
  • the volume of the fibers is determined by the measured weight of the fleece under consideration and the density of the polymer fibers.
  • the large porosity of the fleece also allows a higher porosity of the separator, which means that a higher absorption of electrolytes with the separator can be achieved.
  • the separator consists of a polyethylene glycol terephthalate, a polyolefin, a polyetherimide, a polyamide, a polyacrylonitrile, a polycarbonate, a polysulfone, a polyethersulfone, a polyvinylidene fluoride, a polystyrene, or mixtures thereof.
  • the separator consists of a polyolefin or of a mixture of polyolefins.
  • Particularly preferred in this embodiment is then a separator which consists of a mixture of polyethylene and polypropylene.
  • such separators have a layer thickness of 3 to 14 pm.
  • the polymers are preferably in the form of fiber webs, wherein the polymer fibers preferably have an average diameter of 0.1 to 10 pm, preferably from 1 to 4 pm.
  • the term "mixture” or “mixture” of the polymers means that the polymers are preferably in the form of their nonwovens, which are bonded together in layers. Such nonwovens or nonwoven composites are disclosed, for example, in EP 1 852 926.
  • this consists of an inorganic material.
  • the inorganic material used are oxides of magnesium, calcium, aluminum, silicon and titanium, as well as silicates and zeolites, borates and phosphates.
  • Such materials for separators as well as methods for producing the separators are disclosed in EP 1 783 852.
  • the separator consists of magnesium oxide.
  • separator 50 to 80 wt .-% of the magnesium oxide by calcium oxide, barium oxide, barium carbonate, lithium, sodium, potassium, magnesium, calcium, barium phosphate or by lithium, sodium, potassium borate, or Mixtures of these compounds, be replaced.
  • the separators of this embodiment have a layer thickness of 4 to 25 pm.
  • the invention likewise provides a method for operating an electrochemical cell, the electrochemical cell having at least one stabilizing additive which is at least partially released from the at least one protective device when the SEI layer is or becomes unstable, in particular as soon as a predetermined parameter is reached or exceeded or is fallen short of.
  • the present invention also relates to a process for the production of the electrochemical cell according to the invention, which comprises the following steps:
  • the at least one negative electrode substantially comprises at least one carbon-containing electrochemical active material capable of forming an SEI layer on at least parts of the surface
  • At least one stabilizing additive which is capable of stabilizing an SEI layer
  • Provision of at least one protective device which is capable of at least partially accommodating the at least one stabilizing additive
  • the at least one stabilizing additive is released from the at least one protective device when, with regard to the SEI layer, at least one predetermined parameter is reached or exceeded or
  • the electrochemical cell of the present invention can be used to power mobile information equipment, tools, electric powered automobiles, and hybrid drive automobiles.
  • FIG 1 shows schematically the structure of an embodiment of an electrochemical cell according to the invention
  • Figure 2 shows schematically the structure and the arrangement of a
  • FIG. 3 shows schematically the structure and the arrangement of an embodiment of a protective device and a negative electrode with SEI layer as part of the electrochemical cell according to the invention at the time before and after the unstable become the SEI layer
  • FIG. 1 shows an inventive electrochemical cell 100 comprising a positive electrode with active material 110, a separator 120, a cladding 160, a negative electrode with active material 150, an SEI layer 170 and an active material 150 on the surface of the negative electrode a stabilizing additive or a stabilizing additive mixture 180, which is enclosed by parts of the enclosure 160 by a protective device 190, which is configured as a separation between SEI layer 170 and stabilizing additive 180.
  • the electrochemical cell 100 has a battery management system 131, which is in contact with the positive electrode 110 and the negative electrode 150 and a battery monitoring system 132. Via a transmission device 140, the battery monitoring system 132 is connected to the protective device 190. Parts of the transmission device 140 are in operative connection with the protective device 190.
  • the signal is preferably an electrical signal, which is transmitted to the transmission device 140.
  • the transmission device 140 is designed as an electrical resistance, which converts electrical energy, that is to say the electrical signal, into heat energy, which due to the Actual relationship between transfer device 140 and protection device 190, this heat energy to the protection device 190 at least partially releases, whereby the stabilizing additive or the stabilizing additive mixture 180 is released from the protection device 190.
  • the protective device 190 is at least partially destroyed, for example, is destroyed by melting.
  • the stabilizing additive or additive stabilizing mixture 180 may interact with the SEI layer 170 and preferably stabilize the SEI layer 170.
  • the protection device 190 comprises at least one polymer having a melting temperature higher than the temperature prevailing therein during normal operation of the electrochemical cell 100, but less than the temperature generated by the resistance region of the transfer device 140.
  • Figure 2 shows a negative electrode of an electrochemical cell according to the invention before 201 and after 202 the release of the stabilizing additive or stabilizing additive mixture 250 from parts of the protective device 231, 232 (parts of the protective device before the release of the stabilizing additive 250: 231; the release of the stabilizing additive 250: 232).
  • the negative electrode 201, 202 in this case has an electrochemical active material 210, which is at least partially coated with an SEI layer 220. The side of the SEI layer 220 facing away from the electrochemical active material 210 has been functionalized (not shown in FIG.
  • connections 240 may be, for example, covalent bonds, electrostatic bonds, or other strong interactions or bonds.
  • parts of the protective device 231, 232 which contain the stabilizing additive or the stabilizing additive mixture 250, are also connected to one another via connections 260, so that the parts of the protective device 231, 232 are substantially non-destructive to one another are separable.
  • parts of the protective device 231, 232 have weak points 271, 272, at which the parts of the protective device 231, 232 are preferably destroyed.
  • FIG. 3 shows a negative electrode of an electrochemical cell according to the invention before 301 and after 302 of the release of the stabilizing additive or stabilizing additive mixture 340 from protective devices 331, 332.
  • the negative electrode 301, 302 consists of electrochemical active material 310 which is at least partially covered by an SEI.
  • Layer 320 is coated.
  • Protective means 331, 332 are preferably located in the electrolyte solution 350.
  • the SEI layer 320 becomes unstable, cracking or pore formation may occur within the SEI layer 320, whereby the electrochemical active material 310 of the electrolyte solution 350 may be at least partially exposed .
  • the stabilizing additive or additive stabilizing mixture 340 is released from the guards 332 and stored in the SEI layer 320, stabilizing it again.

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Abstract

L'invention concerne une cellule électrochimique comprenant au moins une électrode négative, au moins une électrode positive et au moins un électrolyte. La ou les électrodes négatives comprennent sensiblement au moins un matériau actif électrochimique contenant du carbone et pouvant former une « interface électrolyte-solide », par conséquent une couche d'interface électrolyte-solide sur au moins des parties de la surface de l'électrode. La cellule électrochimique comprend au moins un additif stabilisant pouvant stabiliser la couche d'interface électrolyte-solide. Un dispositif de protection comprenant le ou les additifs stabilisants et conçu de préférence comme un réservoir de stockage est disposé dans la cellule électrochimique. Le ou les additifs stabilisants sont libérés au moins en partie du ou des dispositifs de protection lorsque, en ce qui concerne la couche d'interface électrolyte-solide, au moins un paramètre prédéfini est atteint, dépassé ou n'est pas atteint.
EP12721419.5A 2011-05-27 2012-05-18 Cellule électrochimique Withdrawn EP2715859A1 (fr)

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DE102011102628A DE102011102628A1 (de) 2011-05-27 2011-05-27 Elektrochemische Zelle
PCT/EP2012/002141 WO2012163485A1 (fr) 2011-05-27 2012-05-18 Cellule électrochimique

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CN109411830A (zh) * 2018-11-02 2019-03-01 温州玖源锂电池科技发展有限公司 一种锂离子电池装置
CN112993410A (zh) * 2021-02-09 2021-06-18 深圳市齐得隆电子有限公司 一种新型大容量固态锂离子电池的制作方法

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US5492781A (en) 1994-01-18 1996-02-20 Pall Corporation Battery separators
PL338562A1 (en) 1998-06-03 2000-11-06 Creavis Ges F Technologie Und Ion-conductive permeable composite material, method of obtaining same and application thereof
DE10308945B4 (de) 2003-02-28 2014-02-13 Dilo Trading Ag Li-Polymer-Batterien mit Separator-Dispersion und Verfahren für ihre Herstellung
DE102006021273A1 (de) 2006-05-05 2007-11-08 Carl Freudenberg Kg Separator zur Anordnung in Batterien und Batterie
DE102007024394A1 (de) * 2007-05-25 2008-11-27 Robert Bosch Gmbh Elektrochemischer Energiespeicher
CN101420048A (zh) 2007-10-26 2009-04-29 比亚迪股份有限公司 一种锂离子二次电池的制备方法

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KR20140031318A (ko) 2014-03-12

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