EP4437598A2 - Energy storage cells with fast charge and discharge capabilities - Google Patents

Energy storage cells with fast charge and discharge capabilities

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Publication number
EP4437598A2
EP4437598A2 EP22800245.7A EP22800245A EP4437598A2 EP 4437598 A2 EP4437598 A2 EP 4437598A2 EP 22800245 A EP22800245 A EP 22800245A EP 4437598 A2 EP4437598 A2 EP 4437598A2
Authority
EP
European Patent Office
Prior art keywords
particles
active material
binder
proportion
vol
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
EP22800245.7A
Other languages
German (de)
French (fr)
Inventor
Pattarachai SRIMUK
Roland VÄLI
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.)
Skeleton Technologies GmbH
Original Assignee
Skeleton Technologies 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
Priority claimed from DE102022100864.9A external-priority patent/DE102022100864A1/en
Application filed by Skeleton Technologies GmbH filed Critical Skeleton Technologies GmbH
Publication of EP4437598A2 publication Critical patent/EP4437598A2/en
Pending legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0409—Methods of deposition of the material by a doctor blade method, slip-casting or roller coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • 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
    • H01M4/36—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
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • 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
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to energy storage cells, e.g. hybrid supercapacitors, with fast charge and discharge capabilities as well as their components, such as electrodes and electrolytes.
  • the cells may serve as traction battery, intermediate energy storage for kinetic energy recovery systems, or energy storage for mechanical assistance systems, such as anti-skid systems or active shock absorbers.
  • energy storage for mechanical assistance systems, such as anti-skid systems or active shock absorbers.
  • grid regulation the cells store excess produced energy, in particular excess wind or solar energy, and help closing the energy gap in situations of high demand.
  • Energy storage cells may generally be divided into batteries and capacitors. While batteries store electric energy in chemical form, capacitors usually store electric energy in the electric field. Batteries are usually not capable of achieving the peak powers that are required for the abovementioned applications.
  • Ultracapacitors also known as supercapacitors, are a kind of capacitor and can be separated into double-layer capacitors and pseudocapacitors.
  • the former store electrical energy in an electrostatic double-layer, whereas the latter store the electrical energy electrochemically, but in a different manner than batteries.
  • hybrid (super)capacitors have been developed that combine the features of double-layer capacitors and pseudocapacitors.
  • capacitors usually exhibit a large voltage variation during charging and discharging, whereas batteries do not.
  • the main advantage for capacitors is that they are great for applications that require large peak powers or - in other words - a large energy transfer within very short time.
  • This capability, in particular for supercapacitors, is not without limits, since in general the actually usable capacity depends on the discharge current: the larger the current, the smaller the usable capacity.
  • US 5 258 245 A discloses a lithium battery comprising a positive electrode mainly of vanadium pentoxide, a negative electrode mainly of lithium doped niobium pentoxide, and an electrolyte mainly of an anhydrous solvent with dissolved lithium salt.
  • US 2021 / 0 110 980 A1 , US 2021 / 0 110 979 A1 , and US 2021 I 0 218 048 A1 disclose cell concepts that employ three or four electrodes.
  • the invention provides a positive active material composition for a positive electrode of an energy storage cell, the composition consisting of:
  • LiNi x Mn2- x O4 particles wherein 0 ⁇ x ⁇ 1.0; optionally 0.1 wt% to 2 wt% carbon nanotubes (CNTs); optionally 0.1 wt% to 2 wt% graphene; and optionally less than 5 wt% of other components or impurities.
  • LNMO LiNi x Mn2- x O4
  • the LNMO particles have a particle size of D90 of 8 pm to 10 pm.
  • the LNMO particles have a particle size of D50 of 6 pm to 7 pm.
  • the LNMO particles have a particle size of D10 of 4 pm to ⁇ 5 pm.
  • the proportion of CB is 1 .5 wt% to 5 wt% or 9 wt% to 11 wt%, preferably 2.0 wt% to 4.0 wt% or 9.5 wt% to 10.5 wt%.
  • the proportion of the at least one binder is 3.5 wt% to 4.5 wt% or 5.5 wt% to 6.5 wt%, preferably 4.0 wt% to 4.4 wt% or 5.5 wt% to 6.5 wt%.
  • the positive active material exclusively consists of LMNO particles, wherein the proportion of the LMNO particles is at least 85 wt%, preferably at least 90 wt%, wherein the total proportion of the remaining components is chosen to complete to 100 wt%.
  • the invention provides a method for manufacturing a positive electrode (32) for an energy storage cell, the method comprising: a) provide 3 wt% to 8 wt% binder in a mixing vessel; b) mixing in the vessel, so as to obtain a slurry:
  • the invention provides a negative active material composition for a negative electrode of an energy storage cell, the composition consisting of:
  • the negative active material consists of Nb2Os particles, activated carbon (MC) particles and optionally of lithium titanate particles.
  • the amount of negative material is 85 wt% to 96 wt%, more preferably 88 wt% to 96 wt%, more preferably 89.5 wt% to 94.5 wt%.
  • the negative active material exclusively consists of Nb2Os particles and MC particles and the proportion of Nb2Os particles is 50% to 95%, preferably 60% to 90%, more preferably 60% to 80%, and the remaining proportion to 100% is MC particles.
  • the negative active material exclusively consists of Nb2Os particles, MC particles, and lithium titanate particles, and the proportion of Nb2Os particles is 20% to 40%, preferably 25% to 35%, more preferably 30%, and the porportion of lithium titanate particles is 20% to 40%, preferably 25% to 35%, more preferably 30%, and the remaining proportion to 100% is MC particles.
  • total amount of the at least one binder is 3 wt% to 6 wt%, preferably 3 wt% to 4.5 wt%.
  • the invention provides a method for manufacturing a negative electrode for an energy storage cell, the method comprising: a) provide 2 wt% to 7 wt% of at least one binder in a mixing vessel; b) mixing in the vessel, so as to obtain a slurry:
  • 82 wt% to 98 wt% of negative active material that consists of 30% to 90% of Nb2C>5 particles, activated carbon (MC) particles and optionally of lithium titanate particles; optionally up to 6 wt% in total of at least one conductive additive; and optionally less than 5 wt% in total of other components; c) coating a conductive electrode substrate with the slurry and heating the coated electrode substrate, thereby generating the negative electrode.
  • the Nb20s particles mostly consist of orthorhombic Nb20s. In an embodiment the Nb20s particles consists of more than 90 wt% of orthorombic Nb20s.
  • the Nb20s particles have a particle size of D90 1 pm to 100 pm, preferably of 2 pm to 60 pm, more preferably of 10 pm to 30 pm.
  • the Nb2C>5 particles have a particle size of D10 0.05 pm to 10 pm, preferably 0.3 pm to 5 pm, more preferably of 0.3 pm to 3 pm.
  • the MC particles have a BET nitrogen surface area of at least 60 m 2 /g, preferably of at least 1000 m 2 /g.
  • the MC particles have a particle size D90 of 5 pm to 30 pm, preferably of 5 pm to 20 pm. In an embodiment the MC particles have a particle size of D10 1 pm to 2 pm. In an embodiment the MC particles comprise carbide derived carbon (CDC) particles.
  • CDC carbide derived carbon
  • each conductive additive is selected from a group consisting of carbon black, carbon nanotubes (CNTs), graphene, and mixtures thereof.
  • CNTs carbon nanotubes
  • the CNTs are multi-walled CNTs (MWCNTs).
  • the composition includes 1 wt% to 5 wt% carbon black as a conductive additive. In an embodiment the composition includes 1 wt% to 4 wt% carbon black as a conductive additive. In an embodiment the composition includes 2 wt% to 4 wt% carbon black as a conductive additive.
  • the composition includes 0.3 wt% to 2 wt% CNTs. In an embodiment the composition includes 0.5 wt% to 1.1 wt% CNTs.
  • the invention provides energy storage cell for storing electrical energy, the cell comprising a plurality of electrodes that are immersed in an organic anhydrous electrolyte, wherein at least one electrode is configured as a negative electrode and at least one electrode is configured as a positive electrode, wherein the positive electrode includes a preferred positive electrode material composition or obtainable by a preferred method according.
  • the negative electrode includes a negative electrode material composition as described herein or obtainable by a method described herein.
  • the organic anhydrous electrolyte consists of one of the following: a) 40 vol% to 60 vol% acetonitrile (ACN), 60 vol% to 40 vol% ethylenecarbonate (EC) and a lithium conductive salt; or b) propylene carbonate (PC) and optionally EC and a lithium conductive salt; or c) EC, ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC).
  • the electrolyte consists of 50 vol% ACN and 50 vol% EC and the lithium conductive salt.
  • the electrolyte consists of 70 vol% PC and 30 vol% EC and the lithium conductive salt.
  • the electrolyte consists of 25 vol% EC, 5 vol% EMC and 70 vol% DMC.
  • the lithium conductive salt is LiPFe.
  • the lithium conductive salt is UBF4.
  • the invention provides an organic anhydrous electrolyte composition for an energy storage cell, the composition consisting of a) 40 vol% to 60 vol% acetonitrile (ACN), 60 vol% to 40 vol% ethylenecarbonate (EC) and a lithium conductive salt; or b) propylene carbonate (PC) and optionally EC and a lithium conductive salt; or c) EC, ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC).
  • ACN acetonitrile
  • EC ethylenecarbonate
  • PC propylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • the electrolyte consists of 50 vol% ACN and 50 vol% EC and the lithium conductive salt.
  • the electrolyte consists of 70 vol% PC and 30 vol% EC and the lithium conductive salt.
  • the electrolyte consists of 25 vol% EC, 5 vol% EMC and 70 vol% DMC.
  • the conductive lithium salt has a concentration of 0.1 mol/l to 3 mol/l, preferably 1 mol/l.
  • the lithium conductive salt is selected from a group consisting of lithium perchlorate (l_iCIC>4), lithium tetrafluoroborate (LiBF4), lithium hexafluorophosphate (LiPFe), lithium hexafluoroarsenate (LiAsFe), lithium trifluoromethanesulfonate (USO3CF3), lithium bis(trifluoromethylsulfonyl)imide (LiN(SC>2CF3)2), lithium bis(pentafluoroethanesulfonyl)imide (LiN(SO2C2Fs)2), lithium bis(oxalato)borate (LiBOB, LiB(C2O4)2), lithium difluoro(oxalato)borate (LiBF2(C2C>4)), lithium tris(pentafluoroethyl)trifluorophosphate (LiPF 3 (C2F 5 )3) and mixtures thereof.
  • the lithium conductive salt is LiPFe.
  • the invention provides an energy storage cell for storing electrical energy, the cell comprising a positive electrode and a negative electrode immersed in an organic anhydrous electrolyte, wherein the negative electrode includes a negative active material composition that has Nb20s particles, activated carbon (MC) particles and optionally of lithium titanate particles.; wherein the positive electrode includes a positive active material composition that for the most part has LiNi x Mn2- x O4 (LNMO) particles, wherein 0 ⁇ x ⁇ 1.0.
  • the negative active material composition includes a negative active material that consists of Nb20s particles and MC particles.
  • the negative active material composition includes a negative active material that consists of Nb20s particles, MC particles and lithium titanate particles.
  • the amount of Nb20s particles and the amount of MC particles is selected from a group consisting of 30 wt%, 40 wt%, 50 wt%, 60 wt%, and 70 wt%, such that the total amount is 100 wt%.
  • the negative electrode composition and/or the positive electrode composition include at least one conductive additive.
  • the at least one conductive additive is selected from a group consisting of carbon black (CB), carbon nanotubes (CNTs), graphene, and mixtures thereof.
  • the negative active material composition consists of more than 50 wt%, preferably of more than 60 wt%, negative active material.
  • the positive active material composition consists of more than 50 wt%, preferably of more than 90 wt%, preferably of more than 95 wt%, preferably of 97 wt% or more, positive active material.
  • the MC particles have a BET nitrogen surface area of at least 60 m 2 /g, preferably of at least 1000 m 2 /g.
  • the MC particles have a particle size D90 of 5 pm to 30 pm, preferably 5 pm to 20 pm. In an embodiment the MC particles have a particle size of D10 1 pm to 2 pm.
  • the MC particles comprise carbide derived carbon particles.
  • CNTs are multi-walled CNTs (MWCNTs).
  • the negative electrode composition includes 1 wt% to 10 wt% carbon black. In an embodiment the negative electrode composition includes 1 wt% to 8 wt% carbon black. In an embodiment the negative electrode composition includes 1 wt% to 3 wt% carbon black. In an embodiment the negative electrode composition includes 2 wt% to 6 wt% carbon black. In an embodiment the negative electrode composition includes 3 wt% to 7 wt% carbon black.
  • the positive electrode composition includes 1 wt% to 10 wt% carbon black. In an embodiment the positive electrode composition includes 1 wt% to 8 wt% carbon black. In an embodiment the positive electrode composition includes 1 wt% to 3 wt% carbon black. In an embodiment the positive electrode composition includes 2 wt% to 6 wt% carbon black. In an embodiment the positive electrode composition includes 3 wt% to 7 wt% carbon black.
  • the negative electrode composition includes 0.3 wt% to 2 wt%, preferably 0.3 wt% to 1 .0 wt% CNTs.
  • the positive electrode composition includes 0.3 wt% to 2 wt%, preferably 0.3 wt% to 1.0 wt% CNTs.
  • the negative electrode composition includes 0.3 wt% to 2 wt%, preferably 0.3 wt % to 1 .0 wt%, graphene.
  • the positive electrode composition includes 0.3 wt% to 2 wt%, preferably 0.3 wt % to 1.0 wt%, graphene.
  • the proportion of CNTs deviates from the proportion of graphene or vice versa by less than 10%. In an embodiment the proportions of CNTs and graphene are identical.
  • the electrolyte includes a lithium conductive salt, 80 vol% to 95 vol% acetonitrile, and 5 vol% to 20 vol% ethylenecarbonate.
  • the lithium conductive salt is selected from a group consisting of lithium perchlorate (l_iCIC>4), lithium tetrafluoroborate (UBF4), lithium hexafluorophosphate (LiPFe), lithium hexafluoroarsenate (LiAsFe), lithium trifluoromethanesulfonate (IJSO3CF3), lithium bis(trifluoromethylsulfonyl)imide (LiN(SC>2CF3)2), lithium bis(pentafluoroethanesulfonyl)imide (LiN(SO2C2Fs)2), lithium bis(oxalato)borate (LiBOB, LiB(C2O4)2), lithium difluoro(oxalato)borate (LiBF2(C2C>4)), lithium tris(pentafluoroethyl)trifluorophosphate (LiPF 3 (C2F 5 )3) and mixtures thereof.
  • an energy storage cell 1 may be configured as a hybrid ultracapacitor.
  • the energy storage cell 1 is preferably formed as a cylinder.
  • the energy storage cell 1 comprises a first electrode arrangement 2 and a second electrode arrangement 3. Both electrode arrangements are immersed in an organic anhydrous electrolyte 4.
  • the energy storage cell 1 comprises a separator 5 that is interposed between the first and second electrode arrangements 2, 3.
  • the energy storage cell 1 usually contains a plurality of windings of the first and second electrode arrangements 2, 3 about the cylinder axis, however for the sake of clarity only portions are shown here.
  • the first electrode arrangement 2 comprises an anode terminal 21.
  • the anode terminal 21 is arranged so that an external electric contact can be formed.
  • the first electrode arrangement 2 comprises a negative electrode 22.
  • the negative electrode 22 is electrically coupled to the anode terminal 21.
  • the negative electrode 22 includes a current collector 23 that is made of metal, preferably aluminium.
  • the current collector 23 contacts the anode terminal 21.
  • the negative electrode 22 includes a negative electrode material 24.
  • the second electrode arrangement 3 comprises a cathode terminal 31.
  • the cathode terminal 31 is arranged so that an external electric contact can be formed.
  • the second electrode arrangement 3 comprises a positive electrode 32.
  • the positive electrode 32 is electrically coupled to the anode terminal 31.
  • the positive electrode 32 includes a current collector 33 that is made of metal, preferably aluminium.
  • the current collector 33 contacts the cathode terminal 31.
  • the positive electrode 32 includes a positive electrode material 34.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water.
  • Styrene butadiene rubber (SBR) is added as a second binder.
  • the total proportion of the binder is 4.2 wt%.
  • Carbon black (CB) is added as a first conductive additive with a proportion of 4.1 wt%.
  • Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 1.1 wt%.
  • Activated carbon (MC) particles and Nb20s particles are added as a negative active material.
  • the Nb20s particles are made of orthorombic Nb20s.
  • the negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities.
  • the negative active material consists of 60 wt% Nb20s particles and 40 wt% MC particles.
  • the MC particles are made from coconut.
  • a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 23.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water.
  • Styrene butadiene rubber (SBR) is added as a second binder.
  • the total proportion of the binder is 4.0 wt%.
  • Carbon black (CB) is added as a first conductive additive with a proportion of 2.0 wt%.
  • Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 0.5 wt%.
  • Activated carbon (MC) particles and Nb2Os particles are added as a negative active material.
  • the Nb2Os particles are made of orthorombic Nb2Os.
  • the negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities.
  • the negative active material consists of 30 wt% Nb2Os particles, 40 wt% MC particles and 30 wt% of lithium titanate (LTO) particles.
  • the MC particles are made from coconut.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water.
  • Styrene butadiene rubber (SBR) is added as a second binder.
  • the total proportion of the binder is 4.3 wt%.
  • Carbon black is added as a first conductive additive with a proportion of 1 .0 wt%.
  • Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 0.5 wt%.
  • Activated carbon (MC) particles and Nb2Os particles are added as a negative active material.
  • the Nb2Os particles are made of orthorombic Nb2Os.
  • the negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities.
  • the negative active material consists of 60 wt% Nb2Os particles and 40 wt% MC particles.
  • the MC particles are made from carbide derived carbon, namely SiC derived carbon.
  • a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 23.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water.
  • Styrene butadiene rubber (SBR) is added as a second binder.
  • the total proportion of the binder is 4.1 wt%.
  • Carbon black (CB) is added as a first conductive additive with a proportion of 2.0 wt%.
  • Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 0.5 wt%.
  • Activated carbon (MC) particles and Nb2Os particles are added as a negative active material.
  • the Nb2Os particles are made of orthorombic Nb2Os.
  • the negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities.
  • the negative active material consists of 60 wt% Nb2Os particles and 40 wt% MC particles.
  • the MC particles are made from carbide derived carbon, namely SiC derived carbon.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water.
  • Styrene butadiene rubber (SBR) is added as a second binder.
  • the total proportion of the binder is 4.0 wt%.
  • Carbon black (CB) is added as a first conductive additive with a proportion of 2.0 wt%.
  • Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 0.5 wt%.
  • Activated carbon (MC) particles and Nb2Os particles are added as a negative active material.
  • the Nb2Os particles are made of orthorombic Nb2Os.
  • the negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities.
  • the negative active material consists of 60 wt% Nb2Os particles and 40 wt% MC particles.
  • the MC particles are made from carbide derived carbon, namely SiC derived carbon.
  • a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 23.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water.
  • Styrene butadiene rubber (SBR) is added as a second binder.
  • the total proportion of the binder is 3.0 wt%.
  • Carbon black (CB) is added as a first conductive additive with a proportion of 2.0 wt%.
  • Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 0.5 wt%.
  • Activated carbon (MC) particles and Nb2Os particles are added as a negative active material.
  • the Nb2Os particles are made of orthorombic Nb2Os.
  • the negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities.
  • the negative active material consists of 60 wt% Nb2Os particles and 40 wt% MC particles.
  • the MC particles are made from coconut.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water.
  • Styrene butadiene rubber (SBR) is added as a second binder.
  • the total proportion of the binder is 3.0 wt%.
  • Carbon black (CB) is added as a first conductive additive with a proportion of 4.1 wt%.
  • Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 0.5 wt%.
  • Activated carbon (MC) particles and Nb2Os particles are added as a negative active material.
  • the Nb2Os particles are made of orthorombic Nb2Os.
  • the negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities.
  • the negative active material consists of 60 wt% Nb2Os particles and 40 wt% MC particles.
  • the MC particles are made from coconut.
  • a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 23.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water.
  • Styrene butadiene rubber (SBR) is added as a second binder.
  • the total proportion of the binder is 4.0 wt%.
  • Carbon black (CB) is added as a first conductive additive with a proportion of 4.0 wt%.
  • Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 0.5 wt%.
  • Activated carbon (MC) particles and Nb2Os particles are added as a negative active material.
  • the Nb2Os particles are made of orthorombic Nb2Os.
  • the negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities.
  • the negative active material consists of 80 wt% Nb2Os particles and 20 wt% MC particles.
  • the MC particles are made from coconut.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water.
  • Styrene butadiene rubber (SBR) is added as a second binder.
  • the total proportion of the binder is 3.0 wt%.
  • Carbon black (CB) is added as a first conductive additive with a proportion of 4.0 wt%.
  • Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 0.5 wt%.
  • Activated carbon (MC) particles and Nb2Os particles are added as a negative active material.
  • the Nb2Os particles are made of orthorombic Nb2Os.
  • the negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities.
  • the negative active material consists of 60 wt% Nb2Os particles and 40 wt% MC particles.
  • the MC particles are made from coconut.
  • a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 23.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water.
  • Styrene butadiene rubber (SBR) is added as a second binder.
  • the total proportion of the binder is 6.0 wt%.
  • Carbon black (CB) is added as a first conductive additive with a proportion of 4.0 wt%.
  • Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 0.5 wt%.
  • Activated carbon (MC) particles and Nb2Os particles are added as a negative active material.
  • the Nb2Os particles are made of orthorombic Nb2Os.
  • the negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities.
  • the negative active material consists of 90 wt% Nb2Os particles and 10 wt% MC particles.
  • the MC particles are made from coconut.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water.
  • Styrene butadiene rubber (SBR) is added as a second binder.
  • the total proportion of the binder is 4.0 wt%.
  • Carbon black (CB) is added as a first conductive additive with a proportion of 4.1 wt%.
  • Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 1.1 wt%.
  • Activated carbon (MC) particles and Nb2Os particles are added as a negative active material.
  • the Nb2Os particles are made of orthorombic Nb2Os.
  • the negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities.
  • the negative active material consists of 60 wt% Nb2Os particles and 40 wt% MC particles.
  • the MC particles are made from coconut.
  • a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 23.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
  • the organic anhydrous electrolyte 4 is obtained by mixing 50 vol % of acetonitrile (ACN) with 50 vol % of ethylenecarbonate (EC) and adding an amount of lithium tetrafluoroborate (LiBF4) so that its concentration in the liquid components is 1 mol/l.
  • ACN acetonitrile
  • EC ethylenecarbonate
  • LiBF4 lithium tetrafluoroborate
  • the organic anhydrous electrolyte 4 is obtained by providing propylene carbonate (PC) with 100 vol% and adding an amount of lithium hexafluorophosphate (LiPFe) so that its concentration in the liquid is 1 mol/l.
  • PC propylene carbonate
  • LiPFe lithium hexafluorophosphate
  • the organic anhydrous electrolyte 4 is obtained by mixing 70 vol % of propylene carbonate (PC) with 30 vol % of ethylenecarbonate (EC) and adding an amount of lithium hexafluorophosphate (LiPFe) so that its concentration in the liquid components is 1 mol/l.
  • PC propylene carbonate
  • EC ethylenecarbonate
  • LiPFe lithium hexafluorophosphate
  • the organic anhydrous electrolyte 4 is obtained by mixing 25 vol % of ethylenecarbonate (EC), 5 vol % of ethyl methyl carbonate (EMC), and 70 vol % of dimethyl carbonate (DMC) and adding an amount of lithium hexafluorophosphate (LiPFe) so that its concentration in the liquid components is 1 mol/l.
  • EC ethylenecarbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4.3 wt%.
  • Carbon black (CB) is added with a proportion of 4 wt%.
  • Carbon nanotubes (CNTs) are added with a proportion of 1 wt%.
  • UNi x Mn2-xO4 (LNMO) particles, where x may range from 0 to 1 .0, are added as a positive active material and make up 90.7 wt% of the positive electrode material.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4.2 wt%.
  • Carbon black (CB) is added with a proportion of 10.1 wt%. No CNTs are added.
  • LiNi x Mn2-xO4 (LNMO) particles where x may range from 0 to 1 .0, are added as a positive active material and make up 85.7 wt% of the positive electrode material.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4.2 wt%.
  • CB is added with a proportion of 2.0 wt%.
  • CNTs are added with a proportion of 1.0 wt%.
  • LiNi x Mn2-xO4 (LNMO) particles where x may range from 0 to 1 .0, are added as a positive active material and make up 92.8 wt% of the positive electrode material.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
  • Example P4 Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4.4 wt%.
  • CB is added with a proportion of 4.1 wt%.
  • CNTs are added with a proportion of 1.0 wt%.
  • LiNi x Mn2-xO4 (LNMO) particles where x may range from 0 to 1 .0, are added as a positive active material and make up 90.5 wt% of the positive electrode material.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4.2 wt%.
  • CB is added with a proportion of 2.0 wt%.
  • CNTs are added with a proportion of 1.0 wt%.
  • LiNi x Mn2-xO4 (LNMO) particles where x may range from 0 to 1 .0, are added as a positive active material and make up 92.8 wt% of the positive electrode material.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4 wt%.
  • CB is added with a proportion of 2.0 wt%.
  • CNTs are added with a proportion of 1.0 wt%.
  • LiNi x Mn2-xO4 (LNMO) particles where x may range from 0 to 1 .0, are added as a positive active material and make up 93.0 wt% of the positive electrode material.
  • a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 33.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4.2 wt%.
  • CB is added with a proportion of 4.0 wt%.
  • CNTs are added with a proportion of 0.5 wt%.
  • Graphene is added with a proportion of 0.5 wt%.
  • LiNi x Mn2-xO4 (LNMO) particles where x may range from 0 to 1 .0, are added as a positive active material and make up 90.8 wt% of the positive electrode material.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4 wt%.
  • CB is added with a proportion of 4.0 wt%.
  • CNTs are added with a proportion of 0.5 wt%.
  • Graphene is added with a proportion of 0.5 wt%.
  • LiNi x Mn2-xO4 (LNMO) particles where x may range from 0 to 1 .0, are added as a positive active material and make up 91 .0 wt% of the positive electrode material.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 6 wt%.
  • CB is added with a proportion of 4.0 wt%.
  • CNTs are added with a proportion of 0.5 wt%.
  • Graphene is added with a proportion of 0.5 wt%.
  • UNi x Mn2-xO4 (LNMO) particles where x may range from 0 to 1 .0, are added as a positive active material and make up 89.0 wt% of the positive electrode material.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4 wt%.
  • Carbon black (CB) is added with a proportion of 10.1 wt%. No CNTs are added.
  • LiNi x Mn2-xO4 (LNMO) particles where x may range from 0 to 1 .0, are added as a positive active material and make up 85.9 wt% of the positive electrode material.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
  • Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4.1 wt%.
  • CB is added with a proportion of 2.0 wt%.
  • CNTs are added with a proportion of 1.0 wt%.
  • LiNi x Mn2-xO4 (LNMO) particles where x may range from 0 to 1 .0, are added as a positive active material and make up 92.9 wt% of the positive electrode material.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
  • Example P12 Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4.1 wt%.
  • CB is added with a proportion of 4.0 wt%.
  • CNTs are added with a proportion of 0.5 wt%.
  • Graphene is added with a proportion of 0.5 wt%.
  • LiNi x Mn2-xO4 (LNMO) particles where x may range from 0 to 1 .0, are added as a positive active material and make up 90.9 wt% of the positive electrode material.
  • the coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
  • Cell 1 has a negative electrode according to Example N1 , a positive electrode according to Example P1 and uses an electrolyte according to Example E1 .
  • the maximum cell voltage is 3.5 V. The following results were achieved:
  • Results Cell 2 Cell 2 has a negative electrode according to Example N1 , a positive electrode according to Example P2 and uses an electrolyte according to Example E1.
  • the maximum cell voltage is 3.5 V. The following results were achieved:
  • Cell 3 has a negative electrode according to Example N2, a positive electrode according to Example P3 and uses an electrolyte according to Example E1.
  • the maximum cell voltage is 3.2 V. The following results were achieved:
  • Cell 4 has a negative electrode according to Example N3, a positive electrode according to Example P4 and uses an electrolyte according to Example E1.
  • the maximum cell voltage is 3.5 V. The following results were achieved:
  • Cell 5 has a negative electrode according to Example N4, a positive electrode according to Example P5 and uses an electrolyte according to Example E1.
  • the maximum cell voltage is 3.5 V. The following results were achieved:
  • Cell 6 has a negative electrode according to Example N5, a positive electrode according to Example P6 and uses an electrolyte according to Example E2.
  • the maximum cell voltage is 3.2 V. The following results were achieved:
  • Cell 7 has a negative electrode according to Example N6, a positive electrode according to Example P5 and uses an electrolyte according to Example E2.
  • the maximum cell voltage is 3.2 V. The following results were achieved:
  • Cell 8 has a negative electrode according to Example N7, a positive electrode according to Example P7 and uses an electrolyte according to Example E2.
  • the maximum cell voltage is 3.2 V. The following results were achieved:
  • Cell 9 has a negative electrode according to Example N5, a positive electrode according to Example P6 and uses an electrolyte according to Example E2.
  • the maximum cell voltage is 3.2 V. The following results were achieved:
  • Results Cell 10 has a negative electrode according to Example N8, a positive electrode according to Example P8 and uses an electrolyte according to Example E3.
  • the maximum cell voltage is 3.2 V. The following results were achieved:
  • Cell 11 has a negative electrode according to Example N9, a positive electrode according to Example P8 and uses an electrolyte according to Example E3.
  • the maximum cell voltage is 3.2 V. The following results were achieved:
  • Cell 12 has a negative electrode according to Example N10, a positive electrode according to Example P9 and uses an electrolyte according to Example E4.
  • the maximum cell voltage is 3.5 V. The following results were achieved:
  • Cell 13 has a negative electrode according to Example N10, a positive electrode according to Example P9 and uses an electrolyte according to Example E3.
  • the maximum cell voltage is 3.5 V. The following results were achieved:
  • Cell 14 has a negative electrode according to Example N11 , a positive electrode according to Example P10 and uses an electrolyte according to Example E1.
  • the maximum cell voltage is 3.5 V. The following results were achieved:
  • Cell 15 has a negative electrode according to Example N5, a positive electrode according to Example P11 and uses an electrolyte according to Example E1.
  • the maximum cell voltage is 3.2 V. The following results were achieved:
  • Cell 16 has a negative electrode according to Example N8, a positive electrode according to Example P12 and uses an electrolyte according to Example E3.
  • the maximum cell voltage is 3.2 V. The following results were achieved:

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Abstract

An energy storage cell (1) for storing electrical energy. the cell (1) comprises a negative electrode (22) and a positive electrode (32) that are immersed in an organic anhydrous electrolyte (4). wherein the negative electrode (22) includes a negative active material composition that has activated carbon (MC) particles; wherein the positive electrode (32) includes a positive active material composition that for the most part has LiMn2O4 (LMO) particles.

Description

Energy storage cells with fast charge and discharge capabilites
The invention relates to energy storage cells, e.g. hybrid supercapacitors, with fast charge and discharge capabilities as well as their components, such as electrodes and electrolytes.
In this disclosure, the classification of pore sizes is followed according to guidelines provided by the ..International Union of Pure and Applied Chemistry" (IUPAC), whereas „micropores“ exhibit a pore diameter between 0-2 nm, „mesopores“ exhibit a pore diameter between 2-50 nm and „macropores“ exhibit a pore diameter above 50 nm.
In recent years the demand for energy storage cells has substantially increased, be it in the field of automobiles, industrial applications, mass transportation, or grid regulation. The cells may serve as traction battery, intermediate energy storage for kinetic energy recovery systems, or energy storage for mechanical assistance systems, such as anti-skid systems or active shock absorbers. In grid regulation the cells store excess produced energy, in particular excess wind or solar energy, and help closing the energy gap in situations of high demand. For all these applications it is useful to have a type of energy storage cell that allows for fast charging or discharging, or in other words a high peak power.
Energy storage cells may generally be divided into batteries and capacitors. While batteries store electric energy in chemical form, capacitors usually store electric energy in the electric field. Batteries are usually not capable of achieving the peak powers that are required for the abovementioned applications.
Ultracapacitors, also known as supercapacitors, are a kind of capacitor and can be separated into double-layer capacitors and pseudocapacitors. The former store electrical energy in an electrostatic double-layer, whereas the latter store the electrical energy electrochemically, but in a different manner than batteries. Recently, hybrid (super)capacitors have been developed that combine the features of double-layer capacitors and pseudocapacitors.
These capacitors usually exhibit a large voltage variation during charging and discharging, whereas batteries do not. The main advantage for capacitors is that they are great for applications that require large peak powers or - in other words - a large energy transfer within very short time. This capability, in particular for supercapacitors, is not without limits, since in general the actually usable capacity depends on the discharge current: the larger the current, the smaller the usable capacity.
US 5 258 245 A discloses a lithium battery comprising a positive electrode mainly of vanadium pentoxide, a negative electrode mainly of lithium doped niobium pentoxide, and an electrolyte mainly of an anhydrous solvent with dissolved lithium salt.
US 2021 / 0 110 980 A1 , US 2021 / 0 110 979 A1 , and US 2021 I 0 218 048 A1 disclose cell concepts that employ three or four electrodes.
DE 10 2018 202 929 A1 discloses a hybrid supercapacitor.
It is the object of the invention to improve energy storage cells with respect to their electrical properties, preferably the actually usable capacity, charge/discharge capability or maximal voltage.
The invention provides a positive active material composition for a positive electrode of an energy storage cell, the composition consisting of:
1 .5 wt% to 11.0 wt% carbon black (CB);
3 wt% to 8 wt% of at least one binder;
72 wt% to 95.5 wt% of positive active material that for the most part includes or for the most part consists of LiNixMn2-xO4 (LNMO) particles, wherein 0 < x < 1.0; optionally 0.1 wt% to 2 wt% carbon nanotubes (CNTs); optionally 0.1 wt% to 2 wt% graphene; and optionally less than 5 wt% of other components or impurities.
Preferably, the LNMO particles have a particle size of D90 of 8 pm to 10 pm. Preferably, the LNMO particles have a particle size of D50 of 6 pm to 7 pm. Preferably, the LNMO particles have a particle size of D10 of 4 pm to < 5 pm.
Preferably, the proportion of CB is 1 .5 wt% to 5 wt% or 9 wt% to 11 wt%, preferably 2.0 wt% to 4.0 wt% or 9.5 wt% to 10.5 wt%.
Preferably, the proportion of the at least one binder is 3.5 wt% to 4.5 wt% or 5.5 wt% to 6.5 wt%, preferably 4.0 wt% to 4.4 wt% or 5.5 wt% to 6.5 wt%.
Preferably, the positive active material exclusively consists of LMNO particles, wherein the proportion of the LMNO particles is at least 85 wt%, preferably at least 90 wt%, wherein the total proportion of the remaining components is chosen to complete to 100 wt%.
The invention provides a method for manufacturing a positive electrode (32) for an energy storage cell, the method comprising: a) provide 3 wt% to 8 wt% binder in a mixing vessel; b) mixing in the vessel, so as to obtain a slurry:
1 .5 wt% to 11.0 wt% carbon black (CB);
72 wt% to 95.5 wt% of positive active that for the most part includes or for the most part consists of LiNixMn2-xO4 (LNMO) particles, wherein 0 < x < 1.0; optionally 0.1 wt% to 2 wt% carbon nanotubes (CNTs); and optionally 0.1 wt% to 2 wt% graphene; c) coating a conductive electrode substrate with the slurry and heating the coated electrode substrate, thereby generating the positive electrode.
The invention provides a negative active material composition for a negative electrode of an energy storage cell, the composition consisting of:
70 wt% to 99 wt% of negative active material;
2 wt% to 7 wt% of at least one binder; optionally up to 6 wt% in total of at least one conductive additive; and optionally less than 5 wt% in total of other components or impurities, wherein the negative active material consists of Nb2Os particles, activated carbon (MC) particles and optionally of lithium titanate particles.
Preferably, the amount of negative material is 85 wt% to 96 wt%, more preferably 88 wt% to 96 wt%, more preferably 89.5 wt% to 94.5 wt%.
Preferably, the negative active material exclusively consists of Nb2Os particles and MC particles and the proportion of Nb2Os particles is 50% to 95%, preferably 60% to 90%, more preferably 60% to 80%, and the remaining proportion to 100% is MC particles.
Preferably, the negative active material exclusively consists of Nb2Os particles, MC particles, and lithium titanate particles, and the proportion of Nb2Os particles is 20% to 40%, preferably 25% to 35%, more preferably 30%, and the porportion of lithium titanate particles is 20% to 40%, preferably 25% to 35%, more preferably 30%, and the remaining proportion to 100% is MC particles.
Preferably, total amount of the at least one binder is 3 wt% to 6 wt%, preferably 3 wt% to 4.5 wt%.
The invention provides a method for manufacturing a negative electrode for an energy storage cell, the method comprising: a) provide 2 wt% to 7 wt% of at least one binder in a mixing vessel; b) mixing in the vessel, so as to obtain a slurry:
82 wt% to 98 wt% of negative active material that consists of 30% to 90% of Nb2C>5 particles, activated carbon (MC) particles and optionally of lithium titanate particles; optionally up to 6 wt% in total of at least one conductive additive; and optionally less than 5 wt% in total of other components; c) coating a conductive electrode substrate with the slurry and heating the coated electrode substrate, thereby generating the negative electrode.
In an embodiment the Nb20s particles mostly consist of orthorhombic Nb20s. In an embodiment the Nb20s particles consists of more than 90 wt% of orthorombic Nb20s.
In an embodiment the Nb20s particles have a particle size of D90 1 pm to 100 pm, preferably of 2 pm to 60 pm, more preferably of 10 pm to 30 pm. In an embodiment the Nb2C>5 particles have a particle size of D10 0.05 pm to 10 pm, preferably 0.3 pm to 5 pm, more preferably of 0.3 pm to 3 pm.
In an embodiment the MC particles have a BET nitrogen surface area of at least 60 m2/g, preferably of at least 1000 m2/g.
In an embodiment the MC particles have a particle size D90 of 5 pm to 30 pm, preferably of 5 pm to 20 pm. In an embodiment the MC particles have a particle size of D10 1 pm to 2 pm. In an embodiment the MC particles comprise carbide derived carbon (CDC) particles.
In an embodiment each conductive additive is selected from a group consisting of carbon black, carbon nanotubes (CNTs), graphene, and mixtures thereof. Preferably, the CNTs are multi-walled CNTs (MWCNTs).
In an embodiment the composition includes 1 wt% to 5 wt% carbon black as a conductive additive. In an embodiment the composition includes 1 wt% to 4 wt% carbon black as a conductive additive. In an embodiment the composition includes 2 wt% to 4 wt% carbon black as a conductive additive.
In an embodiment the composition includes 0.3 wt% to 2 wt% CNTs. In an embodiment the composition includes 0.5 wt% to 1.1 wt% CNTs.
The invention provides energy storage cell for storing electrical energy, the cell comprising a plurality of electrodes that are immersed in an organic anhydrous electrolyte, wherein at least one electrode is configured as a negative electrode and at least one electrode is configured as a positive electrode, wherein the positive electrode includes a preferred positive electrode material composition or obtainable by a preferred method according. Alternatively, or additionally the negative electrode includes a negative electrode material composition as described herein or obtainable by a method described herein.
Preferably, the organic anhydrous electrolyte consists of one of the following: a) 40 vol% to 60 vol% acetonitrile (ACN), 60 vol% to 40 vol% ethylenecarbonate (EC) and a lithium conductive salt; or b) propylene carbonate (PC) and optionally EC and a lithium conductive salt; or c) EC, ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC).
Preferably, the electrolyte consists of 50 vol% ACN and 50 vol% EC and the lithium conductive salt.
Preferably, the electrolyte consists of 70 vol% PC and 30 vol% EC and the lithium conductive salt.
Preferably, the electrolyte consists of 25 vol% EC, 5 vol% EMC and 70 vol% DMC.
Preferably, the lithium conductive salt is LiPFe.
Preferably, the lithium conductive salt is UBF4.
The invention provides an organic anhydrous electrolyte composition for an energy storage cell, the composition consisting of a) 40 vol% to 60 vol% acetonitrile (ACN), 60 vol% to 40 vol% ethylenecarbonate (EC) and a lithium conductive salt; or b) propylene carbonate (PC) and optionally EC and a lithium conductive salt; or c) EC, ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC).
Preferably, the electrolyte consists of 50 vol% ACN and 50 vol% EC and the lithium conductive salt.
Preferably, the electrolyte consists of 70 vol% PC and 30 vol% EC and the lithium conductive salt.
Preferably, the electrolyte consists of 25 vol% EC, 5 vol% EMC and 70 vol% DMC.
In an embodiment the conductive lithium salt has a concentration of 0.1 mol/l to 3 mol/l, preferably 1 mol/l.
In an embodiment the lithium conductive salt is selected from a group consisting of lithium perchlorate (l_iCIC>4), lithium tetrafluoroborate (LiBF4), lithium hexafluorophosphate (LiPFe), lithium hexafluoroarsenate (LiAsFe), lithium trifluoromethanesulfonate (USO3CF3), lithium bis(trifluoromethylsulfonyl)imide (LiN(SC>2CF3)2), lithium bis(pentafluoroethanesulfonyl)imide (LiN(SO2C2Fs)2), lithium bis(oxalato)borate (LiBOB, LiB(C2O4)2), lithium difluoro(oxalato)borate (LiBF2(C2C>4)), lithium tris(pentafluoroethyl)trifluorophosphate (LiPF3(C2F5)3) and mixtures thereof. In an embodiment the lithium conductive salt is LiPFe. The invention provides an energy storage cell for storing electrical energy, the cell comprising a positive electrode and a negative electrode immersed in an organic anhydrous electrolyte, wherein the negative electrode includes a negative active material composition that has Nb20s particles, activated carbon (MC) particles and optionally of lithium titanate particles.; wherein the positive electrode includes a positive active material composition that for the most part has LiNixMn2-xO4 (LNMO) particles, wherein 0 < x < 1.0.
In an embodiment the negative active material composition includes a negative active material that consists of Nb20s particles and MC particles.
In an embodiment the negative active material composition includes a negative active material that consists of Nb20s particles, MC particles and lithium titanate particles.
In an embodiment the amount of Nb20s particles and the amount of MC particles is selected from a group consisting of 30 wt%, 40 wt%, 50 wt%, 60 wt%, and 70 wt%, such that the total amount is 100 wt%.
In an embodiment the negative electrode composition and/or the positive electrode composition include at least one conductive additive.
In an embodiment the at least one conductive additive is selected from a group consisting of carbon black (CB), carbon nanotubes (CNTs), graphene, and mixtures thereof.
In an embodiment the negative active material composition consists of more than 50 wt%, preferably of more than 60 wt%, negative active material. In an embodiment the positive active material composition consists of more than 50 wt%, preferably of more than 90 wt%, preferably of more than 95 wt%, preferably of 97 wt% or more, positive active material.
In an embodiment the MC particles have a BET nitrogen surface area of at least 60 m2/g, preferably of at least 1000 m2/g.
In an embodiment the MC particles have a particle size D90 of 5 pm to 30 pm, preferably 5 pm to 20 pm. In an embodiment the MC particles have a particle size of D10 1 pm to 2 pm.
In an embodiment the MC particles comprise carbide derived carbon particles.
In an embodiment CNTs are multi-walled CNTs (MWCNTs).
In an embodiment the negative electrode composition includes 1 wt% to 10 wt% carbon black. In an embodiment the negative electrode composition includes 1 wt% to 8 wt% carbon black. In an embodiment the negative electrode composition includes 1 wt% to 3 wt% carbon black. In an embodiment the negative electrode composition includes 2 wt% to 6 wt% carbon black. In an embodiment the negative electrode composition includes 3 wt% to 7 wt% carbon black.
In an embodiment the positive electrode composition includes 1 wt% to 10 wt% carbon black. In an embodiment the positive electrode composition includes 1 wt% to 8 wt% carbon black. In an embodiment the positive electrode composition includes 1 wt% to 3 wt% carbon black. In an embodiment the positive electrode composition includes 2 wt% to 6 wt% carbon black. In an embodiment the positive electrode composition includes 3 wt% to 7 wt% carbon black.
In an embodiment the negative electrode composition includes 0.3 wt% to 2 wt%, preferably 0.3 wt% to 1 .0 wt% CNTs. In an embodiment the positive electrode composition includes 0.3 wt% to 2 wt%, preferably 0.3 wt% to 1.0 wt% CNTs.
In an embodiment the negative electrode composition includes 0.3 wt% to 2 wt%, preferably 0.3 wt % to 1 .0 wt%, graphene. In an embodiment the positive electrode composition includes 0.3 wt% to 2 wt%, preferably 0.3 wt % to 1.0 wt%, graphene.
In an embodiment the proportion of CNTs deviates from the proportion of graphene or vice versa by less than 10%. In an embodiment the proportions of CNTs and graphene are identical.
In an embodiment the electrolyte includes a lithium conductive salt, 80 vol% to 95 vol% acetonitrile, and 5 vol% to 20 vol% ethylenecarbonate.
In an embodiment the lithium conductive salt is selected from a group consisting of lithium perchlorate (l_iCIC>4), lithium tetrafluoroborate (UBF4), lithium hexafluorophosphate (LiPFe), lithium hexafluoroarsenate (LiAsFe), lithium trifluoromethanesulfonate (IJSO3CF3), lithium bis(trifluoromethylsulfonyl)imide (LiN(SC>2CF3)2), lithium bis(pentafluoroethanesulfonyl)imide (LiN(SO2C2Fs)2), lithium bis(oxalato)borate (LiBOB, LiB(C2O4)2), lithium difluoro(oxalato)borate (LiBF2(C2C>4)), lithium tris(pentafluoroethyl)trifluorophosphate (LiPF3(C2F5)3) and mixtures thereof. In an embodiment the lithium conductive salt is LiPFe.
Embodiments of the invention are described in more detail with reference to the accompanying schematic drawings. Therein the only Fig. schematically depicts a crosssection through an energy storage cell according to the invention.
Energy storage cell
As depicted in the Fig., an energy storage cell 1 may be configured as a hybrid ultracapacitor. The energy storage cell 1 is preferably formed as a cylinder. The energy storage cell 1 comprises a first electrode arrangement 2 and a second electrode arrangement 3. Both electrode arrangements are immersed in an organic anhydrous electrolyte 4. Furthermore, the energy storage cell 1 comprises a separator 5 that is interposed between the first and second electrode arrangements 2, 3.
It should be noted that the energy storage cell 1 usually contains a plurality of windings of the first and second electrode arrangements 2, 3 about the cylinder axis, however for the sake of clarity only portions are shown here.
The first electrode arrangement 2 comprises an anode terminal 21. The anode terminal 21 is arranged so that an external electric contact can be formed. The first electrode arrangement 2 comprises a negative electrode 22. The negative electrode 22 is electrically coupled to the anode terminal 21. The negative electrode 22 includes a current collector 23 that is made of metal, preferably aluminium. The current collector 23 contacts the anode terminal 21. The negative electrode 22 includes a negative electrode material 24.
The second electrode arrangement 3 comprises a cathode terminal 31. The cathode terminal 31 is arranged so that an external electric contact can be formed. The second electrode arrangement 3 comprises a positive electrode 32. The positive electrode 32 is electrically coupled to the anode terminal 31. The positive electrode 32 includes a current collector 33 that is made of metal, preferably aluminium. The current collector 33 contacts the cathode terminal 31. The positive electrode 32 includes a positive electrode material 34.
Manufacturing the negative electrode - Example N1
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Styrene butadiene rubber (SBR) is added as a second binder. The total proportion of the binder is 4.2 wt%.
Carbon black (CB) is added as a first conductive additive with a proportion of 4.1 wt%. Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 1.1 wt%.
Activated carbon (MC) particles and Nb20s particles are added as a negative active material. The Nb20s particles are made of orthorombic Nb20s. The negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities. The negative active material consists of 60 wt% Nb20s particles and 40 wt% MC particles. The MC particles are made from coconut.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 23. The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
Example N2
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Styrene butadiene rubber (SBR) is added as a second binder. The total proportion of the binder is 4.0 wt%.
Carbon black (CB) is added as a first conductive additive with a proportion of 2.0 wt%. Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 0.5 wt%.
Activated carbon (MC) particles and Nb2Os particles are added as a negative active material. The Nb2Os particles are made of orthorombic Nb2Os. The negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities. The negative active material consists of 30 wt% Nb2Os particles, 40 wt% MC particles and 30 wt% of lithium titanate (LTO) particles. The MC particles are made from coconut.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 23.
The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
Example N3
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Styrene butadiene rubber (SBR) is added as a second binder. The total proportion of the binder is 4.3 wt%.
Carbon black (CB) is added as a first conductive additive with a proportion of 1 .0 wt%. Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 0.5 wt%.
Activated carbon (MC) particles and Nb2Os particles are added as a negative active material. The Nb2Os particles are made of orthorombic Nb2Os. The negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities. The negative active material consists of 60 wt% Nb2Os particles and 40 wt% MC particles. The MC particles are made from carbide derived carbon, namely SiC derived carbon.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 23. The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
Example N4
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Styrene butadiene rubber (SBR) is added as a second binder. The total proportion of the binder is 4.1 wt%.
Carbon black (CB) is added as a first conductive additive with a proportion of 2.0 wt%. Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 0.5 wt%.
Activated carbon (MC) particles and Nb2Os particles are added as a negative active material. The Nb2Os particles are made of orthorombic Nb2Os. The negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities. The negative active material consists of 60 wt% Nb2Os particles and 40 wt% MC particles. The MC particles are made from carbide derived carbon, namely SiC derived carbon.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 23.
The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
Example N5
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Styrene butadiene rubber (SBR) is added as a second binder. The total proportion of the binder is 4.0 wt%.
Carbon black (CB) is added as a first conductive additive with a proportion of 2.0 wt%. Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 0.5 wt%.
Activated carbon (MC) particles and Nb2Os particles are added as a negative active material. The Nb2Os particles are made of orthorombic Nb2Os. The negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities. The negative active material consists of 60 wt% Nb2Os particles and 40 wt% MC particles. The MC particles are made from carbide derived carbon, namely SiC derived carbon.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 23. The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
Example N6
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Styrene butadiene rubber (SBR) is added as a second binder. The total proportion of the binder is 3.0 wt%.
Carbon black (CB) is added as a first conductive additive with a proportion of 2.0 wt%. Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 0.5 wt%.
Activated carbon (MC) particles and Nb2Os particles are added as a negative active material. The Nb2Os particles are made of orthorombic Nb2Os. The negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities. The negative active material consists of 60 wt% Nb2Os particles and 40 wt% MC particles. The MC particles are made from coconut.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 23.
The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
Example N7
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Styrene butadiene rubber (SBR) is added as a second binder. The total proportion of the binder is 3.0 wt%.
Carbon black (CB) is added as a first conductive additive with a proportion of 4.1 wt%. Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 0.5 wt%.
Activated carbon (MC) particles and Nb2Os particles are added as a negative active material. The Nb2Os particles are made of orthorombic Nb2Os. The negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities. The negative active material consists of 60 wt% Nb2Os particles and 40 wt% MC particles. The MC particles are made from coconut.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 23. The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
Example N8
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Styrene butadiene rubber (SBR) is added as a second binder. The total proportion of the binder is 4.0 wt%.
Carbon black (CB) is added as a first conductive additive with a proportion of 4.0 wt%. Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 0.5 wt%.
Activated carbon (MC) particles and Nb2Os particles are added as a negative active material. The Nb2Os particles are made of orthorombic Nb2Os. The negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities. The negative active material consists of 80 wt% Nb2Os particles and 20 wt% MC particles. The MC particles are made from coconut.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 23.
The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
Example N9
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Styrene butadiene rubber (SBR) is added as a second binder. The total proportion of the binder is 3.0 wt%.
Carbon black (CB) is added as a first conductive additive with a proportion of 4.0 wt%. Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 0.5 wt%.
Activated carbon (MC) particles and Nb2Os particles are added as a negative active material. The Nb2Os particles are made of orthorombic Nb2Os. The negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities. The negative active material consists of 60 wt% Nb2Os particles and 40 wt% MC particles. The MC particles are made from coconut.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 23. The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
Example N10
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Styrene butadiene rubber (SBR) is added as a second binder. The total proportion of the binder is 6.0 wt%.
Carbon black (CB) is added as a first conductive additive with a proportion of 4.0 wt%. Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 0.5 wt%.
Activated carbon (MC) particles and Nb2Os particles are added as a negative active material. The Nb2Os particles are made of orthorombic Nb2Os. The negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities. The negative active material consists of 90 wt% Nb2Os particles and 10 wt% MC particles. The MC particles are made from coconut.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 23.
The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
Example N11
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Styrene butadiene rubber (SBR) is added as a second binder. The total proportion of the binder is 4.0 wt%.
Carbon black (CB) is added as a first conductive additive with a proportion of 4.1 wt%. Carbon nanotubes (CNTs) are added as a second conductive additive with a proportion of 1.1 wt%.
Activated carbon (MC) particles and Nb2Os particles are added as a negative active material. The Nb2Os particles are made of orthorombic Nb2Os. The negative active material makes up the remainder to 100 wt%, apart from unavoidable impurities. The negative active material consists of 60 wt% Nb2Os particles and 40 wt% MC particles. The MC particles are made from coconut.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 23. The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the negative electrode 22.
Composition of electrolyte - Example E1
The organic anhydrous electrolyte 4 is obtained by mixing 50 vol % of acetonitrile (ACN) with 50 vol % of ethylenecarbonate (EC) and adding an amount of lithium tetrafluoroborate (LiBF4) so that its concentration in the liquid components is 1 mol/l.
Example E2
The organic anhydrous electrolyte 4 is obtained by providing propylene carbonate (PC) with 100 vol% and adding an amount of lithium hexafluorophosphate (LiPFe) so that its concentration in the liquid is 1 mol/l.
Example E3
The organic anhydrous electrolyte 4 is obtained by mixing 70 vol % of propylene carbonate (PC) with 30 vol % of ethylenecarbonate (EC) and adding an amount of lithium hexafluorophosphate (LiPFe) so that its concentration in the liquid components is 1 mol/l.
Example E4
The organic anhydrous electrolyte 4 is obtained by mixing 25 vol % of ethylenecarbonate (EC), 5 vol % of ethyl methyl carbonate (EMC), and 70 vol % of dimethyl carbonate (DMC) and adding an amount of lithium hexafluorophosphate (LiPFe) so that its concentration in the liquid components is 1 mol/l.
Manufacturing the positive electrode - Example P1
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4.3 wt%.
Carbon black (CB) is added with a proportion of 4 wt%. Carbon nanotubes (CNTs) are added with a proportion of 1 wt%. UNixMn2-xO4 (LNMO) particles, where x may range from 0 to 1 .0, are added as a positive active material and make up 90.7 wt% of the positive electrode material.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 33.
The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
Example P2
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4.2 wt%.
Carbon black (CB) is added with a proportion of 10.1 wt%. No CNTs are added.
LiNixMn2-xO4 (LNMO) particles, where x may range from 0 to 1 .0, are added as a positive active material and make up 85.7 wt% of the positive electrode material.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 33.
The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
Example P3
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4.2 wt%.
CB is added with a proportion of 2.0 wt%. CNTs are added with a proportion of 1.0 wt%.
LiNixMn2-xO4 (LNMO) particles, where x may range from 0 to 1 .0, are added as a positive active material and make up 92.8 wt% of the positive electrode material.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 33.
The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
Example P4 Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4.4 wt%.
CB is added with a proportion of 4.1 wt%. CNTs are added with a proportion of 1.0 wt%.
LiNixMn2-xO4 (LNMO) particles, where x may range from 0 to 1 .0, are added as a positive active material and make up 90.5 wt% of the positive electrode material.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 33.
The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
Example P5
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4.2 wt%.
CB is added with a proportion of 2.0 wt%. CNTs are added with a proportion of 1.0 wt%.
LiNixMn2-xO4 (LNMO) particles, where x may range from 0 to 1 .0, are added as a positive active material and make up 92.8 wt% of the positive electrode material.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 33.
The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
Example P6
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4 wt%.
CB is added with a proportion of 2.0 wt%. CNTs are added with a proportion of 1.0 wt%.
LiNixMn2-xO4 (LNMO) particles, where x may range from 0 to 1 .0, are added as a positive active material and make up 93.0 wt% of the positive electrode material.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 33. The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
Example P7
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4.2 wt%.
CB is added with a proportion of 4.0 wt%. CNTs are added with a proportion of 0.5 wt%. Graphene is added with a proportion of 0.5 wt%.
LiNixMn2-xO4 (LNMO) particles, where x may range from 0 to 1 .0, are added as a positive active material and make up 90.8 wt% of the positive electrode material.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 33.
The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
Example P8
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4 wt%.
CB is added with a proportion of 4.0 wt%. CNTs are added with a proportion of 0.5 wt%. Graphene is added with a proportion of 0.5 wt%.
LiNixMn2-xO4 (LNMO) particles, where x may range from 0 to 1 .0, are added as a positive active material and make up 91 .0 wt% of the positive electrode material.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 33.
The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
Example P9
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 6 wt%.
CB is added with a proportion of 4.0 wt%. CNTs are added with a proportion of 0.5 wt%. Graphene is added with a proportion of 0.5 wt%. UNixMn2-xO4 (LNMO) particles, where x may range from 0 to 1 .0, are added as a positive active material and make up 89.0 wt% of the positive electrode material.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 33.
The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
Example P10
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4 wt%.
Carbon black (CB) is added with a proportion of 10.1 wt%. No CNTs are added.
LiNixMn2-xO4 (LNMO) particles, where x may range from 0 to 1 .0, are added as a positive active material and make up 85.9 wt% of the positive electrode material.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 33.
The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
Example P11
Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4.1 wt%.
CB is added with a proportion of 2.0 wt%. CNTs are added with a proportion of 1.0 wt%.
LiNixMn2-xO4 (LNMO) particles, where x may range from 0 to 1 .0, are added as a positive active material and make up 92.9 wt% of the positive electrode material.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 33.
The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
Example P12 Carboxymethyl cellulose (CMC) binder is provided and optionally mixed with water. Acrylic binder is added as a second binder. The total proportion of binder is 4.1 wt%.
CB is added with a proportion of 4.0 wt%. CNTs are added with a proportion of 0.5 wt%. Graphene is added with a proportion of 0.5 wt%.
LiNixMn2-xO4 (LNMO) particles, where x may range from 0 to 1 .0, are added as a positive active material and make up 90.9 wt% of the positive electrode material.
After mixing a slurry is obtained that can be distributed onto a conductive electrode substrate, such as the current collector 33.
The coated substrate is then heated, so as to remove possible solvents and cure the binder, thereby forming the positive electrode 32.
Experimental results of different cells
Applicant has conducted studies of cells that are composed of different examples of positive electrodes, negative electrodes and electrolytes. The cells were examined for maximum cell voltage (V), specific capacity (mAh/g), 10 ms ans 1 ms equivalent series resistance or ESR (Qcm2), specific energy (Wh/kg), specific power (W/kg). These quantities, except the maximum cell voltage, were measured at different (dis-)charging currents ranging from 10 A to 4000 A.
Results Cell 1
Cell 1 has a negative electrode according to Example N1 , a positive electrode according to Example P1 and uses an electrolyte according to Example E1 . The maximum cell voltage is 3.5 V. The following results were achieved:
Results Cell 2 Cell 2 has a negative electrode according to Example N1 , a positive electrode according to Example P2 and uses an electrolyte according to Example E1. The maximum cell voltage is 3.5 V. The following results were achieved:
Results Cell 3
Cell 3 has a negative electrode according to Example N2, a positive electrode according to Example P3 and uses an electrolyte according to Example E1. The maximum cell voltage is 3.2 V. The following results were achieved:
Results Cell 4
Cell 4 has a negative electrode according to Example N3, a positive electrode according to Example P4 and uses an electrolyte according to Example E1. The maximum cell voltage is 3.5 V. The following results were achieved:
Results Cell 5
Cell 5 has a negative electrode according to Example N4, a positive electrode according to Example P5 and uses an electrolyte according to Example E1. The maximum cell voltage is 3.5 V. The following results were achieved:
Results Cell 6
Cell 6 has a negative electrode according to Example N5, a positive electrode according to Example P6 and uses an electrolyte according to Example E2. The maximum cell voltage is 3.2 V. The following results were achieved:
Results Cell 7
Cell 7 has a negative electrode according to Example N6, a positive electrode according to Example P5 and uses an electrolyte according to Example E2. The maximum cell voltage is 3.2 V. The following results were achieved:
Results Cell 8
Cell 8 has a negative electrode according to Example N7, a positive electrode according to Example P7 and uses an electrolyte according to Example E2. The maximum cell voltage is 3.2 V. The following results were achieved:
Results Cell 9
Cell 9 has a negative electrode according to Example N5, a positive electrode according to Example P6 and uses an electrolyte according to Example E2. The maximum cell voltage is 3.2 V. The following results were achieved:
Results Cell 10 Cell 10 has a negative electrode according to Example N8, a positive electrode according to Example P8 and uses an electrolyte according to Example E3. The maximum cell voltage is 3.2 V. The following results were achieved:
Results Cell 11
Cell 11 has a negative electrode according to Example N9, a positive electrode according to Example P8 and uses an electrolyte according to Example E3. The maximum cell voltage is 3.2 V. The following results were achieved:
Results Cell 12
Cell 12 has a negative electrode according to Example N10, a positive electrode according to Example P9 and uses an electrolyte according to Example E4. The maximum cell voltage is 3.5 V. The following results were achieved:
Results Cell 13
Cell 13 has a negative electrode according to Example N10, a positive electrode according to Example P9 and uses an electrolyte according to Example E3. The maximum cell voltage is 3.5 V. The following results were achieved:
Results Cell 14
Cell 14 has a negative electrode according to Example N11 , a positive electrode according to Example P10 and uses an electrolyte according to Example E1. The maximum cell voltage is 3.5 V. The following results were achieved:
Results Cell 15
Cell 15 has a negative electrode according to Example N5, a positive electrode according to Example P11 and uses an electrolyte according to Example E1. The maximum cell voltage is 3.2 V. The following results were achieved:
Results Cell 16
Cell 16 has a negative electrode according to Example N8, a positive electrode according to Example P12 and uses an electrolyte according to Example E3. The maximum cell voltage is 3.2 V. The following results were achieved:
List of reference signs: energy storage cell first electrode arrangement second electrode arrangement electrolyte separator anode terminal negative electrode current collector negative electrode material cathode terminal positive electrode current collector positive electrode material

Claims

27 Skeleton Technologies GmbH 1562 0045 P-DE Claims
1. A positive active material composition for a positive electrode (32) of an energy storage cell (1), the composition consisting of:
1.5 wt% to 11.0 wt% carbon black (CB);
3 wt% to 8 wt% of at least one binder;
72 wt% to 95.5 wt% of positive active material that for the most part includes or for the most part consists of LiNixMn2-xO4 (LNMO) particles, wherein 0 < x < 1.0; optionally 0.1 wt% to 2 wt% carbon nanotubes (CNTs); optionally 0.1 wt% to 2 wt% graphene; and optionally less than 5 wt% of other components or impurities.
2. The positve active material composition according to claim 1, wherein the LNMO particles have a particle size of D90 of 8 pm to 10 pm and of D50 of 6 pm to 7 pm, wherein preferably, the LNMO particles have a particle size of D10 of 4 pm to < 5 pm.
3. The positive active material composition according to any of the preceding claims, wherein the proportion of CB is 1.5 wt% to 5 wt% or 9 wt% to 11 wt%, preferably 2.0 wt% to 4.0 wt% or 9.5 wt% to 10.5 wt%.
4. The positive active material composition according to any of the preceding claims, wherein the proportion of the at least one binder is 3.5 wt% to 4.5 wt% or 5.5 wt% to 6.5 wt%, preferably 4.0 wt% to 4.4 wt% or 5.5 wt% to 6.5 wt%.
5. The positive active material composition according to any of the preceding claims, wherein the positive active material exclusively consists of LMNO particles, wherein the proportion of the LMNO particles is at least 85 wt%, preferably at least 90 wt%, wherein the total proportion of the remaining components is chosen to complete to 100 wt%.
6. A method for manufacturing a positive electrode (32) for an energy storage cell, the method comprising: a) provide 3 wt% to 8 wt% binder in a mixing vessel; b) mixing in the vessel, so as to obtain a slurry:
1 .5 wt% to 11.0 wt% carbon black (CB);
72 wt% to 95.5 wt% of positive active that for the most part includes or for the most part consists of LiNixMn2-xO4 (LNMO) particles, wherein 0 < x < 1.0; optionally 0.1 wt% to 2 wt% carbon nanotubes (CNTs); and optionally 0.1 wt% to 2 wt% graphene; c) coating a conductive electrode substrate with the slurry and heating the coated electrode substrate, thereby generating the positive electrode.
7. A negative active material composition for a negative electrode (22) of an energy storage cell (1), the composition consisting of:
70 wt% to 99 wt% of negative active material;
2 wt% to 7 wt% of at least one binder; optionally up to 6 wt% in total of at least one conductive additive; and optionally less than 5 wt% in total of other components or impurities, wherein the negative active material consists of Nb2Os particles, activated carbon (MC) particles and optionally of lithium titanate particles.
8. The negative active material composition according to claim 7, wherein the amount of negative material is 85 wt% to 96 wt%, more preferably 88 wt% to 96 wt%, more preferably 89.5 wt% to 94.5 wt%.
9. The negative active material composition according to claim 7 or 8, wherein the negative active material exclusively consists of Nb2Os particles and MC particles and the proportion of Nb2Os particles is 50% to 95%, preferably 60% to 90%, more preferably 60% to 80%, and the remaining proportion to 100% is MC particles.
10. The negative active material composition according to claim 7 or 8, wherein the negative active material exclusively consists of Nb2Os particles, MC particles, and lithium titanate particles, and the proportion of Nb2Os particles is 20% to 40%, preferably 25% to 35%, more preferably 30%, and the porportion of lithium titanate particles is 20% to 40%, preferably 25% to 35%, more preferably 30%, and the remaining proportion to 100% is MC particles.
11. The negative active material composition according to any of the claims 7 to 10, wherein total amount of the at least one binder is 3 wt% to 6 wt%, preferably 3 wt% to 4.5 wt%.
12. A method for manufacturing a negative electrode (22) for an energy storage cell, the method comprising: a) provide 2 wt% to 7 wt% of at least one binder in a mixing vessel; b) mixing in the vessel, so as to obtain a slurry:
82 wt% to 98 wt% of negative active material that consists of 30% to 90% of Nb2C>5 particles, activated carbon (MC) particles and optionally of lithium titanate particles; optionally up to 6 wt% in total of at least one conductive additive; and optionally less than 5 wt% in total of other components; c) coating a conductive electrode substrate with the slurry and heating the coated electrode substrate, thereby generating the negative electrode.
13. An energy storage cell (1) for storing electrical energy, the cell comprising a plurality of electrodes (22, 32) that are immersed in an organic anhydrous electrolyte (4), wherein at least one electrode is configured as a negative electrode (22) and at least one electrode is configured as a positive electrode (32), wherein the positive electrode (32) includes a positive electrode material composition according to any of the claims 1 to 5 or obtainable by a method according to claim 6.
14. The energy storage cell (1) according to claim 13, wherein the organic anhydrous electrolyte consists of one of the following: a) 40 vol% to 60 vol% acetonitrile (ACN), 60 vol% to 40 vol% ethylenecarbonate (EC) and a lithium conductive salt; or b) propylene carbonate (PC) and optionally EC and a lithium conductive salt; or c) EC, ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC).
15. The energy storage cell (1) according to claim 14 a), wherein the electrolyte consists of 50 vol% ACN and 50 vol% EC and the lithium conductive salt.
16. The energy storage cell (1) according to claim 14 b), wherein the electrolyte consists of 70 vol% PC and 30 vol% EC and the lithium conductive salt.
17. The energy storage cell (1) according to claim 14 c), wherein the electrolyte consists of 25 vol% EC, 5 vol% EMC and 70 vol% DMC.
18. The energy storage cell (1) according to claim 14 b) or c) or claim 16 or 17, wherein the lithium conductive salt is LiPFe.
19. The energy storage cell (1) according to claim 14 a) or claim 15, wherein the lithium conductive salt is UBF4.
EP22800245.7A 2021-12-23 2022-10-07 Energy storage cells with fast charge and discharge capabilities Pending EP4437598A2 (en)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
DE102021134642 2021-12-23
DE102021134640 2021-12-23
DE102021134643 2021-12-23
DE102021215133 2021-12-31
DE102022100864.9A DE102022100864A1 (en) 2021-12-23 2022-01-14 Electrode material compositions for electrodes of energy storage cells with fast charging and discharging capability
DE102022100865.7A DE102022100865A1 (en) 2021-12-23 2022-01-14 Energy storage cells with fast charging and discharging capacities
DE102022100867.3A DE102022100867A1 (en) 2021-12-23 2022-01-14 Electrode material compositions for electrodes of energy storage cells with fast charging and discharging capability
DE102022100866.5A DE102022100866A1 (en) 2021-12-23 2022-01-14 Electrolyte compositions for energy storage cells with fast charging and discharging capabilities
PCT/EP2022/077996 WO2023117170A2 (en) 2021-12-23 2022-10-07 Energy storage cells with fast charge and discharge capabilites

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