WO2024059912A1 - Matériau d'électrode - Google Patents

Matériau d'électrode Download PDF

Info

Publication number
WO2024059912A1
WO2024059912A1 PCT/AU2023/050920 AU2023050920W WO2024059912A1 WO 2024059912 A1 WO2024059912 A1 WO 2024059912A1 AU 2023050920 W AU2023050920 W AU 2023050920W WO 2024059912 A1 WO2024059912 A1 WO 2024059912A1
Authority
WO
WIPO (PCT)
Prior art keywords
transition metal
electrode
electrode material
acid
metal salt
Prior art date
Application number
PCT/AU2023/050920
Other languages
English (en)
Inventor
Neeraj Sharma
Matthew James TEUSNER
Jitendra MATA
Original Assignee
Newsouth Innovations Pty Limited
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 AU2022902762A external-priority patent/AU2022902762A0/en
Application filed by Newsouth Innovations Pty Limited filed Critical Newsouth Innovations Pty Limited
Publication of WO2024059912A1 publication Critical patent/WO2024059912A1/fr

Links

Classifications

    • 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
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/26—Processes of manufacture
    • H01M4/28—Precipitating active material on the carrier
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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

Definitions

  • the present invention relates to electrode materials for alkali metal-ion batteries.
  • electrodes comprising the electrode materials of the invention are provided, and methods for preparing such electrodes.
  • alkali metal-ion batteries comprising electrode materials of the invention are provided.
  • the invention is not limited to this particular field of use. BACKGROUND OF THE INVENTION [0002] The following discussion of the prior art is provided to place the invention in an appropriate technical context and enable the advantages of it to be more fully understood.
  • High capacity alkali metal-ion batteries are in high demand for electric vehicle and energy storage systems. However, the capacity of these batteries is constrained by the traditional electrodes used in them. For example, for lithium-ion batteries with traditional graphite anodes, the theoretical specific capacity is only 372 mAh/g.
  • high capacity electrode materials have been investigated. These materials include silicon, tin, transition metal oxides, conductive polymers, sodium carboxylate-derived materials and organic materials. However, these materials do not necessarily exhibit desired capacity and cycling behaviour.
  • anthraquinone has a reversible capacity of about 250 mAh/g in the first cycle, and the capacity drops to 30 mAh/g after 100 cycles.
  • traditional alkali metal-ion batteries use solvents during manufacture, which are toxic, expensive and hard to dispose of in industrial quantities.
  • One example of such a solvent is N-methyl- 2-pyrrolidone (NMP).
  • NMP N-methyl- 2-pyrrolidone
  • a preferred embodiment of the present invention is to provide high capacity electrode materials for alkali metal-ion batteries.
  • a further preferred embodiment of the present invention is to provide manufacturing methods that avoid the use of toxic and expensive solvents, and instead utilise low cost and environmentally friendly solvents.
  • an electrode material for an alkali metal-ion battery comprising: a conductive material; and a water soluble transition metal salt of a carboxylic acid.
  • the performance of alkali metal-ion batteries largely depends on the electrode materials used.
  • the present invention provides an electrode material that yields improved performance over that of conventional lithium ion batteries. It has surprisingly been found that the electrode materials of the present invention provide significantly larger specific capacities than traditional electrode materials (such as LiFePO4, LiCoO2 and graphite).
  • the electrode materials of the invention can be prepared in a water-based solvent system. This is a significant advance in the art, as it avoids the use of traditional toxic solvents such as NMP. Yet further still, it has surprisingly been found that the specific capacity of batteries comprising certain electrode materials of the invention stabilise within relatively few charging/discharging cycles, as will be discussed further below.
  • the electrode material of the present invention uses simple transition metal salts that are easy to synthesise, non-toxic and relatively inexpensive. Therefore, alkali metal-ion batteries comprising such electrode materials are environmentally friendly and can be manufactured relatively easily at low cost.
  • the transition metal salt comprises a row 1 transition metal selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel and zinc, or any combination thereof.
  • the transition metal salt comprises a row 2 transition metal selected from the group consisting of zirconium, niobium, molybdenum and tungsten, or any combination thereof.
  • the transition metal salt comprises transition metals selected from both row 1 and row 2.
  • the transition metal salt comprises a transition metal selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, zinc, niobium, tungsten, molybdenum and zirconium, or any combination thereof.
  • the transition metal salt is not a copper salt.
  • the electrode material comprises a water soluble transition metal salt of a carboxylic acid with the proviso that the transition metal is not copper.
  • the carboxylic acid comprises 1, 2, 3, 4, 5, or 6 carboxylic acid groups.
  • the carboxylic acid comprises 1 carboxylic acid group. [0016] In a preferred embodiment of the invention the carboxylic acid comprises at least two carboxylic acid groups. [0017] In another preferred embodiment of the invention, the carboxylic acid has a molecular weight of less than 500 g/mol.
  • the carboxylic acid is selected from the group consisting of malic acid, maleic acid, tartaric acid, tartronic acid, succinic acid, aspartic acid, malonic acid, methylmalonic acid, ethylmalonic acid, glutamic acid, methylsuccinic acid, ethylsuccinic acid, itaconic acid, citric acid and glutaric acid.
  • the carboxylic acid is selected from the group consisting of tartaric acid, malic acid, maleic acid, citric acid and tartronic acid.
  • the conductive material has a conductivity from about 10 2 S/m to about 5x10 2 S/m, from about 5x10 2 S/m to 10 3 S/m, from about 10 3 S/m to about 5x10 3 S/m, from about 5x10 3 S/m to about 10 4 S/m, from about 10 4 S/m to about 5x10 4 S/m, from about 5x10 4 S/m to about 10 5 S/m, from about 10 5 S/m to about 5x10 5 S/m, or from about 5x10 5 S/m to about 10 6 S/m.
  • the conductive material is a conductive carbon material selected from the group consisting of activated carbon, carbon black, expanded graphite, graphite, shredded carbon felt, carbon nanotubes, carbon fibre, and vitreous carbon.
  • the conductive material has a particle size of between about 0.001 ⁇ m to about 0.005 ⁇ m, or about 0.005 ⁇ m to about 0.01 ⁇ m, or about 0.01 ⁇ m to about 0.05 ⁇ m, or about 0.05 ⁇ m to about 0.1 ⁇ m, or about 0.1 ⁇ m to about 0.2 ⁇ m, or about 0.2 ⁇ m to about 0.3 ⁇ m, or about 0.3 ⁇ m to about 0.4 ⁇ m, or about 0.4 ⁇ m to about 0.5 ⁇ m, or about 0.5 ⁇ m to about 0.6 ⁇ m, or about 0.6 ⁇ m to about 0.7 ⁇ m, or about 0.7 ⁇ m to about 0.8 ⁇ m, or about 0.8 ⁇ m to about 0.9 ⁇ m, or about 0.9 ⁇ m to about 1 ⁇ m, or about 1 ⁇ m to about 5 ⁇ m, or about 5 ⁇ m to about 10 ⁇ m, or about 10 ⁇ m to about 50 ⁇
  • the conductive material has a linear (acicular) morphology, a spheroidal morphology, an ellipsoidal morphology, a branched morphology. In some embodiments, mixtures of conductive materials are provided that have different morphologies, for example, spherical and acicular. Binders [0024]
  • the electrode material further comprises a binder. It will be appreciated by the skilled person that the binder preferably promotes cohesion of the conductive material and the water soluble transition metal salt of a carboxylic acid and/or promotes adhesion of an electrode material comprising said binder to the surface of a current collector (discussed below).
  • the transition metal salt and the conductive material are homogeneously dispersed throughout the binder.
  • the use of a binder is advantageous as it enables a relatively uniform slurry of the conductive material and the transition metal salt to be prepared and applied to the surface of the current collector to form an electrode (as discussed below) with relatively high specific capacity.
  • the binder may be selected to improve the overall stability and chemical resistance of the electrode material formed from the transition metal salt and the conductive material, for example improved corrosion resistance to the corrosive electrolyte typically used in an alkali metal-ion battery.
  • the use of a binder can assist in providing overall thermal resistance to the formed electrode material.
  • the binder is a non-halogenated binder.
  • the non-halogenated binder is soluble in water, promotes desirable adhesion, good wettability, homogeneous material distribution, and has a strong chemical stability in an alkali metal-ion battery with little or no decomposition over a long-cycle life.
  • the binder has an electrical conductivity of from about 10 2 S/m to about 5x10 2 S/m, from about 5x10 2 S/m to about 10 3 S/m, from about 10 3 S/m to about 5x10 3 S/m, from about 5x10 3 S/m to about 10 4 S/m, from about 10 4 S/m to about 5x10 4 S/m, from about 5x10 4 S/m to about 10 5 S/m, from about 10 5 S/m to about 5x10 5 S/m, or from about 5x10 5 S/m to about 10 6 S/m.
  • the binder is non-toxic.
  • the binder is environmentally friendly.
  • the binder is readily dispersible in the NMP- or water-based solvent system.
  • the binder has good thermal resistance such that it is resistant to degradation in standard battery operation temperature, for example, between 20 to 60 °C.
  • Preferred examples of non-halogenated binders are selected from the group consisting of: carboxymethylcellulose (CMC), styrene butadiene rubber (SBR), and sodium alginate, or any combination thereof.
  • the binder is a halogenated binder.
  • halogenated binders are selected from the group consisting of: polytetrafluoroethylene (PTFE), polyvinylidene difluoride-co hexafluoropropylene (PVDF-HFP), and polyvinylidene difluoride (PVDF), or any combination thereof.
  • PTFE polytetrafluoroethylene
  • PVDF-HFP polyvinylidene difluoride-co hexafluoropropylene
  • PVDF polyvinylidene difluoride
  • the electrode material comprises 1 to 99% (w/w) of the conductive material, for example about 1% to about 2%, or about 2% to about 3%, or about 3% to about 4%, or about 4% to about 5%, or about 5% to about 6%, or about 6% to about 7%, or about 7% to about 8%, or about 8% to about 9%, or about 9% to about 10%, or about 10% to about 15%, or about 15% to about 20%, or about 20% to about 25%, or about 25% to about 30%, or about 30% to about 35%, or about 35% to about 40%, or about 40% to about 45%, or about 45% to about 50%, or about 50% to about 55%, or about 55% to about 60%, or about 60% to about 65%, or about 65% to about 70%, or about 70% to about 75%, or about 75% to about 80%, or about 80% to about 85%, or about 85% to about 90%, or about 90% to about 95%, or about 95% to
  • the electrode material comprises 40% (w/w) of the conductive material, 10% (w/w) of the binder, and 50% (w/w) of the transition metal salt.
  • the electrode material comprises 2.5% (w/w) of the conductive material, 2.5% (w/w) of the binder, and 95% (w/w) of the transition metal salt.
  • the binder is a combination of CMC and SBR, in a ratio of from about 1:20 to about 20:1, or from about 1:15 to about 15:1, or from about 1:10 to about 10:1, or from about 1:5 to about 5:1, or from about 1:2 to about 2:1, or from about 1:1.2 to 1.2:1.
  • the ratio may be, for example, about 1:1.5, 1:2, 1:5, 1:10, 1:15, 1:20, 1.5:1, 2:1, 5:1, 10:1, 15:1, or 20:1.
  • the binder consists of 40% (w/w) of CMC and 60% (w/w) of SBR.
  • the conductive material is in the form of particles, wherein the particles are at least partially coated with the transition metal salt.
  • an electrode for an alkali metal-ion battery comprising: a current collector; and an electrode material of the first aspect coated on a surface of the current collector.
  • Current collector In one embodiment of the invention, a current collector is provided in the form of a conductive substrate.
  • the conductive substrate has a conductivity of from about 10 2 S/m to about 5x10 2 S/m, from about 5x10 2 S/m to about 10 3 S/m, from about 10 3 S/m to about 5x10 3 S/m, from about 5x10 3 S/m to about 10 4 S/m, from about 10 4 S/m to about 5x10 4 S/m, from about 5x10 4 S/m to about 10 5 S/m, from about 10 5 S/m to about 5x10 5 S/m, or from about 5x10 5 S/m to about 10 6 S/m.
  • the conductive substrate is preferably corrosion resistant to the potentially corrosive electrolyte in an alkali metal ion battery and is of a suitable size and thickness for the battery.
  • the conductive substrate may have a thickness of about 0.01 cm, about 0.05 cm, about 0.1 cm, about 0.2 cm, about 0.3 cm, about 0.4 cm, about 0.5 cm, about 0.6 cm, about 0.7 cm, about 0.8 cm, about 0.9 cm, about 1.0 cm, about 2.0 cm, about 3.0 cm, about 4.0 cm, or about 5.0 cm.
  • the conductive substrate may have an cross-sectional area of between about 0.01 cm 2 to about 0.05 cm 2 , or about 0.05 cm 2 to about 0.1 cm 2 , or about 0.1 cm 2 to about 0.5 cm 2 , or about 0.5 cm 2 to about 1 cm 2 , or about 1 cm 2 to about 5 cm 2 , or about 5 cm 2 to about 10 cm 2 , or about 10 cm 2 to about 20 cm 2 , or about 20 cm 2 to about 30 cm 2 , or about 30 cm 2 to about 40 cm 2 , or about 40 cm 2 to about 50 cm 2 , or about 50 cm 2 to about 60 cm 2 , or about 60 cm 2 to about 70 cm 2 , or about 70 cm 2 to about 80 cm 2 , or about 80 cm 2 to about 90 cm 2 , or about 90 cm 2 to about 100 cm 2 , or about 100 cm 2 to about 200 cm 2 , or about 200 cm 2 to about 300 cm 2 , or about 300 cm 2 to about 400 cm 2 , or about 400 cm 2 to about 500 cm 2 , or about 500 cm 2
  • the conductive substrate may be circular, rectangular, trapezoidal, ellipsoidal or square in shape.
  • the current collector is a metal foil.
  • the metal foil comprises a metal selected from the group consisting of copper, aluminium, stainless steel, titanium and nickel, or any combination thereof.
  • Electrode material surface coating [0042] In an embodiment of the invention, the electrode material is coated on a surface of the current collector at a thickness of about 10 ⁇ m to about 1000 ⁇ m.
  • the thickness is from about 10 ⁇ m to about 20 ⁇ m, from about 20 ⁇ m to about 30 ⁇ m, from about 30 ⁇ m to about 40 ⁇ m, from about 40 ⁇ m to about 50 ⁇ m, from about 50 ⁇ m to about 60 ⁇ m, from about 60 ⁇ m to about 70 ⁇ m, from about 70 ⁇ m to about 80 ⁇ m, from about 80 ⁇ m to about 90 ⁇ m, from about 90 ⁇ m to about 100 ⁇ m, from about 100 ⁇ m to about 150 ⁇ m, from about 150 ⁇ m to about 200 ⁇ m, from about 200 ⁇ m to about 250 ⁇ m, from about 250 ⁇ m to about 300 ⁇ m, from about 300 ⁇ m to about 350 ⁇ m, from about 350 ⁇ m to about 400 ⁇ m, from about 400 ⁇ m to about 450 ⁇ m, from about 450 ⁇ m to about 500 ⁇ m, from about 500 ⁇ m to about 550 ⁇ m, from about 550 ⁇ m to about 600 ⁇
  • the electrode material is coated on the surface of the current collector at a thickness of about 100 ⁇ m.
  • a water soluble transition metal salt of a carboxylic acid in an electrode material for an alkali metal-ion battery.
  • a water soluble transition metal salt of a carboxylic acid for use or when used in an electrode material for an alkali metal-ion battery.
  • a fifth aspect of the present invention there is provided use of the electrode material according to the first aspect of the invention in an alkali metal- ion battery.
  • the electrode material according to the first aspect of the invention for use or when used in an alkali metal-ion battery.
  • a seventh aspect of the present invention there is provided use of the electrode according to the second aspect of the invention in an alkali metal-ion battery.
  • the electrode according to the second aspect of the invention for use or when used in an alkali metal-ion battery.
  • the alkali metal-ion battery is a lithium- ion battery, a sodium-ion battery, or a potassium-ion battery.
  • a ninth aspect of the present invention there is provided a method of preparing an electrode according to the second aspect of the invention for an alkali metal-ion battery, the method comprising the steps of: (i) preparing a slurry by mixing a conductive material and a water soluble transition metal salt of a carboxylic acid, and optionally a binder, in a solvent, (ii) coating the slurry onto a current collector, and (iii) evaporating the solvent to form a substantially dried coating of the conductive material, water soluble transition metal salt of a carboxylic acid, and binder.
  • the solvent is water, methanol, ethanol, isopropanol, butanol, or a combination thereof.
  • the solvent is water.
  • the solvent is NMP.
  • the electrode is prepared by compressing a mixture of the conductive material and the water soluble transition metal salt, and optionally a binder, thereby forming a compressed layer that can act as an electrode by itself.
  • the electrode is prepared by pressing a mixture of the conductive material and the water soluble transition metal salt, and optionally a binder onto the current collector, thereby forming an electrode without using a solvent.
  • the water soluble transition metal salt is obtained by reacting the transition metal or a salt thereof with carboxylic acid, preferably by: (a) mixing a powder of the transition metal or the transition metal salt with the carboxylic acid in a solvent capable of oxidatively dissolving the transition metal to form a precipitate of the transition metal salt of the carboxylic acid, and (b) collecting the transition metal salt of the carboxylic acid.
  • the solvent capable of oxidatively dissolving the transition metal is water, methanol, ethanol, isopropanol, butanol, NMP, or any combination thereof.
  • the solvent is a mixture of NMP and water in a ratio of from about 1:10 to about 10:1, or from about 1:7 to about 7:1, or from about 1:5 to about 5:1, or from about 1:3 to about 3:1. The ratio may be, for example, about 1:1, 1:2, 1:5, 1:10, 10:1, 5:1, or 2:1.
  • an alkali metal-ion battery comprising the electrode of the second aspect of the invention.
  • the battery has a specific capacity of at least 500 mAh/g after less than 30 charging/discharging cycles.
  • the specific capacity is between about 500 mAh/g to about 550 mAh/g, or between about 550 mAh/g to about 600 mAh/g, or between about 600 mAh/g to about 650 mAh/g, or between about 650 mAh/g to about 700 mAh/g, or between about 700 mAh/g to about 750 mAh/g, or between about 750 mAh/g to about 800 mAh/g.
  • the number of charging/discharging cycles is less than 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11 or 10.
  • FIG. 1 shows a comparison of X-ray powder diffraction (XRD) patterns for a series of water soluble transition metal salts of particular carboxylic acids for use in preparing electrode materials, electrodes prepared from these electrode materials under different solvent systems, and where applicable, with reference to XRD patterns of the native transition metal carboxylate obtained from the literature: (a) copper malate (Cu MAL), electrodes prepared with copper malate (Cu MAL) in NMP and water based solvents; (b) iron (II) tartrate (Fe(II) TAR), electrode prepared with iron (II) tartrate (Fe(II) TAR) in NMP- and water-based solvents, with reference
  • Figure 2 shows scanning electron microscopy (SEM) images of the surface of each of a series of electrodes prepared from the electrode materials identified in Figure 1: (a) electrode prepared from an electrode material comprising copper malate (Cu MAL) in an NMP based solvent; (b) electrode prepared from an electrode material comprising copper malate (Cu MAL) in a water-based solvent; (c) electrode prepared from an electrode material comprising iron (II) tartrate (Fe(II) TAR) in an NMP-based solvent; (d) electrode prepared from an electrode material comprising iron (II) tartrate (Fe(II) TAR) in a water based solvent; (e) electrode prepared from an electrode material comprising iron (III) tartrate (Fe(III) TAR) in an NMP based solvent; (f) electrode prepared from an electrode material comprising iron (III) tartrate (Fe(III) TAR) in a water-based solvent; (g) electrode prepared from an electrode material comprising iron malate (Fe MAL) in an NMP
  • FIG. 3 shows plots of specific capacity (mAh/g) versus number of charging/discharging cycles for a series of batteries comprising the following electrodes: (a) an electrode prepared from an electrode material comprising a 7:2:1 ratio of one of the following transition metal salts Cu CIT, Cu TAR and Fe(II) TAR, with conductive carbon and CMC in a water-based solvent, electrolyte comprising a 1:1:1 ratio of DMC, EMC and EC with 5% (v/v) fluoroethylene carbonate (FEC) additive, cycling at 100mA/g; (b) an electrode from an electrode comprising 5:4:1 of one of the following transition metal salts Cu CIT, Cu TAR, Fe (II) TAR, with conductive carbon and PVDF in an NMP-based solvent, electrolyte comprising a 1:1 ratio of DMC and EC, cycling at 50mA/g; (c) an electrode from an electrode material comprising 5:4:1 of one of the following transition metal salts Fe
  • compositions, mixture, process or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.
  • the transitional phrase "consisting of” excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consisting of" appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
  • transitional phrase “consisting essentially of” is used to define a composition, process or method that includes materials, steps, features, components, or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention.
  • the term “consisting essentially of” occupies a middle ground between “comprising” and “consisting of”.
  • wt.% refers to the weight of a particular component relative to total weight of the referenced composition.
  • wt.% refers to the weight of a particular component relative to total weight of the referenced composition.
  • the terms “preferred” and “preferably” refer to embodiments of the invention that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.
  • alkali metal-ion battery refers to a type of rechargeable battery in which alkali metal ions move from the negative electrode through an electrolyte to the positive electrode during discharge and back when charging.
  • electrode material refers to the material that is usually coated on a surface of a current collector to form an electrode. Alternatively, the electrode material itself may be compressed to form an electrode.
  • water soluble transition metal salt of a carboxylic acid refers to a chemical compound consisting of an ionic assembly of positively charged transition metal ions and negatively charged carboxylic acid group(s).
  • the compound has a water solubility of at least 0.1 g/dL.
  • the water solubility is between about 0.1 g/dL to about 0.5 g/dL, or about 0.5 g/dL to about 1 g/dL, or about 1 g/dL to about 2 g/dL, or about 2 g/dL to about 3 g/dL, or about 3 g/dL to about 4 g/dL, or about 4 g/dL to about 5 g/dL, or about 5 g/dL to about 6 g/dL, or about 6 g/dL to about 7 g/dL, or about 7 g/dL to about 8 g/dL, or about 8 g/dL to about 9 g/dL, or about 9 g/dL to about 10 g/dL, or about 10 g/dL to about 20 g/dL, or about 20 g/dL to about 30 g/dL, or about 30 g/dL to about 40 g/dL, or about 40 g/d
  • the term “specific capacity” refers to the total amount of electricity generated and/or stored due to electrochemical reactions in a battery in comparison to the weight of the active material and is expressed in ampere hours per gram (Ah/g).
  • the term “charging/discharging cycle” refers to the full discharge of a charged battery with subsequent recharge, or the full charge of an empty battery with subsequent recharge, at a specific current.
  • NMP N-methyl-2-pyrrolidone PTFE Polytetrafluoroethylene PVDF Polyvinylidene difluoride PVDF-HFP Polyvinylidene difluoride-co hexafluoropropylene CMC Carboxymethylcellulose SBR Styrene butadiene rubber XRD X-ray powder diffraction Cu TAR Copper tartrate Cu MAL Copper malate Cu MEC Copper maleate Cu CIT Copper citrate Fe (II) TAR Iron (ii) tartrate Fe (III) TAR Iron (iii) tartrate Fe MAL Iron malate Fe CIT Iron citrate Fe MEC Iron maleate Zn TAR Zinc tartrate Zn MAL Zinc malate Zn MEC Zinc maleate DMC Dimethyl carbonate EMC Ethyl methyl carbonate EC Ethylene carbonate FEC Fluoroethylene carbonate DETAILED DESCRIPTION [0083] The skilled addressee will understand that the invention
  • a wide range of water soluble salts of a transitional metal and a carboxylic acid are suitable in the electrode materials of the present invention.
  • the salts include copper tartrate hydrous (Cu 2 (C 4 H 4 O 6 ) 2 (H 2 O) 2 ⁇ xH 2 O), copper malate (C4H4CuO5), copper tartronate (C3H2CuO5), iron (II) citrate (C6H4Fe2O7), iron (II) tartrate (C4H4FeO6), iron (III) tartrate (C12H12Fe2O18), iron malate (C 4 H 4 FeO 5 ), iron maleate (C 4 H 2 FeO 4 ) and zinc malate (C 4 H 4 ZnO 5 ).
  • the conductive material is carbon black in powder form.
  • the electrode material also comprises a binder that binds the conductive material and the water soluble transition metal.
  • the binder consists of 40% (w/w) of carboxymethylcellulose (CMC) and 60% (w/w) of styrene butadiene rubber (SBR).
  • CMC carboxymethylcellulose
  • SBR styrene butadiene rubber
  • conductive carbon can be replaced with biomass waste derived conductive carbon, which significantly reduces cost of production and is more environmentally friendly.
  • the present invention provides a versatile platform for electrode material design to meet various capacity requirements.
  • the performance of the electrode material may be tuned by mixing different transition metals in a ratio based on their specific capacity and cycling performance (as shown in, for example, Figure 3), to meet specific requirements in battery performance.
  • the composition of the electrode material is flexible and can be designed based on the capacity requirement of a battery.
  • the electrode material may comprise about 95% (w/w) of the transitional metal salt, 2.5% (w/w) of the conductive material and 2.5% (w/w) of the binder, while a battery may be custom-designed to comprise an electrode comprising about 50% (w/w) of the transitional metal salt, 40% (w/w) of the conductive material and 10% (w/w) of the binder, to suit different capacity needs.
  • the present invention also relates to a method of preparing an electrode comprising the electrode material.
  • a slurry is prepared by mixing the water soluble transition metal salt of the carboxylic acid, the conductive material and/or the binder in a solvent, which is then applied onto a current collector followed by evaporating the solvent.
  • the solvent may be N-methyl-2-pyrrolidone (NMP)-based and/or water-based. It has been found that the electrode prepared with a water-based solvent system advantageously provides more homogeneous distribution of the transition metal salt in the conductive material, leading to a higher specific capacity.
  • the water soluble transition metal salts of a range of carboxylic acids can be prepared by mixing a powder of the transition metal with the carboxylic acid in a solvent capable of oxidatively dissolving the transition metal to form a precipitate of the transition metal salt.
  • Oxidative dissolution refers to a process of dissolving metals that involves simultaneously an oxidation process.
  • a common salt of the transition metal for example, iron (II) nitrate (Fe(NO3)2 may be used instead of the metal powder.
  • An alkali metal-ion battery comprising an electrode fabricated from electrode materials provides a higher specific capacity than a traditional alkali metal-ion battery materials.
  • a traditional lithium ion battery has a graphite electrode can produce a specific capacity of about 300mAh/g, while in specific embodiments of the present invention the battery has a specific capacity of at least 500mAh/g, or at least 600mAh/g, or at least 700mAh/g.
  • the specific capacity of the batteries fabricated from electrode materials prepared according to embodiments of present invention increase to the above values after charging/discharging cycles. Without being bound by theory, the inventors believe that the specific capacity increase with cycling can be accelerated through a more homogenous distribution of water-soluble transition metal salts in the electrode material as compared to the non-water-soluble transition metal salts.
  • the battery fabricated from electrode materials of the present invention may also be preconditioned by subjecting it to a number of charging/discharging cycles until a desired specific capacity is reached. The exact number of charging/discharging cycles depends on the transition metal salt and the composition of the electrode material.
  • the capacity of the battery fabricated from electrode materials of the present invention may be further increased by blending silicon and/or silicon oxides with the conductive material.
  • Metal powder for example iron powder
  • a carboxylic acid for example tartaric acid
  • the solution is then heated to about 75 to 80 o C, followed by stirring for at least 24 hours.
  • the precipitate formed is collected by vacuum filtration, washed with acetone and dried at 100 o C under vacuum.
  • Example 2 – Synthesis of an electrode A slurry is prepared by dissolving a 5:4:1 ratio of the transition metal salt of the carboxylic acid, conductive carbon black and binder in NMP or water.
  • the binder is a 2:3 mixture of CMC and SBR in water, or PVDF in NMP.
  • the mixture is magnetically stirred overnight, and the slurry is then spread onto a metal foil, for example an iron foil, acting as a current collector, at an approximately 100 ⁇ m thickness using a notch bar, resulting in an active material loading of about 0.8 – 1.0 mg/cm 2 .
  • the resulting electrode sheets are then dried overnight in a vacuum oven at 100 o C under dynamic vacuum.
  • Example 3 – XRD of various water soluble transition salts and electrodes prepared therewith [0099] The XRD patterns of synthesised copper malate (Cu MAL), iron (II) tartrate (Fe(II) TAR), iron (III) tartrate (Fe(III) TAR), iron malate (Fe MAL), iron maleate (Fe MEC), iron citrate (Fe CIT), zinc malate (Zn MAL), electrodes prepared with these salts in different solvent systems, and where applicable, with reference to the XRD pattern of the native transitional metal carboxylate obtained from the literature, are compared in Figure 1.
  • Example 4 SEM of electrodes prepared with various water soluble transition salts in different solvent systems
  • the SEM of electrodes prepared with copper tartrate hydrous (Cu TAR hydrous), copper malate (Cu MAL), iron (II) tartrate (Fe(II) TAR), iron (III) tartrate (Fe(III) TAR), iron malate (Fe MAL), iron maleate (Fe MEC) and zinc malate (Zn MAL) in NMP- and water-based solvents are shown in Figure 2.
  • the electrodes prepared in water-based solvent have an increased homogeneity of transition metal salt distribution through the electrode material compared with the electrode materials prepared in an NMP-based solvent.
  • Example 5 Synthesis of an alkali metal-ion battery
  • Electrode discs of 12 mm are punched from the electrode sheet (for example obtained in Example 2) and then dried for an hour at 70 ° C under vacuum to remove any residual moisture before being transferred into an argon-filled glovebox for assembly.
  • the discs are assembled into CR2032 coin batteries with a glass-fibre separator soaked in an electrolyte, and lithium used as the counter electrode.
  • the electrolyte used is 1 M LiPF6 in 1:1 ethylene carbonate (EC)/dimethyl carbonate (DMC).
  • FIG. 3 shows several plots of specific capacity (mAh/g) versus cycle number at different charging/discharging cycles for a series of batteries comprising electrode materials prepared from a range of transition metal salts of a carboxylic acid (for example, Cu CIT, Cu TAR, Cu MAL, Fe CIT, Fe (II) TAR, Zn MAL) in either an NMP- or water-based solvent system.
  • a carboxylic acid for example, Cu CIT, Cu TAR, Cu MAL, Fe CIT, Fe (II) TAR, Zn MAL
  • the plots in Figure 3 show that, the specific capacity of the battery generally increases with an increasing number of cycles before reaching a substantially steady state. These same plots also show that the specific capacity of the battery is largely affected by the composition of the electrode material used.
  • the battery fabricated from a copper citrate (Cu CIT) electrode material reaches a specific capacity at about 700 mAh/g after about 20 cycles before decreasing to a specific capacity of about 600 mAh/g at about 80 cycles.
  • the battery fabricated from a copper tartrate (Cu TAR) electrode material has a specific capacity that reaches about 600 mAh/g after a greater number of cycles. While the specific capacity of the battery fabricated from an iron (II) tartrate (Fe(II) TAR) electrode material is considerably lower than the specific capacities obtained for the other batteries in Figure 3(a), but reaches a steady state at about 400 mAh/g.
  • the specific capacity of batteries can be tuned with different compositions of the electrode material.
  • the battery fabricated from an iron (II) tartrate (Fe(II) TAR) electrode material reaches a specific capacity of about 800 mAh/g after about 15 cycles, which is a higher specific capacity than that achieved by the battery fabricated from the copper citrate (Cu CIT) electrode material, as shown in Figure 3(a).
  • batteries fabricated with electrodes comprising electrode materials prepared in a water-based solvent have a higher specific capacity than those with electrodes prepared in an NMP- based solvent ( Figure 3(b)), potentially due to the increased homogeneity of transition metal salt distribution in the water-based solvent system.
  • Figure 3(h) shows that a battery fabricated from an iron malate (Fe MAL) electrode material prepared in a water-based solvent has a substantially higher specific capacity than a battery fabricated from the same iron malate (Fe MAL) electrode material prepared in an NMP-based solvent.
  • Fe MAL iron malate
  • NMP-based solvent a battery fabricated from the same iron malate (Fe MAL) electrode material prepared in an NMP-based solvent.
  • Electrodes described in embodiments of the present invention herein provide a number of advantages, as follows: [0114] One advantage of the electrode materials of the present invention over traditional electrode materials is that a battery fabricated from these electrode materials provides a substantially higher specific capacity. For example, as illustrated in Figure 3(c), the specific capacity of a battery fabricated from an iron (II) tartrate (Fe(II) TAR) electrode material is about 800 mAh/g after about 15 cycles.
  • the electrode mateials of the present invention can be prepared in a water-based solvent system. This avoids the use of traditional solvents, such as NMP, which are toxic, expensive and difficult to dispose of. [0116] According to a still further advantage, it has been demonstrated that batteries fabricated with electrodes comprising those electrode materials of the present invention that are prepared in a water-based solvent system, have a higher specific capacity than those with electrodes comprising electrode materials that have been prepared in an NMP-based solvent system.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un matériau d'électrode pour une batterie métal alcalin-ion comprenant un matériau conducteur et un sel de métal de transition soluble dans l'eau d'un acide carboxylique. L'invention concerne également une électrode comprenant ledit matériau d'électrode, un procédé de préparation de ladite électrode et une batterie aux ions de métal alcalin comprenant ladite électrode.
PCT/AU2023/050920 2022-09-23 2023-09-22 Matériau d'électrode WO2024059912A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2022902762 2022-09-23
AU2022902762A AU2022902762A0 (en) 2022-09-23 Electrode material

Publications (1)

Publication Number Publication Date
WO2024059912A1 true WO2024059912A1 (fr) 2024-03-28

Family

ID=90453511

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2023/050920 WO2024059912A1 (fr) 2022-09-23 2023-09-22 Matériau d'électrode

Country Status (1)

Country Link
WO (1) WO2024059912A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07122298A (ja) * 1993-10-21 1995-05-12 Fuji Photo Film Co Ltd 非水二次電池の充放電方法
JPH0864245A (ja) * 1994-08-25 1996-03-08 Fuji Photo Film Co Ltd 非水電解質電池
US20140205909A1 (en) * 2011-08-23 2014-07-24 Nippon Shokubai Co., Ltd. Negative electrode mixture or gel electrolyte, and battery using said negative electrode mixture or said gel electrolyte
CN106207253A (zh) * 2016-09-13 2016-12-07 胡晓光 一种水溶液锂离子二次电池负极、电解液以及电池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07122298A (ja) * 1993-10-21 1995-05-12 Fuji Photo Film Co Ltd 非水二次電池の充放電方法
JPH0864245A (ja) * 1994-08-25 1996-03-08 Fuji Photo Film Co Ltd 非水電解質電池
US20140205909A1 (en) * 2011-08-23 2014-07-24 Nippon Shokubai Co., Ltd. Negative electrode mixture or gel electrolyte, and battery using said negative electrode mixture or said gel electrolyte
CN106207253A (zh) * 2016-09-13 2016-12-07 胡晓光 一种水溶液锂离子二次电池负极、电解液以及电池

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HAILONG FEI: "Metal dicarboxylates: new anode materials for lithium-ion batteries with good cycling performance", DALTON TRANSACTIONS, RSC - ROYAL SOCIETY OF CHEMISTRY, CAMBRIDGE, vol. 44, no. 21, 1 January 2015 (2015-01-01), Cambridge , pages 9909 - 9914, XP093153802, ISSN: 1477-9226, DOI: 10.1039/C5DT00500K *

Similar Documents

Publication Publication Date Title
EP3048659B1 (fr) Matériau stratifié à base d'oxydes et son procédé de préparation, pièce polaire, cellule secondaire et application associée
Moretti et al. Investigation of different binding agents for nanocrystalline anatase TiO2 anodes and its application in a novel, green lithium-ion battery
JP5391337B2 (ja) リチウムイオン二次電池用正極活物質粒子、その正極活物質粒子を用いた正極およびリチウムイオン二次電池
JP3992708B2 (ja) 非水二次電池の電極材料およびその製造方法、並びにそれを用いた非水二次電池
KR101785268B1 (ko) 음극 활물질, 이를 포함하는 리튬 전지 및 상기 음극 활물질의 제조방법
EP2629354B1 (fr) Batterie secondaire non aqueuse dotée d'un matériau actif à cathode mélangée
EP2940762B1 (fr) Matériau actif d'anode revêtu d'oxyde de potassium-manganèse pour batterie rechargeable au lithium et procédé pour sa fabrication
EP3117474B1 (fr) Cathode pour batteries au lithium
JP2017130359A (ja) 電極材料の製造方法及び蓄電装置の製造方法
KR101108189B1 (ko) 음극 활물질 및 이를 채용한 전극과 리튬 전지
KR101458676B1 (ko) 리튬이차전지용 양극 활물질, 이의 제조방법 및 이를 이용한 리튬이차전지
KR20180094747A (ko) 리튬 이차전지용 음극 활물질, 그 제조방법 및 리튬 이차전지용 음극 활물질을 포함하는 리튬 이차전지
WO2009148890A1 (fr) Électrodes négatives à base d'oxydes métalliques pour des piles électrochimiques lithium-ion et batteries
KR20120129816A (ko) 축전 디바이스 및 축전 디바이스용 양극
CN104620425A (zh) 锂离子二次电池用电极材料、该电极材料的制造方法、及锂离子二次电池
KR20130107926A (ko) 양극 활물질, 그 제조방법 및 이를 이용한 리튬 이차 전지
KR20180062237A (ko) 복합양극활물질, 이를 포함하는 양극 및 리튬전지
KR20160138960A (ko) 리튬이온 이차전지 전극용 바인더 조성물, 리튬이온 이차전지 전극용 슬러리 조성물, 리튬이온 이차전지용 전극, 및 리튬이온 이차전지
KR20140104268A (ko) 전지용 바인더, 이를 채용한 음극과 리튬전지
EP3691005A1 (fr) Liant pour électrode de batterie secondaire à électrolyte non aqueux, mélange d'électrode pour batterie secondaire à électrolyte non aqueux, électrode pour batterie secondaire à électrolyte non aqueux, batterie secondaire à électrolyte non aqueux, et appareil électrique
WO2015186325A1 (fr) Procédé de production d'un oxyde métallique composite au lithium
WO2024059912A1 (fr) Matériau d'électrode
US20230041792A1 (en) Binder for secondary batteries
KR101437886B1 (ko) 리튬이차전지용 캐쏘드 활물질 나노복합체, 그 제조방법 및 이를 포함하는 리튬이차전지
US11978906B2 (en) Binder for secondary battery

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23866736

Country of ref document: EP

Kind code of ref document: A1