WO2015062985A1 - Procédé permettant de produire une électrode pour une batterie lithium-ion - Google Patents

Procédé permettant de produire une électrode pour une batterie lithium-ion Download PDF

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Publication number
WO2015062985A1
WO2015062985A1 PCT/EP2014/072847 EP2014072847W WO2015062985A1 WO 2015062985 A1 WO2015062985 A1 WO 2015062985A1 EP 2014072847 W EP2014072847 W EP 2014072847W WO 2015062985 A1 WO2015062985 A1 WO 2015062985A1
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lithium
electrode
range
active material
phosphoric acid
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PCT/EP2014/072847
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German (de)
English (en)
Inventor
Guk-Tae Kim
Nicholas Löffler
Italo Doberdo
Nina Laszczynski
Dominic BRESSER
Prof. Dr. Stefano PASSERINI
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Westfälische Wilhelms-Universität Münster
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Publication of WO2015062985A1 publication Critical patent/WO2015062985A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/48—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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • 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 the field of lithium-based energy storage, in particular the production of composite electrodes for lithium-ion batteries from an aqueous dispersion of the active material.
  • Lithium-ion batteries are currently the leading technology in the field of rechargeable batteries.
  • the electrode for lithium-ion batteries often uses so-called composite electrodes, which are a lithium-ion reversible receiving and donating electrochemical active material, such as a lithium metal oxide Contain that on a metal foil, for example, an aluminum foil, as
  • Pantograph acts, is applied. Applying the active material to the
  • Current collector can be made of an aqueous or non-aqueous dispersion, which further contains a binder and optionally additives such as conductive carbon. Subsequently, the electrode is dried, wherein the aqueous or organic solvent of the dispersion volatilizes.
  • This object is achieved by a method for producing an electrode for a lithium-based energy store comprising applying an aqueous dispersion comprising a lithium-containing active material to a current collector, wherein the aqueous dispersion in the range of> 0.025 mM to ⁇ 0.5 mM phosphoric acid added.
  • Carboxymethylcellulose is possible, which can be dispensed with toxic and expensive organic solvents such as N-methylpyrrolidone.
  • the term “active material” refers to a material which can reversibly take up and release lithium ions, a process which is referred to as “insertion” or else “intercalation”.
  • the active material thus “actively” participates in the electrochemical reactions occurring during charging and discharging, in contrast to other possible constituents of an electrode, for example binders, conductive carbon or current collector.
  • the active material may in particular be a lithium metal oxide or lithium metal phosphate.
  • the active material is usually applied to a metal foil, for example a copper or aluminum foil which acts as a current conductor, from a dispersion which also contains a binder and optionally additives such as conductive carbon in a dispersion medium and is also referred to as "electrode paste".
  • a metal foil for example a copper or aluminum foil which acts as a current conductor
  • a dispersion which also contains a binder and optionally additives such as conductive carbon in a dispersion medium and is also referred to as "electrode paste”.
  • Such an electrode is commonly referred to as a composite electrode.
  • the method is therefore a method for producing a composite electrode.
  • the term "dispersion” is understood to mean a heterogeneous mixture which comprises at least two constituents which do not dissolve or hardly dissolve into one another.
  • a binder such as carboxymethylcellulose may at least partially or completely dissolve in the amounts used in water as the dispersion medium, while the lithium-containing active material, for example, a lithium metal oxide, and carbon which may be added as an additive to aid conductivity, exist as a disperse phase.
  • the lithium-containing active material for example, a lithium metal oxide, and carbon which may be added as an additive to aid conductivity, exist as a disperse phase.
  • the production of an electrode may include the steps of preparing a dispersion medium such as water, dissolving a binder such as carboxymethylcellulose therein, adding the lithium-containing active material such as a lithium metal oxide, and optionally adding carbon, and dispersing by, for example, stirring or using a ball mill include.
  • a dispersion medium such as water
  • a binder such as carboxymethylcellulose
  • carbon optionally adding carbon
  • dispersing by, for example, stirring or using a ball mill include. This can be active material and
  • Carbon may be added together, for example, as a solid mixture or sequentially, with the carbon being added before or after the active material.
  • the time at which phosphoric acid is added to the aqueous dispersion is variable.
  • the phosphoric acid is added to the aqueous dispersion prior to adding the active material.
  • This has the advantage that decomposition of the water on the surface of the lithium metal oxides can be prevented even during the addition. It is preferred that a solution containing in the range of> 0.025 mM to ⁇ 0.5 mM phosphoric acid in water is already present and the binder dissolved therein.
  • the dispersion can then be applied to a metal foil as a conductive substrate, in particular onto an aluminum foil, and dried become.
  • the predried electrode can be pressed before a final drying step.
  • the porosity of the electrode and the layer thickness of the applied composite can be reduced and the volumetric surface loading increased.
  • the aqueous dispersion is in the range of> 0.05 mM to ⁇ 0.3 mM, preferably in the range of> 0.05 mM to ⁇ 0.25 mM, preferably in the range of> 0.1 mM to ⁇ 0.25 mM phosphoric acid, too.
  • An addition of phosphoric acid in the range of> 0.05 mM to ⁇ 0.3 mM shows a particularly good combination of preventing the corrosion of the aluminum current collector and the specific capacity of the electrode prepared from the corresponding aqueous dispersion, while the
  • Active material is hardly attacked.
  • a concentration in the range of> 0.05 mM to ⁇ 0.25 mM phosphoric acid a dissolution of the active material such as NMC (Li [Nii / 3Mni / 3Coi / 3] 0 2 ) can be further reduced.
  • the lithium-containing active material may be selected from lithium metal oxides or lithium metal phosphates such as L 1 O 2 O 2 (LCO), LiNiO 2 , Li [Ni x Coi_ x ] O 2 where 0 ⁇ x ⁇ 1, Li [Ni x Coi_ x _ y Al y ] O 2 wherein 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 0.2 (NCA), Li 4 Ti 5 0i 2 (LTO), Li [Ni x Coi_ x _ y Mn y ] 0 2 where 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 1 (NMC), LiMn 2 0 4 , Li [Ni x Mn 2 _ x ] 0 4 where 0 ⁇ x ⁇ 0.5, Li [Ni x Mn 2 _ x _ y Co y ] 0 4 wherein 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.15 and 0
  • the active material is a
  • Lithium metal oxide selected from the group consisting of Li [Nii / 3 Mni / 3 Coi / 3] O 2 (NMC), LiCoO 2 (LCO), Li [Nio , 8 Coo , i 5 Alo, O5] O 2 (NCA) and / or Li 4 Ti 5 O 2 (LTO).
  • NMC Li [Nii / 3 Mni / 3 Coi / 3] O 2
  • LCO LiCoO 2
  • NCA Li [Nio , 8 Coo , i 5 Alo, O5] O 2
  • LTO Li 4 Ti 5 O 2
  • These lithium-containing active materials are particularly suitable for producing a cathode.
  • the current collector is formed on the basis of or made of aluminum.
  • the current collector may be an aluminum foil. It is advantageous that by adding 0.025 mM to 0.5 mM phosphoric acid
  • Aluminum foil can be used as a current collector.
  • Another object of the invention relates to an aqueous dispersion for producing a composite electrode comprising a lithium-containing active material, wherein the dispersion in the range of> 0.025 mM to ⁇ 0.5 mM phosphoric acid.
  • phosphoric acid in the range of> 0.025 mM to ⁇ 0.5 mM in the manufacture of electrodes can also prevent the corrosion of an aluminum current collector from an aqueous dispersion and thereby improve the specific capacity of the cell in the long term.
  • Binders such as carboxymethyl cellulose allows, which can be dispensed with toxic and expensive organic solvents such as N-methylpyrrolidone.
  • the dispersion contains in the range of> 0.05 mM to ⁇ 0.3 mM, preferably in the range of> 0.05 mM to ⁇ 0.25 mM, preferably in the range of> 0.1 mM to ⁇ 0, 25 mM, phosphoric acid.
  • Phosphoric acid in the range of> 0.05 mM to ⁇ 0.3 mM can prevent corrosion of an aluminum current collector particularly well, while the active material is hardly attacked.
  • dissolution of the active material such as NMC can be further reduced.
  • the dispersion contains in the range of> 0.025 mM to ⁇ 0.5 mM phosphoric acid and a lithium-containing active material and may further contain a binder and optionally carbon or conductive carbonaceous material.
  • the lithium-containing active material may be selected from lithium metal oxides or lithium metal phosphates such as LiCoO 2 (LCO), LiNiO 2 , Li [Ni x Coi_ x ] 0 2 where 0 ⁇ x ⁇ 1, Li [Ni x Coi_ x _ y Al y ] 0 2 wherein 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 0.2 (NCA), Li 4 Ti 5 0i 2 (LTO), Li [Ni x Coi_ x _ y Mn y ] 0 2 where 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 1 (NMC), LiMn 2 0 4 , Li [Ni x Mn 2 _ x ] 0 4 where 0 ⁇ x ⁇ 0.5, Li [Ni x Mn 2 _ x _ y Co y ] 0 4 wherein 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.15 and 0
  • the dispersion contains an active material selected from the group consisting of Li [Nii / 3Mni / 3Coi / 3] O 2 (NMC), LiCoO 2 (LCO), Li [Ni 0.8 Coo , i 5 Al 0, o 5 ] 0 2 (NCA) and / or Li 4 Ti 5 0i 2 (LTO), preferably
  • Suitable binders include poly (vinylidene difluoride-hexafluoropropylene) (PVDF-HFP) copolymer, polyvinylidene fluoride (PVDF), styrene-butadiene rubber (SBR), and carboxymethylcellulose (CMC).
  • PVDF-HFP poly (vinylidene difluoride-hexafluoropropylene)
  • PVDF polyvinylidene fluoride
  • SBR styrene-butadiene rubber
  • CMC carboxymethylcellulose
  • a preferred binder is carboxymethylcellulose (CMC).
  • the binder is also referred to as a binder.
  • Carboxymethylcellulose is more environmentally friendly and less expensive compared to conventional commercial ones
  • the conductivity of the electrode can be further increased.
  • Preferred carbonaceous materials are, for example, carbon black, synthetic or natural graphite, graphene, carbon nanoparticles, fullerenes or mixtures thereof.
  • a preferred carbon black is available, for example, under the trade name Super P® and Super P Li®.
  • the carbon or the carbonaceous material may have an average particle size in the range from 1 nm to 500 ⁇ m, preferably from 5 nm to 1 ⁇ m, preferably in the range from 10 nm to 60 nm.
  • the mean diameter of the carbon particles may be 20 ⁇ m or smaller, preferably 15 ⁇ m or smaller, preferably 10 ⁇ m or smaller, more preferably in the range from 10 nm to 60 nm.
  • Another object of the invention relates to an electrode for a lithium-based energy storage obtainable by the method according to the invention.
  • Another object of the invention relates to an electrode, in particular a composite electrode, for a lithium-based energy storage comprising a lithium-containing active material, wherein the surface of the active material particles in a layer thickness in the range of> 1 nm to ⁇ 10 nm phosphorus.
  • the phosphorus may be in the form of a phosphate salt.
  • the proportion of phosphorus can be determined by X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • the term "atomic%" is understood to mean the percentage of a defined amount of atoms relative to a defined reference quantity of atoms.
  • the phosphor remaining after the electrode has dried does not affect the function and cycling stability of the electrode.
  • the electrode is
  • cathode for the purposes of the present invention, the electrode which receives electrons when connected to a consumer.
  • the cathode is thus in this case the "positive electrode”.
  • the proportion of lithium-containing active material based on the total weight of the electrode material can be in the range of> 50 wt .-% to ⁇ 99 wt .-%, preferably in the range of> 60 wt .-% to ⁇ 95 wt .-%, preferably in Range of> 85 wt .-% to ⁇ 90 wt .-% are.
  • Total weight of the electrode material may range from> 0 wt .-% to ⁇ 50 wt .-%, preferably in the range of> 1 wt .-% to ⁇ 15 wt .-%, preferably in the range of> 3 wt .-% to ⁇ 10% by weight.
  • a lithium-based energy storage preferably a lithium battery, lithium-ion battery, a lithium-ion battery, lithium-polymer battery or lithium-ion capacitor, in particular containing lithium-ion battery an electrode according to the invention or produced according to the invention.
  • energy storage in the context of the present invention comprises primary and secondary electrochemical energy storage devices, ie batteries (primary storage) and accumulators (secondary storage). In general
  • lithium-ion battery is used synonymously with lithium-ion battery.
  • lithium-ion battery in the present case also refer to a “lithium-ion battery”.
  • preferred lithium-based energy storage devices are selected from a lithium accumulator, a lithium ion accumulator or a lithium polymer accumulator.
  • the energy store is preferably a lithium-ion battery or a lithium-ion battery.
  • Counterelectrodes can be used in lithium-based energy stores, for example, anodes based on materials such as graphite, lithium or lithium titanate.
  • Another object of the invention relates to the use of phosphoric acid in an aqueous dispersion comprising a lithium-containing active material in the preparation of an electrode for a lithium-based energy storage to prevent the corrosion of an aluminum current collector, in particular in the range of> 0.025 mM to ⁇ 0 , 5 mM phosphoric acid.
  • an aqueous dispersion also makes it possible to dispense with toxic and expensive organic solvents such as N-methylpyrrolidone.
  • phosphoric acid used.
  • Figure 1 shows the specific capacity of composite electrodes containing
  • FIG. 2 shows the binding energies of X-ray photoelectron spectroscopy (XPS) measurements of the phosphor of Li [Nii / 3Mni / 3Coi / 3] O 2 (NMC), which was mixed with 0.14 mM phosphoric acid in aqueous dispersion and dried (1 PA), and a comparative sample (0) without added acid.
  • XPS X-ray photoelectron spectroscopy
  • Figure 3 shows the Zyklmaschines a lithium-ion full cell with water-based
  • the charge and discharge capacity (left ordinate axis) and efficiency (right ordinate axis) are plotted against the number of charge / discharge cycles.
  • NMC Li [Nii / 3 Mni / 3 Coi / 3] O 2
  • Zyklisier NMC-based electrodes were initially prepared three aqueous solutions as the basis of the dispersions. For this purpose, solutions of 0.1 mM
  • Formic acid (Sigma Aldrich) or 0.1 mM phosphoric acid (Sigma Aldrich) in 7 ml of deionized water.
  • the control was a batch of 7 ml of deionized water.
  • 0.15 g of CMC was added to each of these aqueous solvents, and stirred for three hours at room temperature (20 ⁇ 2 ° C) with a magnetic stirrer to dissolve the binder. Subsequently, in each case 0.21 g Super C 45 carbon was added and the Mixtures dispersed for three hours with a magnetic stirrer.
  • the slurries thus obtained were each applied with a doctor blade having a wet layer thickness of 150 ⁇ m to aluminum foil (thickness 20 ⁇ m, purity> 99.9%, Evonik).
  • the coated films were then immediately dried in an oven (Binder) for one hour at 80 ° C. Subsequently, round electrodes having an area of 1.13 cm 2 were punched out and pressed for 15 seconds with 10 tons cm - " 2 to remove the
  • the electrodes were dried at 180 ° C under vacuum for another 12 hours.
  • the average surface charge of the electrodes was in each case 3.5 mg cm -1 .
  • the area charge was determined by weighing the pure foil and the punched-out electrodes.
  • composition of the dried electrodes was 88% by weight of NMC, 7% by weight of Super C 45 carbon and 5% by weight of CMC, based on the total weight of the
  • the electrochemical investigation of the electrodes prepared according to Example 1 was carried out in so-called pouch bag cells with lithium metal foil (Rockwood Lithium, 50 ⁇ ) as a counter electrode.
  • the cell was assembled in a drying room at 20 ° C.
  • the electrolyte used was a 1 M solution of LiPF 6 (Sigma Aldrich, battery grade) in a 1: 1 by weight mixture of ethylene carbonate and dimethyl carbonate (UBE, Japan, battery grade).
  • the separator used was a sheet of Asahi 718 (Asahi Kasei Chemicals).
  • Constant current electrochemical measurements were performed on a Maccor 4300 battery test system at 20 ° C ⁇ 1 ° C.
  • the cyclization of the NMC half-cells was carried out in a potential range of 3.0 V to 4.3 V versus Li / Li + .
  • a C-rate of IC corresponds to an applied specific current of 161 mAh g -1 . Since lithium foil was used as the counter electrode, the stated voltages refer to the Li / Li + reference.
  • FIG. 1 shows the galvanostatic charge / discharge tests of the NMC composite electrodes produced according to Example 1 from aqueous dispersion without addition of acid or with the addition of 0.1 mM formic acid or 0.1 mM phosphoric acid at a cathodic and anodic cut-off potential of 3 , 0 V and 4.3 V versus Li / Li + at an applied current density corresponding to a charge rate of 0.1 C in the first two cycles and IC in the following cycles.
  • all NMC-based electrodes for the first discharge showed an identical specific capacitance of about 152.5 ⁇ 0.5 mAh g -1 at 0.1 C. Further, it can be seen that as C increases Rates (IC) the
  • Table 1 clearly shows the superiority of the specific capacity of the electrode produced according to the invention from aqueous dispersion with 0.1 mM phosphoric acid.
  • Table 1 clearly shows the superiority of the specific capacity of the electrode produced according to the invention from aqueous dispersion with 0.1 mM phosphoric acid.
  • Electrodes prepared according to Example 1 from aqueous dispersion with the addition of 0.1 mM phosphoric acid and for comparison without addition of acid were used to obtain the
  • the electrode composite was replaced in each case by the aluminum foil used as a current collector.
  • the electrode composite was in each case using a so-called adhesive carbon tapes, a carbon-based adhesive film, separated from the current collector.
  • Lithium and carbon were not detected because of the low molecular weight.
  • Table 2 in the NMC electrode prepared using 0.1 mM phosphoric acid, traces of phosphorus could be detected in the electrode material. However, no aluminum was detected in the electrode according to the invention.
  • Table 3 it can be seen from Table 3 that the comparative electrode prepared from aqueous dispersion without addition of acid significant shares of Aluminum. This shows that the aluminum of the current collector of the electrode according to the invention did not corrode, while the aluminum detected in the reference electrode is attributed to corrosion of the current collector.
  • Table 4 shows the portions of cobalt, nickel and manganese detected in each case in the liquid phase:
  • Table 5 shows the absolute amounts of phosphoric acid solution added and, as a result, of (pure) H 3 PO 4 and its molar amount:
  • Table 5 illustrates that addition of more than 0.4 mM phosphoric acid only slightly dissolves ions from the cathode material.
  • An addition in the range of about 0.1 to 0.3 mM phosphoric acid thus shows a particularly good combination of a better specific capacity of the electrode prepared from an aqueous dispersion and prevention of corrosion of the aluminum current collector, while the cathode material, in contrast to an addition of Formic acid is hardly attacked.
  • the solid phases of the sample “1 PA” and the control "Blank 0" of Example 4 were investigated.
  • the sample “1 PA” was prepared as described in Example 4 by adding 2.64 g of NMC (Li [Nii / 3Mni / 3Coi / 3] 0 2 , Toda, average particle size 10 ⁇ ) were dispersed in 6 ml of demineralized water and then 0.0423 g of an aqueous 4 M solution of phosphoric acid were added. To the blank 0 control, no phosphoric acid was added. The mixtures were then dispersed for a further two hours by means of a magnetic stirrer and the liquid phases decanted. For the X-ray photoelectron spectroscopic examination, the separated solid phases were used and dried analogously to the electrode representation at 180 ° C for 12 hours under vacuum. The samples thus obtained were then by means of
  • XPS X-ray photoelectron spectroscopy
  • KRATOS Axis Ultra HAS spectroscope
  • the examined sample area was about 300 ⁇ 700 mm.
  • the detected layer thickness at the surface of the examined particles was regularly about 1 nm to 10 nm.
  • Table 6 shows the fractions detected in the solid phase in atomic% of cobalt, nickel, manganese and phosphorus, based on the total number of atoms of the investigated layer of the active material particles of a thickness of about 1 nm to 10 nm were:
  • FIG. 2 shows in each case the binding energy for the measurements of the phosphor of the sample, 1 PA 'and the comparative sample, blank 0'.
  • the presence of phosphorus on the particle surface in the sample '1 PA' can be clearly recognized from FIG.
  • Comparative sample 0 'showed no evidence of the presence of phosphorus. Based on the determined binding energy, it was phosphorus in the form of a
  • the active material at the surface of the particles in a layer thickness in the range of> 1 nm to ⁇ 10 nm about 1.85 atomic% of phosphorus, based on the total sum of the atoms of
  • NMC NMC
  • CMC Sodium carboxymethylcellulose
  • TIMCAL conductive carbon
  • CMC was first dissolved in deionized water at room temperature (20 ⁇ 2 ° C.) by means of a magnetic stirrer.
  • NMC-based cathode phosphoric acid (Sigma Aldrich) and NMC were added in a weight ratio of 1 to 100 to the CMC solution.
  • Super C45 carbon was added and the resulting mixture was dispersed for three hours with a magnetic stirrer.
  • the mixture was then dispersed at 5000 rpm for 10 minutes with a high-speed stirrer (Dremel® 4000).
  • SLP 30 graphite was added to the CMC solution.
  • Super C45 carbon was added and the resulting Mixture dispersed for three hours with a magnetic stirrer and then dispersed at 5000 rpm for 10 minutes with a high speed stirrer (Dremel® 4000).
  • the resulting coatings of the cathode and anode materials were each applied with a doctor blade to aluminum foil (cathode, thickness 20 ⁇ m, purity> 99.9%) or copper foil (anode, 10 ⁇ m). Subsequently, the coated films were immediately pre-dried for two hours at 80 ° C in a drying oven. Subsequently, electrodes having an area of 16 (4 ⁇ 4) cm were predried
  • the composition of the dried composite cathode was 88 wt% NMC, 7 wt% Super C 45 carbon and 5 wt% CMC, and the dried composite anode 90 wt% NMC, 5 wt%.
  • Super C 45 carbon and 5 wt .-% CMC each based on the total weight of the electrode material (without current collector).
  • the full cell was fabricated in a so-called pouch bag configuration using aluminum and nickel current collectors to connect the cathodic NMC electrode and the anode.
  • a commercially available single-layer polyethylene membrane (Asahi Kasei Chemicals, Hipore SV718) was used.
  • the cell was assembled in a dry room (relative humidity ⁇ 0.1%) at 20 ⁇ 1 ° C.
  • the electrolyte used was a commercially available 1 M solution of LiPF 6 in a 1: 1 mixture, by weight, of ethylene carbonate and dimethyl carbonate (1: 1 w / w) and 1% vinylene carbonate (1,3-dioxole-2). on, VC).
  • the electrochemical characterization of the whole cell was performed on a MACCOR 4300 battery test system at room temperature (20 ° C ⁇ 1 ° C). The investigation of the full cell was carried out in a potential range of 2.8 V to 4.2 V (cut-off potentials) against Li / Li + .
  • the cyclization protocol included galvanostatic (CC) discharge and galvanostatic potentiostatic (CCCV) charging.
  • FIG. 3 shows the cyclization behavior of a full cell with a cathodic cell
  • Discharge capacity 145.6 mAh g "1 corresponding to a coulombic efficiency of 99.7%
  • the capacity was stable for more than 300 cycles
  • the cell still gave a specific capacity of 122, 6 mAh g "1 (NMC) at IC, corresponding to a very substantial capacity retention of nearly 97.5% compared to 125.7 mAh g " 1 in the seventh cycle (IC) .
  • the average Coulomb efficiency was higher than 99.99% Values are exceptionally high for a laboratory-scale, water-only lithium-ion battery.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
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  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un procédé permettant de produire une électrode pour un accumulateur d'énergie à base de lithium. Ce procédé consiste à appliquer une dispersion aqueuse comportant un matériau actif contenant du lithium sur un collecteur de courant, un acide phosphorique étant ajouté à la dispersion aqueuse dans la plage allant de > 0,025 mM à < 0,5 mM.
PCT/EP2014/072847 2013-10-28 2014-10-24 Procédé permettant de produire une électrode pour une batterie lithium-ion WO2015062985A1 (fr)

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DE201310111826 DE102013111826A1 (de) 2013-10-28 2013-10-28 Verfahren zur Herstellung einer Elektrode für eine Lithium-Ionen-Batterie

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