WO2018220285A1 - Cathode d'accumulateur, accumulateur et batterie associés - Google Patents
Cathode d'accumulateur, accumulateur et batterie associés Download PDFInfo
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- WO2018220285A1 WO2018220285A1 PCT/FR2017/051351 FR2017051351W WO2018220285A1 WO 2018220285 A1 WO2018220285 A1 WO 2018220285A1 FR 2017051351 W FR2017051351 W FR 2017051351W WO 2018220285 A1 WO2018220285 A1 WO 2018220285A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a cathode.
- the invention also relates to an electrochemical accumulator and to a battery comprising such a cathode.
- An electrochemical accumulator typically comprises at least four elements: a positive electrode, a negative electrode, an electrolyte, as well as current collectors for each electrode.
- the set of a negative electrode and a current collector form an anode while the assembly of a positive electrode and a current collector form a cathode.
- the operating principle of these accumulators is based on the reversible storage of electrical energy into chemical energy by the implementation of two separate and coupled electrochemical reactions. It is the positive and negative electrodes that bathe in the electrolyte that are the seat of the so-called faradic electrochemical reactions.
- the electrodes are in particular made of active materials for storing and destocking the ions via oxidation and reduction reactions.
- the active material at the negative electrode oxidizes and releases on the one hand electrons that are routed through the current collector to the external circuit and on the other hand cations that migrate to the through the electrolyte to the positive electrode. Then, the electrons that have passed through the circuit that used the energy, and the cations are captured by the active material to the positive electrode that is reduced.
- the energy density that an accumulator can release is a function of both the potential and the capacity of the electrochemical cell, both of which are directly related to the chemistry of the system.
- the potential of a battery is determined by the difference between the potentials of the oxidation-reduction reactions occurring simultaneously with the positive and negative electrodes.
- the electrodes are made according to a composition, the composition mainly comprising one or more active material (s) (> 90% by weight), conductive particles ensuring a good transport of the electrons towards all the active materials and a binder which makes it possible to ensure the cohesion of the particles, as well as the adhesion to the substrate.
- the whole is manufactured, in general, in the form of a formulation with the aid of a solvent that will allow to coat the electrode.
- an electrolyte This can be liquid, gel form or solid.
- the mass energy or specific energy is defined as the ratio between the energy recoverable at a given speed (discharge regime to which the accumulator is discharged) and the mass of the accumulator.
- the mass energy is expressed in Wh / kg.
- This notion is particularly useful for the dimensioning of a battery in embedded systems where mass is a predominant dimensioning criterion.
- the volume energy is the ratio between the energy recoverable at a given speed and the volume of the accumulator.
- the energy density is expressed in Wh / L. This notion is useful for the dimensioning of a stationary battery because, in these applications, volume is often a more decisive criterion than mass.
- Lithium technologies have the best characteristics in terms of densities of mass and volume energy. These technologies are therefore preferentially chosen for nomadic applications, such as mobile telephony or laptops. On the other hand, because of the high cost of this type of accumulator, the other storage technologies still find many applications. Lead-acid batteries are often preferred for stationary applications (eg storage of renewable energies), or for starting vehicles. With regard to nickel-cadmium (Ni-Cd) or nickel-metal hydride (Ni-MH) batteries, these are still used because of their low cost and reliability, mainly in the portable tooling. power or in hybrid electric vehicles. For many applications, it is therefore desirable to improve the electrical mobility and storage of renewable energy by increasing the performance in terms of specific energy and energy density.
- an electrochemical accumulator cathode comprising an electrode, a current collector, an interfacing layer, the interfacing layer being coated on the current collector, the interfacing layer also being contact with the electrode and having a thickness less than 5 micrometers.
- the cathode comprises one or more of the following characteristics, taken in isolation or in any technically possible combination:
- the electrode is produced according to a first composition, the first composition comprising a first intercalation material, a first binder material and a first conductive additive, the content of the first conductive additive being less than or equal to 2% by weight, preferably less than or equal to 1% by weight.
- the electrode is made according to a first composition, the first composition consisting of a first intercalation material and a first binder material.
- the first binder material consists of one or more polymers.
- the interfacing layer has a thickness greater than or equal to 10 nanometers.
- the interfacing layer has a thickness of between 50 nanometers and 1 micrometer.
- the collector is a metal sheet.
- the interfacing layer is made according to a second composition comprising a second binder material and a second conductive additive.
- the second binder material consists of one or more polymers.
- the content of the second binder material is greater than or equal to 30% by weight of the interfacing layer.
- the content of the second conductive additive is greater than or equal to 10% by weight of the interfacing layer.
- the present description also relates to an electrochemical accumulator comprising a cathode as previously described.
- the accumulator is a lithium-ion battery.
- the present description also describes a battery comprising a set of accumulators, at least one accumulator being an accumulator as previously described.
- FIG. 10 An electric accumulator 10 is shown in FIG.
- the accumulator 10 is intended to be connected to other electric accumulators to form an electrical generator of voltage and capacity desired.
- a generator is called a battery or simply a battery.
- An accumulator 10 uses a reversible energy conversion technique to store energy and restore it later.
- the accumulator 10 described using an electrochemical reaction the accumulator 10 is an electrochemical accumulator.
- the accumulator 10 comprises an electrolyte 12, anode 14 and a cathode 16.
- the accumulator 10 is a lithium-ion battery intended for a lithium-ion battery but the claimed elements could be applicable to other electrochemical accumulator technologies consisting of the same elements as the lead-type accumulators.
- the interaction between the electrolyte 12, the anode 14 and the cathode 16 allows the accumulator 10 to function as an electrochemical accumulator.
- the electrolyte 12 is conventionally composed of different ionic salts providing ions for charge storage or faradic reactions, carbonates and a solvent or solvent mixture to allow the solubilization of the ions.
- the ionic salts are conventionally LiPF6 (Lithium hexafluorophosphate), lithium bis (TriFluoromethane Sulfonyl) Imide salt (LiTFSI), LiBF4 (Lithium tetrafluoroborate) and LiBOB (lithium bis oxalate borate).
- LiDFOB Lithium Difluorooxalatoborate
- the carbonates are, for example, propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) or diethyl carbonate (DEC).
- the anode 14 is made of a material for intercalating ions, for example in a lithium-ion accumulator carbon, which is used for the most part in the form of "MesoCarbon MicroBeads" (MCMB), graphites, whether they are artificial or natural or graphitic materials such as soft or hard carbon or other types of negative electrode materials based on lithium titanate (Li Ti 5 0 12 or LTO), silicon, tin or alloys.
- MCMB Metal Organic Chemical Vaporide
- the cathode 16 is shown in more detail in FIG.
- the cathode 16 comprises an electrode 18, an interfacing layer 20 and a current collector 22.
- the electrode 18, the current collector 22 and the interfacing layer 20 form a stack of layers in a stacking direction denoted Z.
- the electrode 18 is in contact with the electrolyte 12.
- the electrode 18 is made according to a first composition C1 whose properties are now described.
- the first composition C1 comprises a first intercalation material MM, a first binding material ML1 and a first conductive additive AC1.
- the intercalation material is also referred to as "active material”.
- the active material of the electrode 18 is conventionally composed of lithiated metal oxide such as LiCoO 2 (LCO), LiNiMnCoO 2 (NMC), LiNiCoAlO 2 (NCA), LiMn 2 O 4 (LMO) ), LiFePO4 (LFP), Li (LiNiMn) 0 2 or LiNiMnO (LNMO); Lily.
- lithiated metal oxide such as LiCoO 2 (LCO), LiNiMnCoO 2 (NMC), LiNiCoAlO 2 (NCA), LiMn 2 O 4 (LMO) ), LiFePO4 (LFP), Li (LiNiMn) 0 2 or LiNiMnO (LNMO); Lily.
- Other examples of active material of the electrode 18 are possible, for example for sodium-ion batteries, examples are listed in the publication "Advanced Organic Electrode Materials for Rechargeable Sodium-Ion Batterie
- the choice of the first ML1 binder material can vary considerably as long as the first ML1 binder material is inert relative to the other electrode materials.
- the first material ML1 binder is a material, usually polymeric, which facilitates the implementation of the electrodes during their manufacture.
- the first ML1 binder material comprises one or more polymers selected from thermoplastic polymers, thermosetting polymers, elastomers and mixtures thereof.
- thermoplastic polymers include, but are not limited to, polymers derived from the polymerization of aliphatic or cycloaliphatic vinyl monomers, such as polyolefins (among which polyethylenes or polypropylenes), polymers resulting from the polymerization of vinyl aromatic monomers such as polystyrenes, polymers derived from the polymerization of acrylic monomers and / or (meth) acrylates, polyamides, polyetherketones, polyimides.
- polymers derived from the polymerization of aliphatic or cycloaliphatic vinyl monomers such as polyolefins (among which polyethylenes or polypropylenes), polymers resulting from the polymerization of vinyl aromatic monomers such as polystyrenes, polymers derived from the polymerization of acrylic monomers and / or (meth) acrylates, polyamides, polyetherketones, polyimides.
- thermosetting polymers include, but are not limited to, thermosetting resins (such as epoxy resins, polyester resins) optionally in admixture with polyurethanes or with polyether polyols or vice versa.
- elastomeric polymers include, but are not limited to, natural rubbers, synthetic rubbers, styrene-butadiene copolymers (also known by the abbreviation "SBR”), ethylene-propylene copolymers (also known as abbreviations). "EPM”), silicones.
- SBR styrene-butadiene copolymers
- EPM ethylene-propylene copolymers
- silicones silicones.
- the first ML1 binder material may be a mixture of thermoplastic polymer (s), thermosetting polymer (s) and / or elastomeric polymer (s).
- first ML1 binder materials include crosslinked polymers, such as those made from polymers having carboxyl groups and crosslinking agents.
- the content of the first ML1 binder material is less than 5% by weight.
- the first conductive additive AC1 comprises one or more types of conductive elements to improve the electronic conductivity.
- Examples of conductive elements include, but are not limited to, conductive carbons, graphites, graphenes, carbon nanotubes, activated carbon fibers, unactivated carbon nanofibers, metal flakes, metal powders, metal fibers and electrically conductive polymers.
- the content of first conductive additive AC1 is less than or equal to 4% by weight.
- the thickness e18 of the electrode 18 is 50 ⁇ .
- the current collector 22 is made of a sufficiently conductive material to provide electronic transport, light, thin, mechanically resistant to serve as a substrate for the electrode 18.
- the current collector 22 is a metal sheet of iron, copper, aluminum, nickel, titanium or stainless steel.
- the material of the current collector 22 is carbon paper, or a plastic film (such as PET polyethylene terephthalate) coated with graphene or metal particles.
- the thickness e22 of the current collector 22 is 20 ⁇ .
- the interfacing layer 20 provides an interface between the current collector 22 and the electrode 18.
- the interfacing layer 20 is a layer in contact on the one hand with the current collector 22 and on the other hand with the electrode 18.
- the interfacing layer 20 is coated on the current collector 22.
- the interfacing layer 20 has a thickness e20 of less than 5 microns ( ⁇ ).
- the interfacing layer 20 has a thickness e20 greater than or equal to 10 nanometers.
- the interfacing layer 20 has a thickness e20 of between 50 nanometers and 1 micrometer.
- the interfacing layer 20 is made according to a second composition C2.
- the second composition C2 comprises a second binder material ML2 and a second conductive additive AC2.
- the choice of the second ML2 binder material can vary considerably as long as the second ML2 binder material is inert with respect to the other materials of the second composition C2.
- the second ML2 binder material comprises one or more polymers selected from thermoplastic polymers, thermosetting polymers, elastomers, and mixtures thereof.
- thermoplastic polymers include, but are not limited to, polymers derived from the polymerization of aliphatic or cycloaliphatic vinyl monomers, such as polyolefins (among which polyethylenes or polypropylenes), polymers resulting from the polymerization of vinyl aromatic monomers such as polystyrenes, polymers derived from the polymerization of acrylic monomers and / or (meth) acrylates, polyamides, polyetherketones, polyimides, polyvinyl alcohols, fluorinated polymers, polyacrylonitrile.
- polymers derived from the polymerization of aliphatic or cycloaliphatic vinyl monomers such as polyolefins (among which polyethylenes or polypropylenes), polymers resulting from the polymerization of vinyl aromatic monomers such as polystyrenes, polymers derived from the polymerization of acrylic monomers and / or (meth) acrylates, polyamides, polyetherketones, polyimides, polyviny
- thermosetting polymers include, but are not limited to, thermosetting resins (such as epoxy resins, polyester resins) optionally in admixture with polyurethanes or with polyether polyols or vice versa.
- elastomeric polymers include, but are not limited to, natural rubbers, synthetic rubbers, styrene-butadiene copolymers (also known by the abbreviation "SBR”), ethylene-propylene copolymers (also known as abbreviations). "EPM”), silicones.
- SBR styrene-butadiene copolymers
- EPM ethylene-propylene copolymers
- silicones silicones.
- the second binder material ML2 may be a mixture of thermoplastic polymer (s), thermosetting polymer (s) and / or elastomeric polymer (s).
- Suitable second ML2 binder materials include crosslinked polymers, such as those made from polymers having carboxyl groups and crosslinking agents.
- the content of second ML2 binding material is greater than or equal to 30% by weight.
- the content of second ML2 binder material is less than or equal to 80% by weight.
- the content of second ML2 binder material is between
- the second conductive additive AC2 comprises one or more types of conductive elements for improving the electronic conductivity.
- Examples of conductive elements include, but are not limited to, conductive carbons, graphites, graphenes, carbon nanotubes, activated carbon fibers, unactivated carbon nanofibers, metal flakes, metal powders, metal fibers and electrically conductive polymers.
- the content of second conductive additive AC2 is greater than or equal to 20% by weight.
- the content of second conductive additive AC2 is less than or equal to 70% by weight.
- the content of second conductive additive AC2 is between 30% by weight and 60% by weight.
- the operation of the accumulator 10 is in accordance with the operation of an electrochemical accumulator of the state of the art.
- the interfacing layer 20 improves the current collector / electrode interface, by optimizing the adhesion and the contact resistance.
- the contact resistance has a major effect on the electronic conductivity of the assembly, a strong resistance acting as a barrier to electron transfer during cycling.
- the interfacing layer 20 may help reduce this phenomenon, by improving the conduction path.
- the other function of the interfacing layer 20 is to allow protection of the current collector 22, the corrosion of the current collectors being a fairly widespread phenomenon. For good resistance to corrosion it is necessary to cut the access of the electrolyte to the current collector.
- the interfacing layer 20 therefore acts as a physical barrier to the access of the ions responsible for the corrosion, but will also act on the stabilization of the potential of the current collector interface / interfacing layer.
- the accumulator 10 has a specific capacity preserved in comparison with the cathodes of the state of the art whose content of conductive additives is greater than 2%.
- the results of FIG. 13 show that an improvement in energy density (mass energy or volume energy) is possible with a cathode as claimed.
- the retention of the capacity after 500 cycles is about 50% for a cathode according to the state of the art and 60% for a cathode 16 with zero content of conductive additive. This corresponds to a gain of 20% in terms of capacity retention.
- the use of such a cathode 16 in an accumulator 10 makes it possible to improve the cyclability and the life of the accumulators.
- cathode 16 in an accumulator allows its use at high operating speeds to associate with the energy density gain, an improved available power.
- first conductive additive AC1 less than or equal to 2% by weight.
- the content of first conductive additive AC1 less than or equal to 1% by weight
- the first composition C1 consists of an intercalation material and a binder material.
- the first composition C1 is thus devoid of conductive additives.
- the thickness of the coating after drying of the coating is between 1 ⁇ and 1, 5 ⁇ .
- the positive electrode is made from an active material, Nthié iron phosphate (LiFePO 4 - LFP) (Pholicat Fe100, Umicore), carbon black (C65, Timcal) and from a polymeric binder. poly (vinylidene fluoride) - PVdF (Solef 5130, Solvay). The dry weight ratio has been adjusted for each variation in carbon content, to achieve a similar rate of the mass of PVdF and the density of C65 (62 m 2 ⁇ g ”) and LFP (20.9 m 2 .g "1 ), to obtain the same mechanical properties for the composite electrodes. The different ratios by weight of LFP / PVdF / C65 are shown in Table 1. Denomination of LFP PVdF C65 Conductivity of electrode (% by weight) (% by weight) (% by weight) electrode (Sm)
- the different suspensions were prepared under the same conditions.
- N-methyl-2-pyrrolidone (-Pyrol, Ashland) was used to dissolve the PVdF for 2 hours at 60 ° C under magnetic stirring. In order to properly disperse the carbon black, it was thoroughly mixed for 1 hour by mechanical stirring with the PVdF solution. Finally, the LFP powder was added and an agitation machine (IKA) was used for 75 min at room temperature. The dry content was set at 40% regardless of the formulation of the electrode: the rheological properties were not optimized.
- the various mixed suspensions were coated with an automatic film applicator (AAF) from Elcometer: on the bare aluminum sheet on the one hand to constitute the examples of cathode (denoted CaR1, CaR2, CaR3, CaR4, CaR5, in the following) ; on the aluminum sheet previously coated with a interfacing layer on the other hand to form the examples of cathodes (denoted CaE l, CaE2, CaE3, CaE4, CaE5 thereafter).
- AAF automatic film applicator
- the various coated suspensions were dried at 80 ° C. to 130 ° C. in air for 1 hour and maintained for 1 hour at 130 ° C. under vacuum. Typical loading of the active material was 10-1 1 mg.cm -2 .
- the electrodes were sized to a porosity of 38 ⁇ 2% irrespective of their composition.
- On the negative side a graphite electrode from Mti corp. was used without modification.
- the electrode is composed of 95.7% by weight MesoCarbon MicroBeads (MC B) and a mixture of carboxymethylcellulose (CMC) and styrene-butadiene (SBR) as binder.
- the negative composite electrode with a thickness of 40 ⁇ and a loading of active material of 6 mg / cm 2 is supported by a 9 ⁇ m thick copper current collector.
- the specific capacity claimed is 330 mAh.g.
- the accumulators were assembled in a glove box under an argon atmosphere. Two 0.5 mm stainless steel spacers and a wave spring were used to ensure good pressure on the electrodes.
- the positive electrode was cut into 1.27 cm 2 samples and dried at 90 ° C for 1 hour under vacuum prior to assembly.
- the negative electrode was cut out as a 1.13 cm 2 sample in order to maintain a capacity ratio between the positive and the negative side at a typical value of about 20% in favor of the negative side. These samples were treated for 5 hours at 150 ° C. under vacuum before assembly.
- the electrolyte used was a 1M solution of LiPF 6 in ethylene carbonate: dimethyl carbonate (1: 1 by volume, Solvionic), quenched in a fiberglass separator (Whatman). The accumulators finally reach a theoretical capacity of 1, 8 mAh.cm "2 .
- the electrochemical performances of the cells were characterized by a VMP3 multipotentiostat (Biology).
- FIGS. 3 to 13 which respectively correspond to:
- FIGS. 3 to 8 discharge curves for the different examples of electrodes at different speeds or currents. This scheme is expressed as a fraction of the capacity of the battery.
- Figures 3 and 4 show the C / 5 discharge curves, Figure 3 for the CaR cathode examples, Figure 4 for the CaE cathode examples;
- FIGS. 5 and 6 show the discharge curves at C, FIG. 5 for the CaR cathode examples, FIG. 6 for the CaE cathode examples;
- Figs. 7 and 8 show the discharge curves at 5C, Fig. 7 for the CaC cathode examples;
- Fig. 8 for the CaE cathode examples.
- FIGS. 9 and 10 specific capacities available depending on the operating conditions of the accumulators for the various examples of electrodes.
- Figure 9 groups together the observations for the CaR cathode examples, and
- Figure 10 shows the observations for the CaE cathode examples.
- FIG. 11 capacity retained as a function of the number of charge cycles and discharges performed by the accumulator for all the cathode examples
- FIG. 12 specific capacities retained after 200 cycles of charges and discharges at the 2 C regime for all examples of CaRi and CaEi cathodes, as a function of the carbon content in the electrode.
- FIG. 13 energy density versus power density comparing cathodes according to the state of the art and CaEO cathode.
- Figures 3 to 8 show the discharge voltage profiles at the C / 5, C and 5C regimes for all electrodes tested.
- the operation of the accumulators is not affected (or very slightly), regardless of the composition of the electrode.
- the CaRO and CaR1 cathodes At a medium speed (C), the CaRO and CaR1 cathodes have a specific capacitance close to zero, whereas their equivalent electrodes CaEO and CaE1 have a specific capacity of approximately 120 mAh / g.
- the polarization and the specific capacitance remain substantially the same (approximately 80 mAh / g) for all the electrode compositions with CaE1 or CaE5 interface layer, whereas the accumulators comprising electrodes with a content of less than 2% carbon without interface layer (CaR1 and CaR2) no longer work, the polarization being too high to obtain a charge transfer.
- FIGS. 9 and 10 The performances in terms of capacity retention as a function of the discharge regime are shown in FIGS. 9 and 10.
- the rate of retention of capacity decreases when the discharge regime is increased. tendency being accentuated by the decrease of the carbon content of the electrode: the carbon ensuring the maintenance of a good capacity. This deterioration is visible as soon as the carbon content decreases to 3% and becomes critical for the carbon contents of 2 to 0% for which the capacity retention is close to 0 from the regime of 1 C.
- Figure 1 1 shows the retention of capacity versus the number of charge and discharge cycles under difficult conditions of 500 cycles at 2C.
- a reduction of the carbon content of the electrode decreases the cyclability which becomes impossible below 2%.
- Cathodes, as claimed, CaEi show a very different behavior, the reduction of the carbon content of these electrodes improves the cyclability of Accumulators.
- the cathode CaE1 (without carbon) shows a behavior similar to that of the CaE5 cathode of the accumulators over 500 cycles.
- Figure 12 shows the specific capacity retained after 200 cycles of charges and discharges at 2C.
- the capacity retained is lower than the CaEi cathodes, and the reduction of the conductive carbon greatly reduces the capacity retained for the CaRi electrodes.
- the CaEi cathodes show similar behavior, regardless of the carbon content.
- FIG. 13 representing the energy density as a function of the power density, shows that the accumulator comprising the CaEO cathode retains these two quantities, energy and power, at a better level than any of the cathodes of the state of the technical. Finally, these remarkable properties are preserved even after 200 cycles (points indicated in FIG. 13) confirming the improvement of the performances in terms of energy density and battery life including the cathode 16.
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Abstract
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Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP17767860.4A EP3443605A1 (fr) | 2017-05-30 | 2017-05-30 | Cathode d'accumulateur, accumulateur et batterie associés |
CA3011742A CA3011742C (fr) | 2017-05-30 | 2017-05-30 | Cathode d'accumulateur, accumulateur et batterie associes |
PCT/FR2017/051351 WO2018220285A1 (fr) | 2017-05-30 | 2017-05-30 | Cathode d'accumulateur, accumulateur et batterie associés |
US16/068,352 US11217794B2 (en) | 2017-05-30 | 2017-05-30 | Cathode of accumulator, associated accumulator and battery |
AU2017391883A AU2017391883A1 (en) | 2017-05-30 | 2017-05-30 | Cathode of accumulator, associated accumulator and battery |
KR1020187021362A KR102415775B1 (ko) | 2017-05-30 | 2017-05-30 | 전류 콜렉터 및 인터페이스 층의 세트, 관련된 축전지 및 배터리 |
BR112018014287A BR112018014287A2 (pt) | 2017-05-30 | 2017-05-30 | catodo de acumulador eletroquímico, acumulador eletroquímico e bateria |
CN201780007721.7A CN109565025A (zh) | 2017-05-30 | 2017-05-30 | 蓄电池的阴极、相关的蓄电池以及电池组 |
JP2018537768A JP7468991B2 (ja) | 2017-05-30 | 2017-05-30 | 蓄電池のカソード、関連する蓄電池および電池 |
JP2022113119A JP2022140503A (ja) | 2017-05-30 | 2022-07-14 | 蓄電池のカソード、関連する蓄電池および電池 |
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PCT/FR2017/051351 WO2018220285A1 (fr) | 2017-05-30 | 2017-05-30 | Cathode d'accumulateur, accumulateur et batterie associés |
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WO2018220285A1 true WO2018220285A1 (fr) | 2018-12-06 |
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PCT/FR2017/051351 WO2018220285A1 (fr) | 2017-05-30 | 2017-05-30 | Cathode d'accumulateur, accumulateur et batterie associés |
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US (1) | US11217794B2 (fr) |
EP (1) | EP3443605A1 (fr) |
JP (2) | JP7468991B2 (fr) |
KR (1) | KR102415775B1 (fr) |
CN (1) | CN109565025A (fr) |
AU (1) | AU2017391883A1 (fr) |
BR (1) | BR112018014287A2 (fr) |
CA (1) | CA3011742C (fr) |
WO (1) | WO2018220285A1 (fr) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130209889A1 (en) * | 2010-10-21 | 2013-08-15 | Koji Takahata | Battery electrode and use thereof |
US20140322600A1 (en) * | 2011-11-15 | 2014-10-30 | Masahiro Morita | Nonaqueous electrolyte secondary battery |
FR3005207A1 (fr) * | 2013-04-24 | 2014-10-31 | Batscap Sa | Electrode positive pour batterie lithium |
US20160093922A1 (en) * | 2014-09-29 | 2016-03-31 | Panasonic Corporation | Positive electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
US20160254545A1 (en) * | 2015-02-27 | 2016-09-01 | Panasonic Corporation | Nonaqueous electrolyte secondary battery |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0434871A (ja) * | 1990-05-29 | 1992-02-05 | Yuasa Corp | 電池の製造法 |
JPH0434871U (fr) | 1990-07-11 | 1992-03-24 | ||
US5478676A (en) * | 1994-08-02 | 1995-12-26 | Rexam Graphics | Current collector having a conductive primer layer |
JPH11312516A (ja) * | 1998-04-28 | 1999-11-09 | Sanyo Electric Co Ltd | リチウム二次電池用正極及びそれを用いたリチウム二次電池 |
JP3882391B2 (ja) | 1999-05-14 | 2007-02-14 | 三菱化学株式会社 | 二次電池用電極の製造法及び二次電池の製造方法 |
JP4297472B2 (ja) | 2001-08-28 | 2009-07-15 | アオイ電子株式会社 | 二次電池 |
US6881516B2 (en) * | 2002-09-30 | 2005-04-19 | Medtronic, Inc. | Contoured battery for implantable medical devices and method of manufacture |
CN101471435B (zh) * | 2007-12-25 | 2010-12-22 | 比亚迪股份有限公司 | 锂离子二次电池正极及包括该正极的锂离子二次电池 |
JP4352349B2 (ja) * | 2008-01-23 | 2009-10-28 | トヨタ自動車株式会社 | 電極および電極製造方法 |
WO2012046791A1 (fr) | 2010-10-08 | 2012-04-12 | Semiconductor Energy Laboratory Co., Ltd. | Procédé de fabrication de matériau actif d'électrode positive pour dispositif de stockage d'énergie, et dispositif de stockage d'énergie |
KR101271991B1 (ko) | 2011-07-06 | 2013-06-05 | 삼성에스디아이 주식회사 | 이차 전지 |
US9425459B2 (en) * | 2011-12-15 | 2016-08-23 | Samsung Electronics Co., Ltd. | Electrode for solid-state batteries and method of preparing the electrode, solid-state battery containing the electrode, and bonding film used for preparing the electrode |
CN203103398U (zh) * | 2012-12-07 | 2013-07-31 | 深圳市海太阳实业有限公司 | 一种正极极片及电池 |
KR20150011234A (ko) * | 2013-07-22 | 2015-01-30 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 전해질 및 이를 포함하는 리튬 이차 전지 |
JP6252841B2 (ja) | 2013-11-25 | 2017-12-27 | 株式会社Gsユアサ | 蓄電素子 |
KR102183997B1 (ko) * | 2014-02-07 | 2020-11-27 | 삼성에스디아이 주식회사 | 양극 활물질, 이를 채용한 양극과 리튬 전지 및 이의 제조 방법 |
JP2015216008A (ja) * | 2014-05-09 | 2015-12-03 | 凸版印刷株式会社 | リチウムイオン二次電池用正極、その製造方法、及びリチウムイオン二次電池 |
-
2017
- 2017-05-30 AU AU2017391883A patent/AU2017391883A1/en not_active Abandoned
- 2017-05-30 WO PCT/FR2017/051351 patent/WO2018220285A1/fr active Application Filing
- 2017-05-30 BR BR112018014287A patent/BR112018014287A2/pt not_active Application Discontinuation
- 2017-05-30 JP JP2018537768A patent/JP7468991B2/ja active Active
- 2017-05-30 US US16/068,352 patent/US11217794B2/en active Active
- 2017-05-30 KR KR1020187021362A patent/KR102415775B1/ko active IP Right Grant
- 2017-05-30 CA CA3011742A patent/CA3011742C/fr active Active
- 2017-05-30 EP EP17767860.4A patent/EP3443605A1/fr active Pending
- 2017-05-30 CN CN201780007721.7A patent/CN109565025A/zh active Pending
-
2022
- 2022-07-14 JP JP2022113119A patent/JP2022140503A/ja active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130209889A1 (en) * | 2010-10-21 | 2013-08-15 | Koji Takahata | Battery electrode and use thereof |
US20140322600A1 (en) * | 2011-11-15 | 2014-10-30 | Masahiro Morita | Nonaqueous electrolyte secondary battery |
FR3005207A1 (fr) * | 2013-04-24 | 2014-10-31 | Batscap Sa | Electrode positive pour batterie lithium |
US20160093922A1 (en) * | 2014-09-29 | 2016-03-31 | Panasonic Corporation | Positive electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
US20160254545A1 (en) * | 2015-02-27 | 2016-09-01 | Panasonic Corporation | Nonaqueous electrolyte secondary battery |
Non-Patent Citations (1)
Title |
---|
ZHAO, Q.; LU, Y.; CHEN, J.: "Advanced Organic Electrode Materials for Rechargeable Sodium-Ion Batteries", ADVANCED ENERGY MATERIALS, 2016 |
Also Published As
Publication number | Publication date |
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JP7468991B2 (ja) | 2024-04-16 |
CA3011742C (fr) | 2023-10-10 |
AU2017391883A1 (en) | 2018-12-13 |
CA3011742A1 (fr) | 2018-11-30 |
EP3443605A1 (fr) | 2019-02-20 |
JP2020527821A (ja) | 2020-09-10 |
US11217794B2 (en) | 2022-01-04 |
KR20200011861A (ko) | 2020-02-04 |
BR112018014287A2 (pt) | 2020-02-04 |
KR102415775B1 (ko) | 2022-07-01 |
JP2022140503A (ja) | 2022-09-26 |
US20190131629A1 (en) | 2019-05-02 |
CN109565025A (zh) | 2019-04-02 |
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