EP3743954A1 - Matériau d'électrode comprenant des particules de dioxyde de titane revêtues de carbone - Google Patents

Matériau d'électrode comprenant des particules de dioxyde de titane revêtues de carbone

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Publication number
EP3743954A1
EP3743954A1 EP19706374.6A EP19706374A EP3743954A1 EP 3743954 A1 EP3743954 A1 EP 3743954A1 EP 19706374 A EP19706374 A EP 19706374A EP 3743954 A1 EP3743954 A1 EP 3743954A1
Authority
EP
European Patent Office
Prior art keywords
carbon
range
titanium dioxide
particles
electrode material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19706374.6A
Other languages
German (de)
English (en)
Inventor
Jun Wang
Jie Li
Xin He
Xiaofei Zhang
Elie Paillard
Tobias PLACKE
Martin Winter
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.)
Forschungszentrum Juelich GmbH
Westfaelische Wilhelms Universitaet Muenster
Original Assignee
Forschungszentrum Juelich GmbH
Westfaelische Wilhelms Universitaet Muenster
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Filing date
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Application filed by Forschungszentrum Juelich GmbH, Westfaelische Wilhelms Universitaet Muenster filed Critical Forschungszentrum Juelich GmbH
Publication of EP3743954A1 publication Critical patent/EP3743954A1/fr
Pending legal-status Critical Current

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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • Electrode material comprising carbon-coated titanium dioxide particles
  • the invention relates to an electrode material comprising carbon-coated
  • Titanium dioxide particles a process for their preparation and its use as
  • Energy storage systems such as rechargeable batteries and electrochemical
  • capacitors ECs
  • LIBs Lithium ion rechargeable batteries
  • NEBs Rechargeable sodium ion batteries
  • Electrochemical capacitors are power devices that can be fully charged or discharged in seconds; as a result, their energy density (about 5 Wh kg 1 ) is lower than in batteries, but much higher power output (about 10 kW kg 1 ) can be achieved within a shorter time, for example a few seconds. Electrochemical capacitors therefore play an important role in supplementing or replacing batteries in the field of power supply such as uninterruptible power supplies (backup accessories to protect against power supply disruptions) and load balancing.
  • Transition metal oxides became titanium dioxide (Ti0 2 ) because of its exceptional stability as a potential active material for lithium and sodium ion batteries as well
  • carbon films are known to be a successful strategy for improving electrochemical performance.
  • Vinod Mathew et al. in Journal of The Electrochemical Society, 162 (7) A1220-A1226 (2015) an anode of porous titanium dioxide prepared by a polyol-based pyrosynthetic process.
  • known methods of carbon coating lead to a phase separation or agglomeration of TiCh nanoparticles and / or an inhomogeneous distribution of Carbon layer, which leads to a relatively low electronic conductivity, slow ion diffusion and low electrochemical performance.
  • an electrode material with a porous agglomeration of carbon-coated titanium dioxide particles, wherein titanium dioxide particles are coated with carbon and form spherical Ti0 2 / C particles, which agglomerate into a porous three-dimensional structure, wherein the average diameter of the Pore between the TiCh / C particles in the range of> 50 nm to ⁇ 200 nm.
  • Contain agglomeration or structure of carbon-coated titanium dioxide particles as electrode material have a very high capacity.
  • the electrodes demonstrated a stable cycle capacity of over 500 cycles in lithium and sodium ion batteries and over 2000 cycles in lithium and sodium ion based
  • the agglomerated particles form a three-dimensional structure in which small, primary TiCh nanoparticles are coated with carbon and thereby form spherical TiCh / C secondary particles, which in turn agglomerate into a three-dimensional structure.
  • the agglomerated structure has a platelike morphology.
  • the term “particles” is used synonymously with “particles” in the sense of the present invention.
  • the term “average diameter” is understood to mean the average value of all diameters or the arithmetically averaged diameters relative to the respective particles or pores.
  • the pore size or pore diameter can be evaluated using field emission scanning electron microscopy (SEM). The pore volume of the electrode material was measured using
  • the average diameter of the pores between the spherical TiO 2 / C particles is in the range of> 50 nm to ⁇ 200 nm.
  • the average diameter of the pores between the primary titanium dioxide particles is preferably in the range of> 2 nm to ⁇ 10 nm, preferably in the range of> 3 nm to ⁇ 6 nm.
  • the pore structure provides the electrode material with outstanding capacitive performance for both lithium ion and sodium ion batteries and supercapacitors, as demonstrated by electrochemical studies.
  • the average pore volume of the porous agglomeration is in the range of> 0.05 cm 3 / g to ⁇ 0.2 cm 3 / g, preferably in the range of> 0.06 cm 3 / g to ⁇ 0.14 cm 3 /G.
  • the middle one is in the range of> 0.05 cm 3 / g to ⁇ 0.2 cm 3 / g, preferably in the range of> 0.06 cm 3 / g to ⁇ 0.14 cm 3 /G.
  • Pore volume may for example be 0.1 cm 3 / g.
  • the high pore volume can contribute to a high capacity of an electrochemical cell.
  • the high pore volume can contribute to a high capacity of an electrochemical cell.
  • the BET surface area of the porous agglomeration is in the range of> 60 m 2 / g to ⁇ 100 m 2 / g, preferably in the range of> 65 m 2 / g to ⁇ 70 m 2 / g.
  • the BET surface area can be, for example, 68 m 2 / g.
  • the BET surface can through
  • Determination of the specific surface area of solids by gas adsorption after Brunauer-Emmett-Teller (BET) method can be determined by means of the adsorption of nitrogen, for example using a porosimeter.
  • the electrode material advantageously has a high pore volume and a large Brunauer-Emmett-Teller (BET) surface. It is believed that the large pore volume and large BET surface area lead to the high measured capacities of about 300 mAh g 1 in lithium ion cells and about 280 mAh g 1 in sodium ion cells.
  • the titanium dioxide particles have a size in the nanometer range.
  • the titanium dioxide particles have an average
  • Diameter in the range of> 1 nm to ⁇ 50 nm preferably in the range> 1 nm to ⁇ 10 nm, more preferably in the range of> 2 nm to ⁇ 10 nm, on.
  • a small size of the primary TiCh particles enables the electrochemical performance of the
  • Titanium dioxide is a stable and abundant and
  • Titanium dioxide is chemically resistant. Titanium dioxide (TiO 2 ) is understood as meaning titanium-valent oxides of titanium. Titanium dioxide forms a polymorphic oxide which, in addition to the three naturally occurring modifications, rutile, anatase and brookite, are synthetically engineered modifications. Useful polymorphic modifications are selected from fluorite, pyrite, rutile, anatase, hollandite, brookite, ramsdellite, columbite, cotunnite, modified fluorite, bronze, baddeleyite, the Fe 2 P-type hexagonal phase, and mixtures thereof. Preferred polymorphic
  • Modifications are selected from the types rutile, anatase and brookite.
  • the carbon-coated titanium dioxide particles also referred to as TiO 2 / C particles, have a spherical or spherical shape.
  • Spherical or spherical particles have the advantage of allowing good contact as electrode material.
  • the spherical TiO 2 / C particles have an average diameter in the range of> 10 nm to ⁇ 1 pm, preferably in the range of> 50 nm to ⁇ 500 nm.
  • spherical particles in particular with a size in the nanometer range, can provide a high specific surface area put. This allows a large contact surface of the particles with the electrolyte and thus a high number of possible reaction sites with those contained in the electrolyte
  • Charge-bearing ions in particular Li + - or nations.
  • the spherical Ti0 2 / C secondary particles agglomerate into a three-dimensional structure.
  • the porous three-dimensional structure comprises platelet-shaped particles, wherein the platelet-shaped particles preferably have an average diameter in the range of> 1 gm to ⁇ 100 gm, preferably in the range of> 2 pm to ⁇ 50 pm.
  • the free volume between the platelet-shaped particles can in the
  • the carbon coating of the titanium dioxide particles advantageously increases the electronic conductivity of the material.
  • the proportion of carbon based on the total weight of the porous agglomeration, in the range of 0.1 wt .-% to ⁇ 30 wt .-%, preferably in the range of 2 wt .-% to ⁇ 10 wt. %.
  • the proportion of carbon can be determined gravimetrically as shown in the examples.
  • the carbon may be formed of amorphous carbon, carbon nanotubes, graphene and mixtures thereof.
  • the coating of the titanium oxide particles with carbon can be achieved and controlled by calcining a carbonaceous compound and a titanium compound.
  • a preferred carbonaceous compound is graphene oxide.
  • Graphene oxide is understood to mean an oxidized and oxygenated functional grouped, single-ply or low-lathing graphene derivative.
  • Graphene oxide can be prepared by reacting naturally occurring graphite with strong oxidants and provides a starting material for the recovery of graphene in high yields Available.
  • Graphene oxide decomposes already at temperatures around 100 ° C to graphene and C0 / C0 2 .
  • the superior electrochemical performance is overall the structure of the
  • Electrode material that combines the advantages of a small primary particle size, large voids between the agglomerated platelet particles, and a homogeneous carbon coating.
  • Another object of the present invention relates to a method for producing a porous agglomeration of carbon-coated titanium dioxide particles, comprising the following steps:
  • step f) freeze-drying the precipitate of the precursor compound obtained from step e); g) calcining the precursor obtained from step f) to produce the porous agglomeration of carbon-coated titanium dioxide particles.
  • the method is in particular a method for producing an electrode material, in particular for lithium and sodium ion-based energy storage and
  • Supercapacitors in particular lithium and sodium ion-based supercapacitors, containing a porous agglomeration of carbon-coated titanium dioxide particles.
  • a solution (I) containing a titanium compound is prepared.
  • the titanium compound may be an organic or inorganic titanium (IV) salt.
  • the salt may be, for example, a sulfate, acetate, carbonate, nitrate, chloride, oxalate, an alkyl titanate, or a mixture thereof.
  • the solution (I) may contain a chelating agent.
  • the chelating agent is selected from the group comprising glutamic acid, histidine,
  • the weight ratio of the chelating agent to the titanium compound in the solution (I) may be in the range of 0: 1 to 1: 1.
  • the solvent may be selected from water, an alcohol or a mixture thereof. Preference is given to an alcoholic solvent.
  • the solvent for solution (I) is selected from methanol, ethanol, propanol, butanol or mixtures thereof.
  • the weight ratio of the solvent to the titanium compound and the chelating agent in step a) is in the range of> 1: 1 to ⁇ 999: 1, preferably in the range of> 2: 1 to ⁇ 99: 1.
  • a solution (II) containing a reducing agent and a carbon source is prepared.
  • the reducing agent is selected from formic acid, oxalic acid, ascorbic acid and mixtures thereof.
  • the carbon source is selected from organic carbon compounds, carbon nanotubes, graphene and
  • Graphene oxide or mixtures thereof.
  • the carbon source is graphene oxide.
  • the solution (II) may contain a surfactant.
  • the surfactant is selected from
  • Disodium monolauryl sulfosuccinate (disodium 4-dodecyl-2-sulfonato succinate),
  • the solvent may be selected from water, an alcohol or a mixture thereof.
  • the solvent for solution (II) is a mixture of alcohol and water.
  • the alcohol is preferably selected from methanol, ethanol, propanol, butanol or mixtures thereof.
  • the weight ratio of the alcohol to water in step b) is in the range of> 1: 99 to ⁇ 99: 1, preferably in the range of> 1: 9 to ⁇ 9: 1.
  • the weight ratio of the reducing agent to the solvent in step b) is in the range of> 1: 999 to ⁇ 1: 9.
  • the weight ratio of the carbon source to the solvent in step b) is in the range of> 1: 99 to ⁇ 1: 1, preferably in the range of> 1: 99 to ⁇ 1: 2.
  • the weight ratio of the surfactant to the solvent in Step b) in the range of> 1: 999 to ⁇ 1: 9, preferably in the range of> 1: 999 to ⁇ 1: 99.
  • step c) The solutions (I) and (II) are combined in step c) to form a slurry.
  • the reaction temperature in step c) may be in the range of 0 ° C to 100 ° C.
  • the slurry is mixed in step d), in particular mixed homogeneously. This can be assisted by stirring, especially for several hours, for example for 6 to 12 hours, and aging of the slurry. Subsequently, in step e), a precipitate obtained from the slurry from step d) is obtained
  • Isolated precursor compound This can be achieved in particular by repeated washing and centrifuging. It is believed that the precipitate is formed from a precursor compound of the carbon-coated particles to be formed, with the carbon source depositing on the titanium compound.
  • the precipitate of the precursor compound obtained from step e) is freeze-dried in step f).
  • the precursor obtained from step f) is calcined to produce the porous agglomeration of carbon-coated titanium dioxide particles.
  • the term "calcining” is understood as meaning the heating of a material in order to produce a state of thermal decomposition.
  • the calcining For example, a titanium hydroxide or other titanium compound converts to titanium oxide.
  • the calcination is preferably carried out under a protective gas atmosphere, for example in a reaction atmosphere of argon, a mixture of hydrogen and argon,
  • the reaction temperature of the calcining is in the range of> 400 ° C to ⁇ 1000 ° C.
  • the reaction time for calcining is in the range of 1 to 100 hours.
  • the titanium dioxide particles of the porous agglomeration obtained are coated with carbon and form spherical TiO 2 / C particles which agglomerate into a porous three-dimensional structure, the average diameter of the pores between the TiO 2 / C particles in the range of> 50 nm to ⁇ 200 nm.
  • the resulting porous agglomeration of carbon-coated titanium dioxide particles is particularly useful as electrode material for lithium ion and sodium ion batteries and supercapacitors, particularly lithium and sodium ion based supercapacitors.
  • Another object relates to a porous agglomeration of carbon-coated titanium dioxide particles obtainable by the process according to the invention.
  • This material can be used in particular for the production of electrodes, in particular anodes.
  • Another object of the invention relates to an electrode containing a
  • Inventive electrode material with a porous agglomeration of carbon-coated titanium dioxide particles or a porous agglomeration of carbon-coated titanium dioxide particles obtainable by the process according to the invention.
  • the titanium dioxide particles are coated with carbon and form spherical TiO 2 / C particles, which agglomerate into a porous three-dimensional structure, wherein the middle
  • porous agglomeration of carbon-coated titanium dioxide particles form the material, commonly referred to as "active material", of an electrode capable of reversibly receiving and releasing lithium or sodium ions.
  • active material of an electrode capable of reversibly receiving and releasing lithium or sodium ions.
  • An electrode containing an electrode material according to the invention can advantageously be a very good
  • an electrode In addition to the active material, an electrode usually still contains binder and conductive carbon. These are usually applied to a metal foil, such as a copper or aluminum foil, as a current conductor. Such an electrode is
  • the electrode is a composite electrode comprising an electrode material according to the invention with a porous agglomeration of carbon-coated titanium dioxide particles. It can be provided to add further carbon for the production of an electrode.
  • Preferred carbonaceous materials are, for example, carbon black, synthetic or natural graphite, graphene, carbon nanoparticles, fullerenes, or mixtures thereof.
  • a usable carbon black is, for example, carbon black.
  • Leitruß is understood to mean a carbon black which has small primary particles and widely branched aggregates, and thus enables good electronic conductivity.
  • a preferred carbon black is available, for example, under the trade designation Super C65 (Imerys).
  • the composite electrode may comprise a binder. Suitable binders are, for example
  • PVdF Polyvinylidene difluoride
  • Na-CMC sodium carboxymethylcellulose
  • the dry weight of a mixture of the porous agglomeration of carbon-coated titanium dioxide particles, binder and conductive carbon may be 80% by weight of the agglomerate, 10% by weight carbon black and 10% by weight of binder, for example PVdF, based on the total dry weight the mixture.
  • the production of The electrode may include the steps of mixing the porous agglomeration with carbon black, mixing the solid mixture with a binder dissolved in a solvent, applying the slurry to an electronically conductive substrate, and drying the resulting electrode.
  • Another object relates to an electrochemical energy store, in particular a lithium or sodium ion-based electrochemical energy store or a supercapacitor, in particular a lithium and sodium ion-based
  • the electrode contains an electrode material with a porous agglomeration of carbon-coated
  • Titanium dioxide particles are coated with carbon and form spherical TiO 2 / C particles, which agglomerate into a porous three-dimensional structure, wherein the average diameter of the pores between the TiCh / C particles in the range of> 50 nm to ⁇ 200 nm ,
  • the electrode material For the further description of the electrode material, reference is made to the above description.
  • energy storage in the context of the present invention includes primary and secondary electrochemical energy storage devices and energy storage systems, ie batteries (primary storage) and accumulators (secondary storage).
  • primary and secondary electrochemical energy storage devices and energy storage systems ie batteries (primary storage) and accumulators (secondary storage).
  • Electrochemical energy storage for the purposes of the present invention also includes electrochemical capacitors or supercapacitors (English: electrochemical (super) capacitors). Electrochemical capacitors, also known in the literature as
  • Double-layer capacitors, or supercapacitors are electrochemical energy storage devices that stand out from batteries by a significantly higher power density, compared to conventional capacitors by a orders of magnitude higher
  • Electrochemical energy stores are preferably selected from the group comprising lithium ion batteries, lithium ion accumulators,
  • Sodium ion batteries and sodium ion accumulators Preferably, the
  • the electrochemical energy store is a supercapacitor, in particular a lithium and sodium ion-based supercapacitor.
  • the electrochemical energy store is a lithium or sodium ion battery comprising a positive electrode, a negative electrode, an electrolyte between the electrodes, the negative electrode containing the
  • the electrochemical energy storage is a supercapacitor comprising a working electrode, a counter electrode, a reference electrode and an electrolyte, wherein the
  • Working electrode comprises the electrode material according to the invention.
  • the electrochemical energy store is a lithium- and sodium-ion-based supercapacitor comprising a positive electrode, a negative electrode, and an electrolyte between the electrodes, the negative electrode comprising the electrode material according to the invention.
  • Preferred conducting salts are LiPF ö and NaCl0. 4
  • the solvent of the electrolyte mixtures of ethylene carbonate (EC) and dimethyl carbonate (DMC) or ethylene carbonate (EC) and propylene carbonate (PC) are particularly preferred.
  • FIG. 2 shows the X-ray diffractogram of the carbon-coated titanium dioxide particles obtained.
  • Titanium dioxide particles are used.
  • Figure 4 shows the Raman spectrum of the porous agglomeration of carbon-coated
  • Titanium dioxide particles are used.
  • FIG. 5 shows the X-ray diffractogram of a porous agglomeration of carbon
  • coated titanium dioxide particles according to a second embodiment of the invention.
  • FIG. 6 shows the results of the cyclization of a lithium-ion cell using a porous agglomeration of carbon-coated titanium dioxide particles as electrode material.
  • Figure 6a) shows a plot of voltage versus capacitance for the first five cycles
  • Figure 6b) shows the capacitance of the electrode at various C rates plotted against the number of charge / discharge cycles
  • Figure 6c) shows the charge capacity (left ordinate axis).
  • FIG. 7 shows the results of the cyclization of a sodium ion cell using a porous agglomeration of carbon-coated titanium dioxide particles as electrode material.
  • Figure 7a) shows a plot of voltage versus capacitance for the first five cycles
  • Figure 7b) shows the capacitance of the electrode at various C rates plotted against the number of charge / discharge cycles
  • Figure 7c) shows the charge capacity (left ordinate axis). and Coulomb efficiency (right ordinate axis) of the electrode plotted against the number of charge / discharge cycles at an applied current density of 85 mA g 1 .
  • FIG. 8 shows the results of the cyclization of a lithium-ion-based supercapacitor.
  • Figure 8a) shows a plot of voltage vs. time for different current densities
  • Figure 8b) shows capacitance retention of the electrode versus scan rate
  • Figure 8c) shows capacitance retention versus number of cycles.
  • FIG. 9 shows the results of the cyclization of a sodium ion-based supercapacitor.
  • Figure 9a shows a plot of potential versus time for different current densities
  • Figure 9b shows capacitance retention of the electrode plotted against current density
  • Figure 9c shows capacitance retention versus number of cycles.
  • SAED selected-area electron diffraction
  • FIG. 1 a shows a representative scanning electron micrograph of the resulting composite.
  • the composite comprises platelet-like particles.
  • the plate-like particles have a length of several micrometers. Between the platelets large cavities can be seen. These are particularly advantageous for electron transport and electrolyte wetting.
  • the platelet-like particles are composed of agglomerated, spherical secondary particles which are formed from graphene-coated TiO 2 primary particles. In particular, a homogeneous carbon coating can be seen.
  • HRTEM images showed that the Ti0 2 primary particles had a mean diameter smaller than 10 nm.
  • the X-ray diffractometry signals shown in FIG. 2 showed that the signals of the obtained TiO 2 coincide with those of the anatase phase.
  • FIG. 3 shows the signal of the thermogravimetric analysis of the obtained TiO 2 graph Composite. As can be seen from Figure 3, a major weight loss of 8.5% by weight was observed between 300 ° C and 600 ° C. This is attributed to the combustion of carbon into C0 2 and CO, suggesting that the content of
  • the Raman spectrum of the TiO 2 graphite composite shown in FIG. 4 shows typical bands from the anatase phase at 150, 390, 510 and 635 cm 1, respectively.
  • the characteristic bands of graphene are visible at 1343 cm 1 (D band) and 1597 cm 1 (G band).
  • the BET surface area was determined by determining the specific surface area of solids by gas adsorption by the Brunauer-Emmett-Teller (BET) method using a Micromeritics ASAP-2020 M apparatus using nitrogen adsorption isotherms.
  • the BET surface area of the produced carbon-coated spherical Ti0 2 / C secondary particles was calculated to be 67.9 m 2 g 1 .
  • the result of the pore size distribution calculated from the desorption isotherm using the Barrett-Joyner-Halenda (BJH) method showed the presence of nanopores with an average pore diameter of 5 nm.
  • the average diameter of the pores between the TiO 2 / C secondary particles was at 128 nm.
  • the X-ray diffractometry signals shown in FIG. 5 showed that the resulting TiO 2 had a brookite structure.
  • the content of carbon was determined by thermogravimetric analysis (TGA) to be 28% by weight based on the total weight of the composite.
  • the TiO 2 / C composites of anatase-structure carbon-coated titanium dioxide particles prepared according to Example 1 together with a conductive carbon (Super C65, Imerys) and polyvinylidene difluoride (PVdF, ARKEMA KYNAR) as a binder were in a weight ratio of 80:10:10 in 1-methyl-2-pyrrolidinone (NMP, ACROS Organics).
  • NMP 1-methyl-2-pyrrolidinone
  • the 2032-type button cells were assembled in a dry room.
  • electrolyte was a Solution of 1 M LiPF ö used in a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) in the volume ratio 1: 1.
  • the separator used was an electrolyte-impregnated glass fiber filter (Whatman, GF / D).
  • the cells were activated at a current density of 0.1 C corresponding to 17 mA g 1 for the first cycle and then cycled at 0.5 C for 50 cycles in a voltage range of 1.0-3.0 V against lithium.
  • Figure 6 shows the results of the cyclization.
  • Figure 6a) shows a plot of voltage versus capacitance for the first five cycles
  • Figure 6b) shows the specific capacitance of the electrode at different C rates plotted against the number of charge / discharge cycles
  • Figure 6c) shows the charge and discharge Capacitance (left ordinate axis) and efficiency (right ordinate axis) of the electrode plotted against the number of charge / discharge cycles at an applied current density of 85 mA g 1 over 500 cycles.
  • the cell provided a very high charge capacity of about 310 mAh g 1 and had a constant capacity over 500 cycles.
  • the electrochemical examination of the sodium ion battery was carried out using a TiO 2 / C composite electrode prepared according to Example 3 as an anode in three-electrode Swagelok TM cells with sodium metal foil as counter and reference electrodes.
  • the 2032-type button cells were assembled in a dry room.
  • the electrolyte used was a solution of 1 M NaClO 4 in a mixture of EC and propylene carbonate (PC) in the volume ratio 1: 1.
  • the separator was an electrolyte-soaked Glass fiber filter (Whatman, GF / D) used.
  • the cells were activated at a current density of 0.1 C corresponding to 17 mA g 1 for the first cycle and then cycled at 0.5 C for 50 cycles in a voltage range of 0.05-2.0 V versus sodium.
  • Figure 7 shows the results of the cyclization of the sodium ion cell.
  • Figure 7a) shows a plot of voltage versus capacitance for the first five cycles
  • Figure 7b) shows the capacitance of the electrode at various C rates plotted against the number of charge / discharge cycles
  • Figure 7c) shows the charge and discharge Capacity (left
  • the electrochemical examination of a lithium-ion supercapacitor was carried out in three-electrode Swagelok TM cells using a TiO 2 / C composite electrode prepared according to Example 3 as the anode and commercial activated carbon as the cathode.
  • the preparation of the cathode was analogous to the production of the anode, wherein 90 wt .-% activated carbon, 5 wt .-% Super C65 and 5 wt .-% sodium carboxymethyl cellulose (Na CMC) were used.
  • the mass loading was between 2, 4-3.0 mg cm 2 .
  • Lithium metal foil served as the third electrode for the pre-lithiation.
  • the lithium ion supercapacitor was assembled in a dry room.
  • electrolyte was a Solution of 1 M LiPF ö used in a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) in the volume ratio 1: 1.
  • the separator used was an electrolyte-impregnated glass fiber filter (Whatman, GF / D).
  • the working electrode was first pre-lithiated by the third electrode at a current density of 10 mA g 1 for the first discharge. Subsequently, the lithium ion capacitor was cycled at various different C rates between 1.0V and 3.0V.
  • Figure 8 shows the results of the cyclization of the lithium ion-based
  • the electrochemical examination of a sodium ion supercapacitor was carried out in three-electrode Swagelok TM cells using a TiCh / C composite electrode prepared according to Example 3 as the anode and commercial activated carbon as the cathode.
  • the preparation of the cathode was analogous to the production of the anode, wherein 90 wt .-% activated carbon, 5 wt .-% Super C65 and 5 wt .-% sodium carboxymethyl cellulose (Na CMC) were used.
  • the mass loading was between 2, 4-3.0 mg cm 2 .
  • Sodium metal foil served as the third electrode for the pre-sodiation.
  • the supercapacitor was assembled in a dry room.
  • the electrolyte used was a solution of 1 M NaClO 4 in a mixture of EC and PC in a volume ratio of 1: 1.
  • the separator used was an electrolyte-impregnated glass fiber filter (Whatman, GF / D).
  • the working electrode was first pre-natriumzed by the third electrode at a rate of 0.1C for the first discharge. Subsequently, the sodium ion capacitor was cycled at various different C rates between 1.0V and 3.8V.
  • FIG. 9 shows the results of the cyclization of the sodium ion supercapacitor.
  • Figure 9a) shows a plot of potential versus time for different current densities
  • Figure 9b) shows capacitance retention of the electrode versus current density
  • Figure 9c) shows capacitance retention versus number of cycles.
  • the sodium ion-based supercapacitor provided good capacity retention under high current densities and good cycle performance.
  • Agglomerations of carbon-coated titanium dioxide particles can represent a favorable anode material with high cycle stability.

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Abstract

L'invention concerne un matériau d'électrode comprenant une agglomération poreuse de particules de dioxyde de titane revêtues de carbone, les particules de dioxyde de carbone étant revêtues de carbone et formant des particules TiO2/C sphériques lesquelles s'agglomèrent pour former une structure tridimensionnelle poreuse, le diamètre moyen des pores entre les particules TiO2/C étant compris dans la plage de valeurs supérieures ou égales à 50 nm et inférieures ou égales à 200 nm. Cette invention se rapporte en outre aux électrodes ainsi produites.
EP19706374.6A 2018-01-23 2019-01-14 Matériau d'électrode comprenant des particules de dioxyde de titane revêtues de carbone Pending EP3743954A1 (fr)

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DE102018101484.8A DE102018101484A1 (de) 2018-01-23 2018-01-23 Elektrodenmaterial umfassend Kohlenstoff-beschichtete Titandioxid-Partikel
PCT/EP2019/050831 WO2019145181A1 (fr) 2018-01-23 2019-01-14 Matériau d'électrode comprenant des particules de dioxyde de titane revêtues de carbone

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