WO2013012334A1 - Ensemble électrode pour accumulateur au lithium-ion, procédé de production d'un tel ensemble électrode et accumulateur au lithium-ion comprenant de tels ensembles électrodes - Google Patents

Ensemble électrode pour accumulateur au lithium-ion, procédé de production d'un tel ensemble électrode et accumulateur au lithium-ion comprenant de tels ensembles électrodes Download PDF

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Publication number
WO2013012334A1
WO2013012334A1 PCT/NL2012/050521 NL2012050521W WO2013012334A1 WO 2013012334 A1 WO2013012334 A1 WO 2013012334A1 NL 2012050521 W NL2012050521 W NL 2012050521W WO 2013012334 A1 WO2013012334 A1 WO 2013012334A1
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lithium storage
electrode assembly
carbon
layer
assembly according
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PCT/NL2012/050521
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English (en)
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Fokko Marten MULDER
Marnix WAGEMAKER
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Technische Universiteit Delft
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • Electrode assembly for a lithium ion battery process for the production of such electrode assembly, and lithium ion battery comprising such electrode assemblies
  • the invention relates to an electrode assembly for a lithium ion battery, to a process for the production of such electrode assembly, and to a lithium ion battery comprising such electrode assemblies as anode and cathode, respectively.
  • Lithium ion batteries and high capacity lithium ion batteries are known in the art.
  • WO2011056847 describes a high capacity silicon based anode active materials for lithium ion batteries. These materials are suggested to be effective in combination with high capacity lithium rich cathode active materials. Supplemental lithium is suggested to improve the cycling performance and reduce irreversible capacity loss for at least certain silicon based active materials.
  • silicon based active materials can be formed in composites with electrically conductive coatings, such as pyrolytic carbon coatings or metal coatings, and composites can also be formed with other electrically conductive carbon components, such as carbon nanofibers and carbon nanoparticles. Additional alloys with silicon are explored in this document.
  • WO2009131700 describes combinations of materials in which high energy density active materials for negative electrodes of lithium ion batteries.
  • metal alloy/intermetallic compositions can provide the high energy density. These materials can have moderate volume changes upon cycling in a lithium ion battery. The volume changes can be accommodated with less degradation upon cycling through the combination with highly porous electrically conductive materials, such as highly porous carbon and/or foamed current collectors. Whether or not combined with a highly porous electrically conductive material, metal alloy/intermetallic compositions with an average particle size of no more than a micron can be advantageously used in the negative electrodes to improve cycling properties.
  • WO2009131700 describes a lithium ion battery comprising a positive electrode, a negative electrode, a separator between the positive electrode and the negative electrode and an electrolyte comprising lithium ions, wherein the negative electrode comprises a foamed current collector impregnated with an active material comprising a metal alloy/intermetallic material and wherein the negative electrode lacks a foil current collector or a grid current collector separate from the foamed current collector.
  • this document describes a powder comprising amorphous metal alloy/intermetallic particles wherein the particles have an average particle size of no more than about 1 micron.
  • WO2009131700 describes a method for forming a metal alloy/intermetallic composition having a reduced degree of crystallinity, the method comprising milling amorphous elemental powders to form the alloy/ intermetallic composition.
  • JP2005158401 describes a manufacturing method of manufacturing effectively a positive electrode active material having a porous structure, a positive electrode active material manufactured by this method, and a secondary battery using the active material.
  • the manufacturing method comprises a process of obtaining a mixture containing a primary particle of lithium-containing complex oxide and a pore forming particle, a process of producing a compound particle of the primary particle and the pore forming particle from the mixture, and a process of forming a porous particle made mainly of lithium-containing complex oxide by removing and/or melting the pore-forming particle constituting material contained in the compound particle.
  • This positive electrode active material according to JP2005158401,is suitable as a positive electrode active material of lithium-ion secondary battery using a normal temperature molten salt electrolyte.
  • a battery bi-layer cell comprises an anode structure comprising a conductive collector substrate, a plurality of pockets formed on the conductive collector substrate by conductive microstructures comprising a plurality of columnar projections, and an anodically active powder deposited in and over the plurality of pockets, an insulative separator layer formed over the plurality of pockets, and a cathode structure joined over the insulative separator.
  • US2011052997 scribes a negative electrode for a lithium battery including an active material layer and a current collector.
  • the active material layer has a plurality of crystal grains and the plurality of crystal grains include a plurality of pores.
  • a first pore of the plurality of pores has a first length and a second length, the first length being the maximum length orthogonal to the current collector and the second length being the maximum length orthogonal to the first length, and the first length is greater than the second length.
  • WO2010050347 describes a sintered lithium complex oxide having excellent high-rate discharge characteristics; a positive electrode composition for batteries, which uses the sintered lithium complex oxide; a positive electrode for batteries; and a lithium ion battery.
  • the sintered lithium complex oxide is obtained by sintering fine particles of lithium complex oxide together, and is characterized in that the peak pore size giving the maximum differential pore volume is 0.80-5.00 ⁇ , that the total pore volume is 0.10-2.00 mL/g, that the average particle size is not less than the above-specified peak pore size but not more than 20 ⁇ , that there is a sub-peak giving a differential pore volume not less than 10% of the maximum differential pore volume on the smaller pore size side with respect to the above- specified peak pore size, that the pore size corresponding to the sub-peak is more than 0.50 ⁇ but not more than 2.00 ⁇ , that the BET specific surface area of the sintered lithium complex oxide is 1.0-10.0 m 2 /g, and that the half width of the maximum
  • US2010159346 describes an electrode comprising a carbon material obtained from an azulmic acid and a current collector and/or a binder.
  • Lithium ion batteries consist of an anode, cathode and in between an electrolyte.
  • the electrodes contain the active materials in which Li can be stored in order to store energy.
  • the design of the battery is such that a large amount of inactive materials is necessary, reducing the weight percentage of the amount of active electrode materials, and with it the energy density of the battery.
  • the physically limited diffusion of lithium ions and electrons through the electrodes are the reason why currently only small amounts of active material can be used on the metal current collector foils.
  • the basic problem is how to increase the amount of active material on the current collector foils, leading to a high energy density battery by the reduction of inactive materials.
  • an alternative electrode or electrode assembly
  • a lithium ion battery comprising such alternative electrode (or electrode assembly).
  • the invention provides an electrode assembly for a lithium ion battery, the electrode assembly comprising a lithium storage electrode layer on a current collector, wherein the lithium storage electrode layer comprises an active lithium storage material, carbon and binder, and wherein the lithium storage electrode layer is a porous layer, especially having a porosity in the range of 5-45 %, such as 10-40%, like 30-40%).
  • the pores may have pore widths in the range of 0.5-50 ⁇ , and having a porous layer thickness in the range of 5-500 ⁇ .
  • the porosity is in the range of 10-40%>, wherein the pores have widths in the range of 1-30 ⁇ , and having a porous layer thickness in the range of 10-200 ⁇ . Even more especially, the porosity is in the range of 30-40%>, wherein the pores have widths in the range of 1-30 ⁇ , and having a porous layer thickness in the range of 10-200 ⁇ .
  • the invention further provides an electrode assembly for a lithium ion battery, the assembly comprising a lithium storage electrode layer on a current collector, wherein the lithium storage electrode layer is a porous layer having a porosity in the range of 5-35 %, with pores having pore widths in the range of 0.5-100 ⁇ , especially 1-10 ⁇ , and having a porous layer thickness in the range of 5-500 ⁇ , especially 10-200 ⁇ .
  • the term “electrode assembly” is used to indicate that the electrode or electrode assembly comprises the active layer, herein indicated as lithium storage electrode layer (which is a porous layer)(and which may comprise the active lithium storage material), and a current collector, on which the active layer is arranged (see also below).
  • the term “electrode” is used for the active layer only, although the electrode also comprises a current collector. Therefore, for the sake of understanding, herein the term “electrode assembly” is further applied.
  • the term “lithium storage electrode layer” may also refer to a plurality of layers (i.e. a multi-layer structure). Such multi-layer structure may in an embodiment comprise layers with different compositions, such as different types of active material.
  • a specific feature of the electrode assembly is its porous layer.
  • Porosity or void fraction is a measure of the void spaces in the layer and is a fraction of the volume of voids over the total volume as a percentage between 0-100%.
  • the porosity is in the range of 5-45%, such as 5-40%, like 5-35 %, such as in the range of 10- 30 %.
  • the porosity may be determined.
  • the chemical composition, the density, the thickness and the weight can be used to evaluate the porosity.
  • the pore widths are preferably in the range of 0.5-100 ⁇ , such as 0.5-80 ⁇ , especially 0.5-50 ⁇ , more especially at least 1 ⁇ , even more especially in the range of 1- 50 ⁇ , such as at least 30 ⁇ , like in the range ofl-30 ⁇ , such as 1-10 ⁇ .
  • at least 50% more especially at least 80%>, yet even more especially at least 90% of the pores have such pore dimensions.
  • the lithium storage electrode layer has its above indicated porosity.
  • Width may for instance also refer to diameter of substantially circular cross-sections of pores. Not all pores may substantially have circular cross-sections, hence the pore width is chosen.
  • the pores show interconnectivity, which may be beneficial for good access of the liquid electrolyte in the battery.
  • the effective diameter may be chosen, which is preferably also in the range of 0.5-100 ⁇ , such as 0.5-80 ⁇ , especially 0.5-50 ⁇ , more especially at least 1 ⁇ , even more especially in the range of 1-50 ⁇ , such as at least 30 ⁇ , like in the range of 1-30 ⁇ , such as 1-10 ⁇ .
  • the effective diameter can be evaluated by calculating the circumferential length of the cross-section of the pore, using the length as circumferential length of a (virtual) circle, and based thereon calculating the diameter of that circle. In this way, the effective diameter can be estimated of the pore.
  • the porous layer thickness will be at least 5 ⁇ , such as 5-500 ⁇ , preferably at least 10 ⁇ , such as 10-200 ⁇ .
  • the term "porous layer thickness" is used to indicate the thickness of the porous layer (on the current collector).
  • the invention provides an electrode assembly as indicated above, wherein the porosity is in the range of 10-30%, wherein the pores have widths in the range of 1-100 ⁇ , especially 1-30 ⁇ , even more especially 1-10 ⁇ , and having a porous layer thickness in the range of 10-200 ⁇ .
  • the lithium storage electrode layer further comprises carbon
  • Carbon will in general be present in the lithium storage electrode layer in the range of at least 1.5 wt.%, such as especially about 1.5-20 wt.%, such as 5-20 wt.%, like 5-15 wt.%.
  • the active material will in general be present in the lithium storage electrode layer in the range of 60-95 wt.%, such as 75-95 wt.%, like at least 85 wt.%.
  • Remaining binder may be present in an amount of about 0-20 wt.%, such as 0.5-20 wt.%, like e.g. 5-20 wt.%, such as 10-15 wt.%.
  • Remaining pore former material will in general be in the amount of 1 wt.% or less, such as 0.5 wt.% or less, like 0.1 wt.% or less. In an embodiment, the remaining amount of pore former material is in the range of 100 ppm - 0.05 wt.%. These amounts are relative to the total weight of the lithium storage electrode layer.
  • the presence (or absence) of the pore former material and traces thereof may be detected with X-ray scattering (assuming crystalline pore former material) and/or elemental analysis (EDX, as is often possible with SEM apparatus) and/or MR spectroscopy.
  • EDX elemental analysis
  • carbon is the active material, as in an anode embodiment, this material may then be present in the lithium storage electrode layer in the range 85-95 wt.%.
  • the electrode is assembled in the battery configuration the liquid electrolyte will penetrate into the porous electrode.
  • the lithium storage electrode layer may especially comprise particulate active lithium storage material, particulate carbon, and binder.
  • the porosity may be due to channels within the lithium storage electrode layer between the particles of the particulate active lithium storage material and the particulate carbon.
  • the number average particle size of the particulate active lithium storage material is in the range of 50 nm - 1 ⁇ , and wherein the number average particle size of the particulate carbon is in the range of 1 nm - 0.1 ⁇ .
  • the particle size may be determined.
  • the lithium storage electrode layer may have a density in the range of 50 - 90 % of the theoretical density of packed active lithium storage material, carbon, and binder.
  • the theoretical density is about 60-65% of the density of the materials due to the packing of the particles. From this theoretical density, the lithium storage electrode layer has a density of at least 50%, such as 50-90%, especially at least 80%, such as 80-90%.
  • the lithium storage electrode layer comprises as active material an active lithium storage material.
  • an active lithium storage material In uncharged state, substantially all mobile or free lithium will be present in the cathode, whereas in the charged state, a substantial part may (also) be present in the anode. However, in uncharged state, the anode (or more especially the lithium storage electrode layer of the anode) may comprise substantially no free lithium.
  • mobile Li ions are always present in the electrolyte present between the electrodes and inside the porous electrodes.
  • 1 molar LiPF 6 dissolved in 50%-50% EC (ethylene carbonate) - DMC (dimethyl carbonate) is applied as electrolyte. The electrolyte penetrates in the pores and thus provides rapid Li ion access throughout the electrode.
  • the electrode assembly can be used as cathode or as anode, based on the active materials used.
  • the lithium storage electrode layer may comprise a material selected from the group consisting of LiFePC>4, LiMn 2 04, LiNio.5Mn1.5O4, L1C0O2, and Li[Ni,Mn,Co]i0 2 , Li[Li,Ni,Mn,Co]i0 2 , LiCoi / 3Nii / 3Mni /3 0 2 , LiNi0 2 , Li 3 V 2 (P0 4 ) 3, Li 2 FePC" 4 F, LiC 6 , Li 4 Ti 5 0i 2 , Si(for Li 4;4 Si), and Ge (for Li 4 4 Ge).
  • These materials can have a carbon coating and/or can be doped with transition metals when required for electrical conductivity. Carbon itself can also be used as active lithium storage material for the anode (see also below).
  • the lithium storage electrode layer may comprise > 75 wt.% of a material selected from the group consisting of LiFePC>4, LiMn 2 0 4 , LiNio.5Mn1.5O4, LiCo0 2 , and Li[Ni,Mn,Co]i0 2 , Li[Li,Ni,Mn,Co]i0 2 , LiCoi /3 Nii /3 Mni /3 0, LiNio . 8Coo . i5Alo . o50 2 , LiNi0 2 , Li 3 V 2 (P0 4 ) 3 , and Li 2 FeP0 4 F.
  • the lithium storage electrode layer may comprise > 75 wt.% of a material selected from the group consisting of Li 4 Ti 5 0i 2 , Ti0 2 , Si, Ge, and C. Again, these materials can have a carbon coating, though the pure carbon material may not need such coating.
  • silicon may also refer to carbon coated silicon (core shell particles). When carbon is applied as active lithium storage material in an anode, this may be one or more of hard, soft, or graphitic carbon.
  • the active lithium storage material not being carbon, is carbon coated.
  • the lithium storage electrode layer may comprise for instance LiFeP0 4 , Li[Ni,Mn,Co]20 4 , such as LiMn 2 0 4 or LiNi 0. 5Mn 1 . 5 O 4 , or Li[Ni,Mn,Co]i0 2 , such as LiCo0 2 , or other high potential materials.
  • the lithium storage electrode layer may comprise at least 75 wt.% of one of those materials. In another embodiment, the lithium storage electrode layer may comprise at least 75 wt.% of one of those materials.
  • the invention provides the electrode assembly as indicated above, especially for use as cathode, wherein the lithium storage electrode layer comprises > 75 wt.% of a material selected from the group consisting of LiFeP0 4 , LiMn 2 0 4 , LiNi 0.5 Mn 1.5 O 4 , LiCo0 2 , and Li[Ni,Mn,Co]i0 2 .
  • the lithium storage electrode layer may also refer to a layer comprising different types of active materials. These materials are herein also indicated as active lithium storage material.
  • the lithium storage electrode layer may comprise for instance Li Ti 5 0i 2 , Ti0 2 , Si (including carbon coated Si) and C, or other high potential materials, may be applied.
  • the lithium storage electrode layer may in an embodiment comprise at least 75 wt.% of one of those materials.
  • the lithium storage electrode layer may comprise at least 75 wt.% of one or more of those materials. Therefore, in a specific embodiment, the invention provides the electrode assembly as described above, (however) for use as anode, wherein the lithium storage electrode layer comprises > 75 wt.% of one of those material selected from the group consisting of Li Ti 5 0i 2 , Ti0 2 , Si and C.
  • the cathode in general starts as lithium based lithium storage electrode layer
  • the anode may originally be provided as lithium based and as non-lithium based lithium storage electrode layer (for instance based on Si or on C).
  • the lithium storage electrode layer has a porous layer thickness in the range of 5-500 ⁇ . In a variant, the lithium storage electrode layer has a porous layer thickness of at least 5 ⁇ . Especially, the lithium storage electrode layer has a porous layer thickness of at least 100 ⁇ . In a specific embodiment, the porous layer thickness is at least 80 ⁇ , more especially at least 100 ⁇ , such as 100-500 ⁇ , like 100- 200 ⁇ , such as especially 120-200 ⁇ . Hence, in an embodiment, lithium storage electrode layer has a porous layer thickness of at least 100 ⁇ . These relative thick layers (>100 ⁇ ) may especially be of interest for use in high capacity batteries.
  • the amounts of active material (and Li capacity that can be contained in that) which is related to the layer thicknesses, as well as the porosities and (mean) pore widths will in general be similar for both the cathode and anode, such as values for those respective features differing not more than 20%, preferably not more than 10%, of each other. In this way the Li contained in one electrode can be charged completely and most rapidly into the other and vice verse.
  • the capacities of a couple of a cathode and anode (which are separated by the electrolyte) preferably do not differ more than 20%.
  • the pore widths for instance when averaged over the number of pore widths measured (for instance with SEM), may be about 25 ⁇ for the cathode and 30 ⁇ for the anode (or vice versa).
  • the value for the layer with the larger value may be taken.
  • the anode may have mean pore widths of 30 ⁇ , and thus the cathode may have mean pore widths in the range of 24-36 ⁇ .
  • other values may also be possible, and were also obtained. This may e.g. depend upon the particle size of the pore former, the amount of pore former, the way the pore former is removed and the (amount of) liquid used.
  • the pore widths for instance when averaged over the number of pore widths measured (for instance with SEM), may be about 2.5 ⁇ for the cathode and 3 ⁇ for the anode (or vice versa).
  • the value for the layer with the larger value may be taken.
  • the anode may have mean pore widths of 3 ⁇ , and thus the cathode may have mean pore widths in the range of 2.5-3.6 ⁇ .
  • the current collector in general comprises a foil. This foil may be used as support for the lithium storage electrode layer.
  • the current collector may for instance comprise a Cu (copper) foil or an Al (aluminum) foil.
  • the current collector comprises a multi-layer foil.
  • the current collector comprises a foil selected from the group consisting of a Cu foil and an Al foil, and preferably, the foil has a foil thickness in the range of 1-40 ⁇ , such as in the range of 5-30 ⁇ , such as in the range of 5-25 ⁇ .
  • the current collector is a non massive layer, for instance comprising holes.
  • the current collector has a gauze shape. In an embodiment, the lithium storage electrode layer will substantially adopt such shape.
  • such foil may be coated with carbon, for instance with a layer of a few micron (this may add to the total thickness as indicated above.
  • Such carbon layer may facilitate layer formation of the lithium storage electrode layer and better contact with and adhesion to the current collector.
  • the current collector comprises a foil selected from the group consisting of a Cu foil and an Al foil, and the foil has a foil thickness in the range of 1- 30 ⁇ .
  • Cu foil may have a thickness of at least 6 ⁇ ;
  • Al foil may have a thickness in the range of e.g. 10-20 ⁇ .
  • the current collector comprises a carbon coated Al foil. As indicated above, this may further be beneficial in view of adhesion of the lithium active storage material to the foil.
  • the lithium storage electrode layer comprises at least 85 wt.% of the active lithium storage material and at least 1.5 wt.% carbon, related to the total weight of the lithium storage electrode layer.
  • the lithium storage electrode layer comprises at least 85 wt.% of the active lithium storage material and at least 5 wt.%) carbon, related to the total weight of the lithium storage electrode layer, and especially the active lithium storage material is selected from the group consisting ofLiFeP0 4 , LiMn 2 0 4 , LiNio.5Mn1.5O4, L1C0O2, Li[Ni,Mn,Co]i0 2 , Li[Li,Ni,Mn,Co]i0 2 , LiCoi / sNii / sMni / sO, LiNi 0.8 Coo .
  • lithium storage electrode layer may especially give good results.
  • the lithium storage electrode layer comprises at least 85 wt.%> of the active lithium storage material and at least 5 wt.%> carbon, related to the total weight of the lithium storage electrode layer, and wherein the active lithium storage material is selected from the group consisting ofLiFeP0 4 , LiMn 2 0 4 , LiNi 0.5 Mn 1.5 O 4 , LiCo0 2 , Li[Ni,Mn,Co]i0 2 , Li[Li,Ni,Mn,Co]i0 2 , LiCoi / sNii / sMm / sO, LiNio .8 Coo . i 5 Alo .
  • the lithium storage electrode layer comprises at least 85 wt.% of the active lithium storage material and at least 5 wt.%) carbon, related to the total weight of the lithium storage electrode layer, and wherein the lithium storage electrode layer has a porous layer thickness of at least 100 ⁇ .
  • the mass loading of the active lithium storage material in the lithium storage electrode layer on the current collector is at least 10 mg/cm 2 , and especially 80% of said active lithium storage material can be charged within 1 hour. This may provide an assembly (and a battery), with a high energy density. State of the art cathodes or anodes may have a higher loading, but then have relatively bad charging characteristics.
  • the mass loading of the active lithium storage material in the lithium storage electrode layer on the current collector is at least 15 mg/cm 2 , and 70% of said active lithium storage material can be charged within 1 hour.
  • the invention provides a lithium ion battery comprising a cathode and an anode, wherein one or more of the cathode and the anode comprise an electrode assembly as defined herein.
  • the invention provides a lithium ion battery comprising a cathode and an anode, wherein the cathode and anode comprise electrode assemblies as described herein. Such battery may be charged quickly and/or may have a high capacity.
  • the invention provides such lithium ion battery, wherein the lithium storage electrode layers of the electrode assembly have porous layer thicknesses of at least 80 ⁇ , especially at least 100 ⁇ , and wherein the lithium ion battery has a capacity of at least 2.5 mAh/cm 2 , especially at least 3 mAh/cm 2 .
  • Prior art high performance lithium ion batteries may not have capacities over about 1 mAh/cm 2 , especially not larger than about 2.5 mAh/cm 2 .
  • the invention provides a lithium ion battery, such as defined above, wherein the lithium storage electrode layers of the electrode assemblies have porous layer thicknesses of at least 100 ⁇ .
  • the lithium storage electrode layers of the electrode assemblies have porous layer thicknesses of at least 100 ⁇ , and wherein the lithium ion battery has a capacity of at least 3 mAh/cm 2 .
  • the lithium ion comprises a first electrode assembly and a second electrode assembly according to any one of the preceding claims, with liquid electrolyte configured between the first and the second electrode assembly, wherein the pores of the porous layers are at least partly filed with said electrolyte.
  • the invention provides in a further aspect a process for the production of an electrode assembly.
  • the process may for instance involve the mixing of (10-40 wt.%) (micron sized) NaHCC crystals (or an equally suitable other material) into the slurry that is used to produce a cathode.
  • slurry may for instance include in the order of about of 80 wt.% LiFeP0 4 active material, 10 wt.% PVDF (polyvinylidene fluoride) binder, and 10 wt.% conducting carbon altogether dissolved in a suitable organic solvent such as MP (N-methylpyrrolidone).
  • the NaHC03 (or equivalent) should not (substantially) dissolve in the NMP (or other solvent) because these crystallites are present to produce after removing them the porous structure.
  • the NaHC03 that does dissolve in NMP can recrystallize when the NMP is removed by evaporation. After casting the electrode, evaporation of the solvent, pressing for a compacted and well contacted layer, and drying in an oven, the NaHC03 is washed away in water upon which C0 2 gas evolves and NaOH is dissolved and washed away through the pores. The gas evolution is expected to especially contribute to the formation of connected pores. After thorough drying in a vacuum oven the electrode is ready for use in a battery with a liquid electrolyte. For producing the anodes a similar method may be applied with Ti0 2 , or other materials, such as carbon or carbon coated silicon.
  • An alternative material for NaHC0 3 and water may for instance be other carbonate salts, like ( H 4 ) 2 C0 3 or H 4 HC0 3 that can be removed by thermal treatment, NaCl (and/or LiCl) that can be dissolved in water.
  • ( H 4 ) 2 C0 3 is suitable in combination with Li 4 Ti 5 0i 2 anode material.
  • salts that do not dissolve in MP, and that show no H (or other ion exchange) for Li exchange with the electrode materials are used.
  • the advantage of NaHC0 3 and/or similar systems, is that it forms C0 2 gas at room temperature, while the other materials do not. The emerging gas may help to form the pores and connect them.
  • the binder is selected from the group consisting of PVDF (polyvinylidene fluoride) and PTFE (polytetrafluoroethylene).
  • the mixture may in an embodiment comprise 5-40 parts pore former material, 6-90 parts active material, 1-15 parts binder, and 1-20 parts (conductive) carbon.
  • the mixture may in an embodiment comprise 5-40 wt.% pore former material, 6-90 wt.% active material, 1-15 wt.% binder, and 1-20 wt.% (conductive) carbon. This mixture is then used and dissolved in a sufficient amount of solvent to dissolve the binder but not the pore former material (and applied to the (optionally carbon coated) current conductor).
  • the invention also provides a process for the production of an electrode assembly, for instance as described herein, comprising:
  • a current collector such as a foil as indicated above
  • the process may comprise applying pressure to the thus formed layer.
  • the mixture may for instance be a slurry or a suspension.
  • active lithium storage material a material selected from the group comprising LiFeP0 4 , Li[Ni,Mn,Co] 2 0 4 , such as LiMn 2 0 4 or LiNi 0.5 Mn 1.5 O 4 , or Li Ni,Mn,Co]i0 2 , such as LiCo0 2 for the cathode may be applied, and for the anode a material selected from the group comprising Li Ti 5 0i 2 , Ti0 2 , Si, C coated Si, and C may be applied (see also above, especially for further possible active materials).
  • the binder may comprise one or more of PVDF (polyvinylidene fluoride), CMC (carboxymethyl cellulose), and PTFE (polytetrafluoroethylene), although other materials may be applied as well.
  • the binder may be a solid material, but may also be a liquid material.
  • the binder may be a liquid material during processing and/or a liquid is part of the mixture (and may be used to provide the liquid properties of the slurry or suspension).
  • the liquid is especially chosen that the pore former material does not (substantially) solve therein.
  • the liquid comprises one or more of NMP (N-methylpyrrolidone), acetone, and (dissolved) THF (tetrahydrofuran), but also other liquids may be applied.
  • the binder may especially be solved in a solvent. In this way a liquid is obtained which may be used to form for instance the liquid material, such as a slurry or suspension, with the other herein indicated ingredients.
  • any suitable material may be applied, but preferably a pore former material that may easily be solvable in water or ethanol, especially in water. Further, preferably materials are used that may also form, upon salvation or reaction with a solvent a gas, as gas formation may contribute to pore formation.
  • the pore former material comprises one or more of NaHC03, NaCl, MgCl 2 , and (NH ) 2 C03, though other systems may also be applied (see above).
  • the pore former material is a solid, crystalline material. Hence, in an embodiment the pore former material may be removed by dissolving the pore former material in a solvent for the pore former material.
  • the pore former material is preferably not (well) solvable in the liquid (such as one of the indicated solvents).
  • the pore former comprises a crystalline material.
  • the pore former is soluble in water.
  • the pore former is non-soluble in water.
  • the binder may be soluble in water (may be on a water basis).
  • the solvent for the pore former material is not a solvent for the binder (an in an embodiment vice versa).
  • PVDF or PTFE solvable in organic solvents
  • CMC or SBD are solvable in water.
  • the pore former material is removed by thermal treatment of the layer obtained as described herein.
  • the pore former comprises (NH 4 ) 2 C03, and/or (NH 4 )HC03. These materials may thermally be removed (due to decomposition upon heating). Thermal treatment may especially beneficial in view of processing considerations.
  • the pore former is applied to provide a porous structure. Interconnection of the pores with the present process may especially be created.
  • the pore former is used as a kind of templating agent, and is therefore also indicated as template, templating material, etc.
  • the liquid is a solvent for the binder, and the pore former material does not or only partly dissolve in the solvent for the binder.
  • the pore former material is removed by dissolving the pore former material in a solvent for the pore former material.
  • Carbon may be provided per se, and may be present as coating on the active material.
  • carbon coated Li 4 Ti 5 0i 2 is commercially available.
  • the addition of carbon may be desired, in order to further improve electrical conductivity.
  • the mixture may be applied by casting the mixture to the current collector.
  • the mixture is melted to the current collector.
  • the process comprises applying pressure to the thus formed layer.
  • pressure may be applied after drying, and in another embodiment, pressure may be applied during drying.
  • the process comprises applying pressure to the thus formed layer.
  • pressure may be applied after drying, and in another embodiment, pressure may be applied during drying.
  • the invention further provides a process comprising:
  • the lithium storage material comprises LiFeP0 4 or Li 4 Ti 5 0i 2
  • the binder comprises one or more of PVDF, CMC, and PTFE
  • the liquid comprises one or more of NMP, acetone, and THF
  • the pore former material comprises one or more of NaHCOs, NaCl, MgCl 2 , (NH 4 ) 2 C0 3 and NH 3 HC0 3 .
  • other combinations of materials may be applied.
  • the lithium ion storage material comprises particulate active lithium storage material, wherein the carbon comprises particulate carbon, and binder.
  • the number average particle size of the particulate active lithium storage material may be in the range of 100 nm - 1 ⁇ , and the number average particle size of the particulate carbon is in the range of 1 nm - 0.1 ⁇ .
  • the amount of lithium ion storage material is at least 85 wt.%, wherein the amount of carbon is at least 2 wt.%, and the amount of binder is at least 2 wt.% relative to the total amount of active lithium storage material, carbon and binder.
  • the active lithium ion storage material comprises LiFeP0 4 or Li Ti 5 0i 2
  • the binder comprises one or more of PVDF, CMC, and PTFE
  • the liquid comprises one or more of NMP, acetone, and THF
  • the pore former material comprises one or more of NaHC0 3 , NaCl, LiCl, MgCl 2 , and (NH 4 ) 2 C0 3 , NH 3 HC0 3
  • the binder comprises one or more of PVDF and PTFE. Especially such embodiment may give good Li storage properties.
  • the invention provides also a lithium storage electrode layer on a current collector, obtainable by the process as defined herein. Further, the invention also provides an electrode assembly according to any one of the preceding claims, wherein the lithium storage electrode layer is obtainable by the process as defined herein.
  • a combination of two or more different pore formers is applied.
  • a combination of two or more different liquids especially solvents
  • a combination of two or more different binders is applied.
  • the improved performance is explained by improved Li + ion electrolyte accessibility through the interconnected network in the electrode matrix, effectively lifting constraints of through solid ionic diffusion. This enables high energy density LiFePC>4 electrodes to retain good capacity during (dis)charging at relatively high current i.e., up to 60C. Such facile templating methods will be more generally applicable for other types of Li-ion insertion electrode materials.
  • the term “substantially” herein will be understood by the person skilled in the art.
  • the term “substantially” may also include embodiments with “entirely”, “completely”, “all”, etc. Hence, in embodiments the adjective substantially may also be removed.
  • the term “substantially” may also relate to 90% or higher, such as 95% or higher, especially 99% or higher, even more especially 99.5% or higher, including 100%.
  • the term “comprise” includes also embodiments wherein the term “comprises” means "consists of.
  • Fig. 2a schematically depicts a SEM figure of the macro porous lithium storage electrode layer (here a LiFeP0 4 -based layer);
  • FIG. 2b-2c schematically depict some aspects of the invention
  • FIGS. 3a-3b schematically depict some embodiments of a battery; These drawings are not necessarily on scale; and
  • Figs. 4a-4d (a) show the charging voltage profiles with respect to a Li/Li + reference electrode for different rates for a non-templated electrode with 2.6 mg/cm 2 active material loading; (b) Charging voltage profile for different rates for a templated electrode with 2.7 mg/cm 2 active material loading; (c) Charging voltage profile for different rates for a templated electrode with 7.5 mg/cm 2 active material loading; (d) Charge rate comparison between templated and non-templated electrodes.
  • Fig. la schematically depicts an electrode assembly 100 ("assembly 100") for a lithium ion battery, the assembly 100 comprising a lithium storage electrode layer 110 on a current collector 120, such as a Cu foil, wherein the lithium storage electrode layer 110 is a porous layer 10 having a porosity in the range of 5-35 %, comprising pores 11 having pore widths d (see below) in the range of 1-100 ⁇ , and having a porous layer thickness hi in the range of 5-500 ⁇ .
  • the current collector 120 has a height h2; the total height of the electrode assembly 100 is indicated with h.
  • Reference 7 indicates carbon, such as present as particulate carbon.
  • Reference 17 indicates lithium active storage material, such as present as particulate lithium active storage material, and reference 27 indicates a binder.
  • Fig. lb very schematically depicts a lithium ion battery 200, with anode 101 and cathode 102.
  • Both the anode 101 and the cathode 102 are electrode assemblies 100 as described herein, but with different properties, such as for instance the lithium storage electrode layer 110 of the cathode 102 being based on LiFeP0 4 as Li storage material, and the lithium storage electrode layer 110 of the anode 101 being based on C.
  • Li ions will enter the anode (for instance via the electrolyte in the pores of the lithium storage electrode layer 110 of the anode 101).
  • Reference 201 indicates a separator(which is soaked in the liquid electrolyte).
  • Reference 103 indicates electrolyte, that is in between the electrode assemblies 100, and which also penetrates the pores.
  • electrolytes are 1 molar LiPF 6 dissolved in a mixture of EC/DMC (ethyl enecarbonate / dimethylcarbonate), or 1 molar LiPF 6 dissolved in a mixture of EC/DEC (diethylenecarbonate) or L1CIO 4 dissolved in 1M LiC10 4 in propylene carbonate.
  • pores 11 can also be interconnected. Especially when the pore former material has a volume fraction of at least 7 wt.%, and expands when removed interconnection may be achieved. Interconnection of the pores 11 is preferred.
  • Fig. 2a is a SEM picture of the lithium storage electrode layer 110 based on LiFePC In this example, the presence of pore former after removal was below the detection limit of the elemental analysis unit of the SEM.
  • Fig. 2b is another schematical drawing of the lithium storage electrode layer, with a phase of particles, carbon 7 and active lithium storage material 17, and in between binder 27. Large pores 11, substantially not in the particulate material, but as pores in the entire layer are the basis of the porosity. The figure shows interconnectivity of the pores.
  • Fig. 2c shows schematically the impact of templating.
  • the spheres represent the active lithium storage material.
  • the pathway 47 of Li + is much shorter and for a large part through a liquid electrolyte, leading to better properties.
  • the liquid pathway may sometimes be blocked.
  • Li+ may finally reach the current collector through the solid electrode material, this may be slow or very slow, which is indicated with the dashed line 57.
  • Figs. 3a and 3b schematically depict two different embodiments of a lithium ion battery 200.
  • References 120a and 120c indicate current collector anode and current collector cathode respectively.
  • a separator 103 soaked in a liquid electrolyte.
  • the lithium storage electrode layers 110 which sandwich the respective current collector anodes and current collector cathodes are relatively thin, leading to a battery that may be charged and discharged fast (e.g. for high power applications).
  • the lithium storage electrode layers 110 are much thicker. This may be a high energy density application where there is realized a relatively large amount of active material in the battery compared to the other materials such as current collectors, separator and electrolyte.
  • Figs. 4a-4d (a) show the charging voltage profiles relative to a Li/Li + counter electrode for different rates for a non-templated electrode with 2.6 mg/cm 2 active material loading; (b) Charging voltage profile for different rates for a templated electrode with 2.7 mg/cm 2 active material loading; (c) Charging voltage profile for different rates for a templated electrode with 7.5 mg/cm 2 active material loading; (d) Charge rate comparison between templated and non-templated electrodes.
  • the method involves the mixing of 10 - 40% micron sized NaHC03 crystals (or an equally suitable other material) into the normal slurry that is used to produce a cathode.
  • Such slurry involves of the order of 80 wt.% LiFeP0 4 active material, 10 wt.% PVDF binder, and 10wt.% conducting carbon altogether dissolved in a suitable organic solvent such as MP.
  • the NaHC03 (or equivalent) should not dissolve in the NMP (or other solvent) because these crystallites are present to produce after removing them the porous structure.
  • Lithium ion batteries with electrode assemblies as described herein were made and compared to similar systems, but without porosity of the lithium storage electrode layer of the anode and cathode.
  • LiFeP0 4 cathodes were prepared by thoroughly mixing carbon coated LiFeP0 4 (140nm, Phostech) powder with PVDF (Aldrich), and Super P carbon black (TAMCIL) in a 90:5:5 weight ratio using NMP as solvent.
  • For preparing templated electrodes 20% to 50 wt% NaHC0 3 (Aldrich) is added to the electrode slurry. First the NaHC0 3 is stirred in MP forming a sodium hydrogen carbonate suspension followed by the addition of PVDF and again stirring until the binder is dissolved. Part of the NaHC0 3 dissolves as is evident from the formation of long, thin, ribbon like crystals, while the remainder forms micron sized crystals in a slightly turbid suspension.
  • the carbon coated LiFeP0 4 and the carbon black are added and stirred for approximately 12 hours.
  • the resulting slurry was casted using different doctor blade thicknesses onto carbon coated Al foils (Exopad) and the resultant electrode thickness is measured by using a Timos Vectra-Touch precession instrument.
  • the electrodes are dried at 40°Cfor 48 hours in a vacuum oven to evaporate the NMP.
  • it is essential to mechanically compress the dried electrodes using a roller hand press. This also makes the electrode density high.
  • the NaHC0 3 templated electrodes are washed with demineralized water which reacts with the NaHC0 3 towards water soluble NaOH and gaseous C0 2 , resulting in a compacted but porous electrode.
  • the gas formation is visible as tiny gas bubbles evolving at the electrode surface (see Supporting Information). From the fact that all NaHC0 3 can be removed (elemental analysis) it is clear that the crystals are providing connected pathways that the water is capable of opening connected pores completely.
  • the washing step is followed by drying the electrodes for a few hours at 100°C to 140°C.
  • Battery cells were assembled in Swagelok type cells under argon atmosphere ( ⁇ 0.1 ppm 0 2 / ⁇ 2 0). Lithium metal was used as anode and glass fiber disks (Whatman) as separators.
  • the electrolyte used was 1.0 molar LiPF 6 in EC/DMC (ethylene carbonate and dimethyl carbonate in a 1 : 1 ratio) (Novolyte, battery grade). To characterize the obtained batteries the cells were tested at variable charge rate between C/20 up to 60C and always discharged with a C/5 rate within a voltage window of 4.2 and 2.5 V vs Li/Li + using a Maccor 4300 battery cycler.
  • the electrode thickness and microstructure were studied by a scanning electron microscope JEOL 7500F.
  • the characteristic Sodium energy levels observed in the Energy Dispersive X-Ray spectra in Figure 1 confirm the presence of NaHC0 3 in the dried electrodes before washing.
  • Element mapping suggested and confirmed a distribution of NaHC0 3 in the LiFeP0 4 electrode composite where the largest distances between NaHC0 3 concentrations are a few ⁇ and apparent concentration area's are ranging from 0.5 to 1.5 ⁇ .
  • the presence of NaHC0 3 in the LiFeP0 4 electrodes before washing is also confirmed by the characteristic XRD (X-Ray Diffraction) reflections of NaHC0 3 . Electron micrographs showed that the NaHC0 3 also forms ribbons with a thickness of less than 50nm and a length of more than 10 ⁇ on top of the LiFeP0 4 electrodes.
  • the NaHC0 3 partly dissolves in the MP and recrystallizes forming ribbons upon drying, a surprising and interesting process that we are currently studying in further detail.
  • the solid NaHC0 3 acts as temporary rigid support preventing the collapse of the interconnected porous structure.
  • the result after washing and subsequent drying is a highly porous network with micrometer dimensions.
  • the EDX spectrum and the XRD pattern after washing showed the complete removal of the Na, suggesting that the NaHC0 3 was completely decomposed through the following reaction: NaHC0 3 + H 2 0 ⁇ NaOH + C0 2 + H 2 0.
  • C0 2 is clearly observed during the washing step which most likely also attributes to the interconnectivity of the porous network.
  • the electrodes without the NaHC0 3 template also have a high degree of porosity; however, the pores appear much less well connected.
  • Table 2 Prepared electrodes listing the thickness, active material loading, electrode density, porosity and tap density. The porosity is calculated from the apparent weights and thickness. Measurement of the electrode thickness and weight per cm 2 electrode is used to determine the porosity and tap density as shown for all electrodes in Table 2. The increase in porosity for both, templated and non templated electrodes with increasing loading density is due to application of the same calendaring pressure during electrode fabrication. Table 2 also illustrates that the templated electrodes have typically only 2 to 3% higher porosity due removal of the NaHC0 3 template.
  • Fig. 4b shows the charge voltage profiles for the NaHC0 3 templated LiFeP0 4 electrode with comparable loading density and porosity compared to one of the non- templated electrodes, 2.7 mg/cm 2 (porosity ⁇ 34%).
  • the higher charge capacities at all rates decreasing from ⁇ 163mAh/g at C/5, to -60 mAh/g at 60C illustrate the superior performance of the templated electrode (see also fig. 4d).
  • Such rate performances should be compared in the context of the active material loading density, which strongly affects the rate dependent capacity and the tap density of the electrode which determines the volumetric energy density.
  • the nano-sizing is very effective for improving the rate performance, it negatively affects the tap density (inversely related to the porosity) generally towards values below 1 g/cm 3 leading to low volumetric energy densities.
  • the templated materials with tap density close to 2 g/cm 3 result in almost 120 mAh/g at 20C charge (albeit with C/5 discharge) illustrating the excellent performance in combination with high volumetric energy density of the templated electrodes.
  • recently high performance monodisperse porous microspheres were reported to reach less than half at 20C with a lower tap density around 1.2 g/cm 3 .
  • Higher charge rates are reported in literature, 90 mAh/g at 60C for core-shell nanostructured LiFeP0 4 /carbon composites and 80 mAh/g at 60C for 50 nm LiFeP0 4 coated with a fast ionic conducting phases , however, these electrodes have only a very limited active material loading of less than 1 mg/cm 2 .

Abstract

L'invention concerne un ensemble électrode pour accumulateur au lithium-ion, l'ensemble électrode comprenant une couche d'électrode de stockage de lithium formée sur un collecteur de courant, ladite couche constituant une couche poreuse dont la porosité est comprise dans la plage de -35 %, les pores présentant des dimensions de pores comprises dans la plage de 1-100 µm, et l'épaisseur de la couche poreuse étant comprise dans la plage de 5-500 µm. L'invention concerne aussi un accumulateur au lithium-ion qui comprend de tels ensembles électrodes comme anode et cathode. Un procédé de production est également décrit.
PCT/NL2012/050521 2011-07-21 2012-07-20 Ensemble électrode pour accumulateur au lithium-ion, procédé de production d'un tel ensemble électrode et accumulateur au lithium-ion comprenant de tels ensembles électrodes WO2013012334A1 (fr)

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