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WO2025097293A1 - Cathode compositions containing piperazine derivatives - Google Patents

Cathode compositions containing piperazine derivatives Download PDF

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Publication number
WO2025097293A1
WO2025097293A1 PCT/CN2023/130144 CN2023130144W WO2025097293A1 WO 2025097293 A1 WO2025097293 A1 WO 2025097293A1 CN 2023130144 W CN2023130144 W CN 2023130144W WO 2025097293 A1 WO2025097293 A1 WO 2025097293A1
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Prior art keywords
cathode
cathode composition
component
composition
lithium
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PCT/CN2023/130144
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French (fr)
Inventor
Qinyuan GUI
Xue CHEN
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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Priority to PCT/CN2023/130144 priority Critical patent/WO2025097293A1/en
Priority to TW113137823A priority patent/TW202520525A/en
Publication of WO2025097293A1 publication Critical patent/WO2025097293A1/en
Pending legal-status Critical Current
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • 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

  • LFP lithium iron phosphate
  • NMP N-methyl-2-pyrrolidone
  • the LFP particles tend to aggregate, and this aggregation makes it difficult to disperse these particles in the solvent. Furthermore, LFP particles may also interact with the conductive agent and the binder to form an aggregation. Because of the aggregation, the viscosity of the cathode slurry increases dramatically. During the cathode manufacturing, the LFP slurry will be coated onto an aluminum foil. Subsequently, the NMP will evaporate, leaving only the active materials, binder and conductive agent on the foil surface. Regarding this process, the high viscosity of the LFP slurry will lead to two problems, a low coating rate and a prolonged evaporation rate, each as discussed below.
  • the high viscosity of the slurry will hinder the coating of the slurry on the foil, and thus decrease the manufacturing efficiency of the cathode. Furthermore, the high viscosity will increase the risk of generating defects on the electrode, which will significantly increase the amount of defective cathodes and reduce the manufacturing efficiency.
  • cathode compositions that help to prevent the aggregation of the LFP particles.
  • This reduction in aggregation will, in turn, reduce the viscosity of an LFP slurry.
  • the reduced viscosity will increase the coating rate on the metal foil, decrease the risk of generating defects on the cathode, and allow for an increase in the solid content of the slurry, which will decrease the evaporation time of the solvent.
  • the overall manufacturing efficiency will increase.
  • the cathode active material layer comprises multiple cathode active material particles and an optional conductive additive that are bonded together by a binder comprising a high-elasticity polymer (see abstract) .
  • the cathode active material may contain an organic material or a polymeric material selected from poly (anthraquinonyl sulfide) (PAQS) ; a lithium oxocarbon; 3, 4, 9, 10-perylenetetracarboxylic dianhydride (PTCDA) ; poly (anthraquinonyl sulfide) ; pyrene-4, 5, 9, 10-tetraone (PYT) ; polymer-bound PYT; quino (triazene) ; a redox-active organic material; tetracyanoquinodimethane (TCNQ) ; tetracyanoethylene (TCNE) ; 2, 3, 6, 7, 10, 11-hexamethoxytriphenylene (HMTP) ; poly (5-amino-l, 4-dyhydroxy anthraquinone) (PADAQ) ; phosphazene disulfide polymer ( [ (NPS 2 ) 3 ] n ) ,
  • U.S. Patent 10,388,990 discloses an electrolyte for a lithium secondary battery, and where the electrolyte includes the following: a lithium salt; a non-aqueous organic solvent; and a piperazine derivative represented by Formula 1, as described therein, having an oxidation potential lower than an oxidation potential of the non-aqueous organic solvent by about 2 V to about 4 V. See the abstract. See also U.S. Patent 9,819,054.
  • International Publication WO2018/222348 discloses a method of preparing an alkali metal cell, the method comprising: (a) combining a quantity of an active material, a quantity of an electrolyte, and a conductive additive to form a deformable and conductive electrode material; (b) forming the electrode material into a quasi-solid polymer electrode; (c) forming a second electrode; and (d) forming an alkali metal cell by combining the quasi-solid electrode and the second electrode. See abstract.
  • the cathode active material may contain an organic material or a polymeric material selected from poly (anthraquinonyl sulfide) (PAQS) ; a lithium oxocarbon; 3, 4, 9, 10-perylenetetracarboxylic dianhydride (PTCDA) ; poly (anthraquinonyl sulfide) ; pyrene-4, 5, 9, 10-tetraone (PYT) ; polymer-bound PYT; quino (triazene) ; a redox-active organic material; tetracyanoquinodimethane (TCNQ) ; tetracyanoethylene (TCNE) ; 2, 3, 6, 7, 10, 11-hexamethoxytriphenylene (HMTP) ; poly (5-amino-l, 4-dyhydroxy anthraquinone) (PADAQ) ; phosphazene disulfide polymer ( [ (NPS 2 ) 3 ] n ) ,
  • the binder cathode composition which has a reduced viscosity, while keeping the bonding performance thereof during the production of an electrode.
  • the binder cathode composition can be used for bonding an electrode active material to a current collector, and is characterized by containing an adhesive resin and a dispersant, wherein the dispersant is a compound represented by formula (I) or formula (II) , each as described therein. See English abstract.
  • U.S. Publication 2011/0206979 discloses a lithium ion rechargeable accumulator or secondary battery comprising a negative electrode, the active material of which is graphite carbon; a positive electrode, the active material of which is LiFePO 4 ; and an ionic liquid electrolyte comprising at least one ionic liquid of formula C + A - wherein C + represents a cation and A - represents an anion; and at least one conducting salt.
  • the ionic liquid electrolyte further comprising an organic additive which is vinyl ethylene carbonate (VEC) . See abstract.
  • the cation C + of the ionic liquid may be selected from hydroxonium, oxonium, ammonium, amidinium, phosphonium, uronium, thiouronium, guanidinium, sulfonium, phospholium, phosphorolium, iodonium, carbonium cations; heterocyclic cations such as pyridinium, quinolinium, isoquinolinium, imidazolium, pyrazolium, imidazolinium, triazolium, pyridazinium, pyrimidinium, pyrrolidinium, thiazolium, oxazolium, pyrazinium, piperazinium, piperidinium, pyrrolium, pyrizinium, indolium, quinoxalinium, thiomorpholinium, morpholinium, and indolinium cations; and the tautomeric forms of the latter (see paragraph [0078] ) .
  • CN102491304B (machine translation) discloses a method for preparing lithium iron phosphate, which serves as a lithium ion battery cathode material in an ionic eutectic mixture.
  • an ionic eutectic mixture is obtained by compounding urea/carboxylic acid/alcohols with a quaternary ammonium salt, and an organic amine or an organic alkali serving as a regulating agent.
  • the mixture is taken as a reaction solvent as well as a template agent, and a pure-phase lithium iron phosphate with high crystallizing performance is directly obtained with an ionic thermosynthesis method.
  • the organic amine may be thanomin, trolamine, hexahydroaniline, hexanediamine.
  • Organic bases may be piperazine anhydrous (see claim 3) .
  • CN103943825A (machine translation) discloses a method for supplementing the lithium element in a new lithium ion battery.
  • a liquid solution method is used for supplementing lithium for an electrode. The method comprises the following steps: a) preparing a solvent which can dissolve the metal lithium, and dissolving the metal lithium to form a lithium solution; b) enabling an electrode sheet to be in full contact with the lithium solution and enabling the lithium solution to infiltrate into the electrode; c) removing the solvent in the electrode sheet to obtain the electrode sheet after lithium supplementation. See abstract.
  • the solvent may contain polyamine compounds such as ethylenediamine, N, N′-dimethyl-ethylenediamine, piperazine, diaminopropanes, diaminobutane, dimethyl diaminobutane, triamido ethylamine, tertiary benzyl amine, tertiary sulfo group amine, N-benzyl, N-methyl capric acid amine (see claim 3) .
  • polyamine compounds such as ethylenediamine, N, N′-dimethyl-ethylenediamine, piperazine, diaminopropanes, diaminobutane, dimethyl diaminobutane, triamido ethylamine, tertiary benzyl amine, tertiary sulfo group amine, N-benzyl, N-methyl capric acid amine (see claim 3) .
  • CN115579460A (machine translation) discloses a water-based positive electrode slurry of a lithium iron phosphate battery, a preparation method of the water-based positive electrode slurry, the lithium iron phosphate battery and a positive electrode plate.
  • the preparation method comprises the following steps: (1) mixing the lithium iron phosphate powder with the conductive agent and the first part of the thickening agent in a dry mixing manner to obtain a mixed material; (2) adding water and a surfactant to the mixture obtained in the step (1) , to obtain a first mixed slurry with a solid content of 80-90 wt%; (3) dispersing water into the first mixed slurry obtained in the step (2) , to obtain a second mixed slurry with the solid content of 75-80 wt%; (4) dispersing a second portion of the thickener and water into the second mixed slurry from step (3) ; (5) dispersing the aqueous binder and water into the third mixed slurry.
  • the surfactant and the thickening agent are added, and the aqueous positive slurry of the lithium iron phosphate battery is prepared by a multi-step high-viscosity and high-temperature stirring preparation method, so that the aqueous positive slurry of the lithium iron phosphate battery is uniformly dispersed and has good stability.
  • the surfactant is at least one selected from 2-amino-2-methyl-1-propanol, styrene-acrylate copolymer and polyvinylpyrrolidone (see claim 2) .
  • Batteries, electrodes and/or compositions are also discloses in U.S. Patent 10,741,832; US Publication 2019/0296360; CN102130338A (machine translation) and CN106663802B (machine translation) .
  • a cathode composition comprising at least the following components a) and b) :
  • R1 and R2 are each independently a C1-C6 alkylene.
  • Figure 1 is a bar graph showing the viscosity of the noted cathode compositions.
  • compositions have been discovered that reduce the aggregation of LFP particles, leading to a decrease in the viscosity of the composition. Such compositions also have negligible corrosion, and can be prepared in water, providing a greener impact on the environment.
  • a cathode composition comprising at least the following components a) and b) :
  • R1 and R2 are each independently a C1-C6 alkylene.
  • the above cathode composition may comprise a combination of two or more embodiments, as described herein.
  • Each component may independently comprise a combination of two or more embodiments, as described herein.
  • Structure 1 may, comprise a combination of two or more embodiments, as described herein.
  • An “alkylene” group may be linear, branched, cyclic, or any combination thereof.
  • the cathode composition is a slurry.
  • component b is selected from Structures 1b) , as shown below:
  • n is an integer from 1 to 6, or from 1 to 5, or from 1 to 4, or from 2 to 4, or from 2 to 3, or 2; and m is an integer from 1 to 6, or from 1 to 5, or from 1 to 4, or from 2 to 4, or from 2 to 3, or 2.
  • component a is selected from lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, or a combination thereof. In one embodiment, or a combination of two or more embodiments, each described herein, component a is lithium iron phosphate.
  • component a is in particle form. In one embodiment, or a combination of two or more embodiments, each described herein, each described herein, the cathode composition further comprises a carbon coating over the particles of component a, to form carbon coated particles.
  • component b is present in an amount ⁇ 0.05 wt%, or ⁇ 0.06 wt%, or ⁇ 0.08 wt%, or ⁇ 0.10 wt%, or ⁇ 0.12 wt%, or ⁇ 0.14 wt%, or ⁇ 0.16 wt%, or ⁇ 0.18 wt%, or ⁇ 0.20 wt%, based on the weight of the cathode composition.
  • component b is present in an amount ⁇ 1.00 wt%, or ⁇ 0.90 wt%, or ⁇ 0.80 wt%, or ⁇ 0.70 wt%, or ⁇ 0.60 wt%, or ⁇ 0.50 wt%, or ⁇ 0.40 wt%, or ⁇ 0.30 wt%, based on the weight of the cathode composition.
  • the weight ratio of component a to component b is ⁇ 150, or ⁇ 200, or ⁇ 250, or ⁇ 300, or ⁇ 350, or ⁇ 400, or ⁇ 450. In one embodiment, or a combination of two or more embodiments, each described herein, the weight ratio of component a to component b is ⁇ 700, or ⁇ 650, or ⁇ 600, or ⁇ 550, or ⁇ 500.
  • component a is present in an amount ⁇ 35%, or ⁇ 40 wt%, or ⁇ 45 wt%, or ⁇ 50 wt%, or ⁇ 52 wt%, or ⁇ 54 wt%, or ⁇ 55 wt%, or ⁇ 56 wt%, or ⁇ 58 wt%, or ⁇ 60 wt%, based on the weight of the cathode composition.
  • component a is present in an amount ⁇ 80 wt%, or ⁇ 75 wt%, or ⁇ 70 wt%, or ⁇ 68 wt%, or ⁇ 66 wt%, or ⁇ 65 wt%, or ⁇ 64 wt%, or ⁇ 62 wt%, based on the weight of the cathode composition.
  • the cathode composition further comprises a solvent as component c.
  • the solvent (component c) is N-methyl-2-pyrrolidone (NMP) .
  • component c is present in an amount ⁇ 20.0 wt%, or ⁇ 22.0 wt%, or ⁇ 25.0 wt%, ⁇ 28.0 wt%, or ⁇ 30.0 wt%, or ⁇ 32.0 wt%, or ⁇ 34.0 wt%, or ⁇ 66.0 wt%, based on the weight of the cathode composition.
  • the component c is present in an amount ⁇ 60.0 wt%, or ⁇ 58.0 wt%, or ⁇ 56.0 wt%, or ⁇ 54.0 wt%, or ⁇ 52.0 wt%, or ⁇ 50.0 wt%, or ⁇ 48.0 wt%, or ⁇ 46.0 wt%, or ⁇ 44.0 wt%, or ⁇ 42.0 wt%, or ⁇ 40.0 wt%, or ⁇ 38.0 wt%, based on the weight of the cathode composition.
  • the weight ratio of component a to component c is ⁇ 1.30, or ⁇ 1.35, or ⁇ 1.40, or ⁇ 1.45, or ⁇ , or 1.50, or ⁇ 1.52, or ⁇ 1.54, or ⁇ 1.56, or ⁇ 1.58, or ⁇ 1.60. In one embodiment, or a combination of two or more embodiments, each described herein, the weight ratio of component a to component c is ⁇ 2.00, or ⁇ 1.95, or ⁇ 1.90, or ⁇ 1.85, or ⁇ 1.80, or ⁇ 1.78, or ⁇ 1.76, or ⁇ 1.74, or ⁇ 1.72, or ⁇ 1.70, or ⁇ 1.65.
  • the cathode composition further comprises at least one conductive agent as component d.
  • the cathode composition further comprises at least one binder as component e.
  • the sum of components a and b is present in an amount ⁇ 40.0 wt%, or ⁇ 45.0 wt%, or ⁇ 50.0 wt%, or ⁇ 52.0 wt%, or ⁇ 54.0 wt%, ⁇ 56.0 wt%, or ⁇ 58.0 wt%, or ⁇ 60.0 wt% and/or ⁇ 80.0 wt%, or ⁇ 78.0 wt%, or ⁇ 76.0 wt%, or ⁇ 74.0 wt%, or ⁇ 72.0 wt%, or ⁇ 70.0 wt%, based on the weight of the cathode composition.
  • the sum of components a, b and c is present in an amount ⁇ 80.0 wt%, or ⁇ 82.0 wt%, or ⁇ 84.0 wt%, or ⁇ 86.0 wt%, or ⁇ 88.0 wt%, ⁇ 90.0 wt%, or ⁇ 92.0 wt%, or ⁇ 94.0 wt%, or ⁇ 96.0 wt% and/or ⁇ 100.0 wt%, or ⁇ 99.5 wt%, or ⁇ 99.0 wt%, or ⁇ 98.5 wt%, or ⁇ 98.0 wt%, based on the weight of the cathode composition.
  • the sum of components a, b, c and d is present in an amount ⁇ 85.00 wt%, or ⁇ 88.00 wt%, or ⁇ 90.00 wt%, or ⁇ 92.00 wt%, or ⁇ 94.00 wt%, ⁇ 96.00 wt%, or ⁇ 97.00 wt%, or ⁇ 98.00 wt% and/or ⁇ 100.00 wt%, or ⁇ 99.50 wt%, or ⁇ 99.00 wt%, or ⁇ 98.50 wt%, based on the weight of the cathode composition.
  • a cathode comprising an active layer formed from the cathode composition of any one embodiment, or a combination of two or more embodiments, each described herein.
  • the cathode further comprises a metal foil (or a metal foil current collector) .
  • the metal of the metal foil is selected from aluminum, aluminum alloy, copper, copper alloy, further from aluminum or copper, and further aluminum.
  • cathode assembly comprising at least one cathode of any one embodiment, or a combination of two or more embodiments, each described herein.
  • a battery comprising the cathode assembly of any one embodiment, or a combination of two or more embodiments, each described herein.
  • the battery is a lithium battery.
  • a process to form a cathode comprising applying to one planar surface of a metal foil, the cathode composition of any one embodiment, or a combination of two or more embodiments, each described herein.
  • the metal of the metal foil is selected from aluminum, aluminum alloy, copper, copper alloy, further from aluminum or copper and further aluminum.
  • a process to form a cathode assembly comprising compacting at least one cathode of any one embodiment, or a combination of two or more embodiments, each described herein. In one embodiment, or a combination of two or more embodiments, each described herein, the process comprises compacting at least two cathodes.
  • N, N'-substituted piperazines are known in the art, and various ether amines are also commercially available.
  • the N, N'-substituted piperazines can be generated by reacting the oxides with the piperazine.
  • 1, 4-bis- (2-hydroxyethyl) piperazine can be synthesized by reacting the EO (ethylene oxide) and the piperazine at the targeted ratio of 2 ⁇ 1. This N, N'-substituted piperazine can be recovered using conventional technologies.
  • composition includes a mixture of materials, which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition. Any reaction product or decomposition product is typically present in trace or residual amounts.
  • cathode composition includes a mixture of materials, which comprise the cathode composition, as well as reaction products and decomposition products formed from the materials of the cathode composition. Any reaction product or decomposition product is typically present in trace or residual amounts.
  • polymer refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
  • the generic term polymer thus includes the term homopolymer (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure) , and the term interpolymer as defined hereinafter. Trace amounts of impurities, such as catalyst residues, can be incorporated into and/or within the polymer.
  • ppm amounts
  • interpolymer refers to a polymer prepared by the polymerization of at least two different types of monomers.
  • the term interpolymer thus includes the term copolymer (employed to refer to polymers prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.
  • lithium phosphate compound refers to a compound comprising at least one lithium cation (Li +1 ) and at least one phosphate anion (PO 4 -3 ) . Typically such a compound also comprises at least one other cation, such as a metal cation.
  • slurry refers to a mixture comprising one or more insoluble materials, such as particles, suspended in a solvent, such as water.
  • the mixture may also comprise one or more soluble materials, such as glucose, dissolved in the solvent, such as water.
  • solvent refers to a liquid substance of one or more compounds capable of dissolving and/or dispersing one or more other substances.
  • carbon coated particles refers to particles coated with a layer of carbon. Typically, 50%or more of the surface area of the particles is coated with carbon. Preferably, 90%or more of the surface area of the particles is coated with carbon.
  • cathode refers to an electrode through which current flows out, in a polarized electrical device.
  • anode refers to an electrode in a polarized electrical device, through which current flows in, from an outside circuit.
  • active layer in reference to an electrode, refers to a layer that adheres to the current collector, thus enabling the transport of electrons.
  • conductive agent refers to a material (for example, a carbon material) added to the composition to increase the ability of the active layer to charge and discharge electrons.
  • binder refers to a material (for example, a polymer) added to the composition to provide adhesion of the components within the active layer and with the metal foil.
  • dispenser refers to a substance, that is typically added to a suspension of solid or liquid particles, in a liquid (such as a slurry or an emulsion) , to improve the separation of the particles and to prevent their settling or clumping.
  • dispenser for conductive agent in reference to a cathode composition refers to a substance, used improve the separation of a conductive agent within the composition and to prevent the settling or clumping of the conductive agent.
  • the cathode composition is coated onto one planar surface of the metal foil
  • similar phrases, used herein in reference to the process of preparing a cathode refer to the act of contacting the metal surface with the cathode composition. This contact may occur by wetting the metal surface with the cathode composition using a brush, a spray, a roller, or by any other means known in the art.
  • planar surface refers to the surface area formed by the width and length, or the surface area formed by the diameter, or the surface area formed from the larger dimensions of the foil.
  • cathode assembly refers to battery component that comprises one or more cathodes.
  • electrolyte refers to a solution capable of carrying ions back and forth between a cathode and an anode of a battery.
  • electrochemical cell refers to a device that generates electrical energy from chemical energy. Electrical energy can also be applied to these cells to cause one or more chemical reactions to occur.
  • battery refers to a container containing one or more electrochemical cells, in which chemical energy is converted to electrical energy.
  • lithium battery refers to a battery that uses a lithium source in one or more electrochemical cells.
  • Examples of lithium batteries include, but are not limited to, a lithium-ion battery, a lithium metal battery, a lithium-sulfur battery, a lithium-selenium battery, or a lithium-air battery.
  • water refers to H 2 O.
  • H 2 O water
  • Such a water (H 2 O) is virtually pure water, and as such, may or may not contain one or more impurities, such as, for example, dissolved inorganic ions.
  • the impurities are present in an amount ⁇ 1000 ppm, preferably ⁇ 100 ppm, more preferably ⁇ 10 ppm, more preferably ⁇ 1 ppm, based on the weight of a sample of the water.
  • thermoally treating, ” “thermally treated, ” “thermal treatment, ” and similar terms, as used herein, in reference to a cathode composition or a compound or a coated foil, each as discussed herein, refer to increasing the temperature of the “material at issue” by application of heat.
  • heat may be applied, for example, by electrical means (for example, a heating coil in an oven) .
  • the temperature at which the thermal treatment takes place refers to the temperature of the “heat-applying” device, or, if the device contains an enclosed or semi-enclosed atmosphere, the temperature of the atmosphere within the device, such as, for example, the atmosphere within an oven or a tunnel (for example, the air temperature in an hot air oven or a hot air tunnel) .
  • compositions claimed through use of the term “comprising” may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary.
  • the term, “consisting essentially of” excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability.
  • the term “consisting of” excludes any component, step or procedure, not specifically delineated or listed.
  • a cathode composition comprising at least the following components a) and b) :
  • R1 and R2 are each independently a C1-C6 alkylene.
  • R1 is a C1-C5 alkylene, or a C1-C4 alkylene, or a C1-C3 alkylene, or a C1-C2 alkylene, or a C2 alkylene.
  • R2 is a C1-C5 alkylene, or a C1-C4 alkylene, or a C1-C3 alkylene, or a C1-C2 alkylene, or a C2 alkylene.
  • n is an integer from 1 to 6, or from 1 to 5, or from 1 to 4, or from 2 to 4, or from 2 to 3, or 2; and m is an integer from 1 to 6, or from 1 to 5, or from 1 to 4, or from 2 to 4, or from 2 to 3, or 2.
  • component a is selected from lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, or a combination thereof.
  • P1 The cathode composition of any one of A] -O] above, wherein the component b is present in an amount ⁇ 0.05 wt%, or ⁇ 0.06 wt%, or ⁇ 0.08 wt%, or ⁇ 0.10 wt%, or ⁇ 0.12 wt%, or ⁇ 0.14 wt%, or ⁇ 0.16 wt%, or ⁇ 0.18 wt%, or ⁇ 0.20 wt%, based on the weight of the cathode composition.
  • T The cathode composition of any one of A] -S] above, wherein the component a is present in an amount ⁇ 35%, or ⁇ 40 wt%, or ⁇ 45 wt%, or ⁇ 50 wt%, or ⁇ 52 wt%, or ⁇ 54 wt%, or ⁇ 55 wt%, or ⁇ 56 wt%, or ⁇ 58 wt%, or ⁇ 60 wt%, based on the weight of the cathode composition.
  • C2 The cathode composition of any one of X] -B2] above, wherein the weight ratio of component a to component c is ⁇ 2.00, or ⁇ 1.95, or ⁇ 1.90, or ⁇ 1.85, or ⁇ 1.80, or ⁇ 1.78, or ⁇ 1.76, or ⁇ 1.74, or ⁇ 1.72, or ⁇ 1.70, or ⁇ 1.68, or ⁇ 1.66, or ⁇ 1.64, or ⁇ 1.62.
  • cathode composition of any one of A] -G2] , wherein the cathode composition further comprises at least one binder as component e.
  • J2] The cathode composition of H2] or I2] above, wherein component e is present in an amount ⁇ 0.50 wt%, or ⁇ 0.70 wt%, or ⁇ 1.00 wt%, ⁇ 1.20 wt%, or ⁇ 1.40 wt%, or ⁇ 1.60 wt%, or ⁇ 1.70 wt%, or ⁇ 1.80 wt% and/or ⁇ 5.00 wt%, or ⁇ 4.50 wt%, or ⁇ 4.00 wt%, or ⁇ 3.50 wt%, or ⁇ 3.00 wt%, or ⁇ 2.50 wt%, or ⁇ 2.00 wt%, based on the weight of the cathode composition.
  • M2 The cathode composition of L2] , wherein the component fis polyvinyl pyrrolidone, and further PVP K30.
  • R2 The cathode composition of any one of X] -Q2] above, wherein the sum of components a, b and c is present in an amount ⁇ 80.0 wt%, or ⁇ 82.0 wt%, or ⁇ 84.0 wt%, or ⁇ 86.0 wt%, or ⁇ 88.0 wt%, ⁇ 90.0 wt%, or ⁇ 92.0 wt%, or ⁇ 94.0 wt%, or ⁇ 96.0 wt%, or ⁇ 97.0 wt% and/or ⁇ 100.0 wt%, or ⁇ 99.5 wt%, or ⁇ 99.0 wt%, or ⁇ 98.5 wt%, or ⁇ 98.0 wt%, based on the weight of the cathode composition.
  • T2 The cathode composition of any one of H2] -S2] above, wherein the sum of components a, b, c, d and e is present in an amount ⁇ 90.00 wt%, or ⁇ 91.00 wt%, or ⁇ 92.00 wt%, or ⁇ 93.00 wt%, or ⁇ 94.00 wt%, ⁇ 95.00 wt%, or ⁇ 96.00 wt%, or ⁇ 97.00 wt%, or ⁇ 97.50 wt%, or ⁇ 98.00 wt or ⁇ 98.50 wt%, ⁇ 99.00 wt% and/or ⁇ 100.00 wt%, or ⁇ 99.98 wt%, based on the weight of the cathode composition.
  • cathode composition of any one of A] -U2] above, wherein the cathode composition comprises ⁇ 1.0 ppm, or ⁇ 0.50 ppm, or ⁇ 0.20 ppm, or ⁇ 0.10 ppm, or ⁇ 0.05 ppm, or ⁇ 0.02 ppm, or ⁇ 0.01 ppm of “2-amino-2-methyl-1-propanol, ” based on the weight of the cathode composition, and further the cathode composition does not comprise a “2-amino-2-methyl-1-propanol. ”
  • a cathode comprising an active layer formed from the cathode composition of any one of A] -V2] above.
  • C3 The cathode of B3] above, wherein the metal of the metal foil is selected from, aluminum, aluminum alloy, copper, copper alloy, further from aluminum or copper and further aluminum.
  • D3 The cathode of B3] or C3] above, wherein the metal has a thickness ⁇ 10, or ⁇ 12, or ⁇ 14 ⁇ m and/or ⁇ 25, or ⁇ 22, or ⁇ 20, or ⁇ 18, ⁇ 16 ⁇ m.
  • G3 The cathode of F3] above, wherein the coated foil is thermally treated at a temperature ⁇ 50°C, or ⁇ 55°C, or ⁇ 60°C, or ⁇ 65°C, or ⁇ 70°C, or ⁇ 75°C, or ⁇ 80°C and/or ⁇ 120°C or ⁇ 115°C, or ⁇ 110°C or ⁇ 105°C, or ⁇ 100°C, or ⁇ 95°C, or ⁇ 90°C, or ⁇ 85°C.
  • I3 The cathode of H3] above, wherein the pressure is ⁇ 5.0 MT, or ⁇ 10 MT, or ⁇ 15 MT, or ⁇ 20 MT, or ⁇ 22 MT, or ⁇ 24 MT, or ⁇ 26 MT (Millitorr) and/or ⁇ 40 MT, or ⁇ 38 MT or ⁇ 36 MT, or ⁇ 34 MT, or ⁇ 32 MT, or ⁇ 30 MT, or ⁇ 28 MT (Millitorr) .
  • a cathode assembly comprising at least one cathode of any one of A3] -I3] above.
  • L3 A battery comprising the cathode assembly of J3] or K3] above.
  • a process to form a cathode comprising applying to one planar surface of a metal foil, the cathode composition of any one of A] -V2] above, to form a coated foil.
  • H4 The process of F4] or G4] above, wherein the metal has a thickness ⁇ 10, or ⁇ 12, or ⁇ 14 ⁇ m and/or ⁇ 25, or ⁇ 22, or ⁇ 20, or ⁇ 18, ⁇ 16 ⁇ m.
  • N4 A process to form a battery, the process comprising inserting the cathode assembly of J3] or K3] into an electrolyte.
  • each component, except for the NMP was dried in an oven, at 80°C, for 24 hours, under circulating air.
  • the NMP was dried, at room temp, with 5A molecular sieve, to remove the trace amount of water.
  • the slurry preparation is described in the following steps: 1) the PVDF (2.0 g) was added to NMP (18 g) , and the resulting mixture was thermally treated in an oven set at 50°C, until complete dissolution of the PVDF, to form a “PVDF/NMP” solution; 2) the Super P (SP, 0.060 g) , PVP K30 (PVP, 0.006 g) and NMP (1.194 g) were mixed in a high speed mixer (SPEEDMIXER DAC 150) , at 3000 rpm for three minutes, to form a “SP/PVP/NMP” mixture; 3) the LFP (6.000 g) and NMP (0.940 g) were added to the above “SP/PVP/NMP” mixture, and the resulting mixture was mixed in the high speed mixer, at 3000 rpm, for three minutes, to form a “LFP/SP/PVP/NMP” mixture; 4) the “PVDF/NMP” solution (1.800 g) was
  • the viscosity of each cathode composition was measured using a BROOKFIELD CAP 2000+ viscometer. To be specific, 0.5 mL of the cathode composition was put under the spindle (#10) , maintained at 22°C, under ambient atmosphere. The spindle was rotated at 50 rpm during the determination of the viscosity. The cathode composition was maintained at 22°C for 30 seconds, and then the motor to the spindle was started. As the spindle rotated, the viscosity data was displayed after of 30 seconds. For each cathode composition, one viscosity measurement was taken. The results are shown in Figure 1.
  • Each dispersant (0.2 g, Piperazine, HEP or Di-HEP) was added to water (19.8 g) , and the resulting mixture was mixed in the high speed mixer at 2000 rpm for three minutes, for complete dissolution of the dispersant.
  • the resulting dispersant solution was “1 wt%dispersant, ” based on the weight of the solution.
  • the LFP particles (0.2 g) were added to the dispersant solution, and the resulting slurry was shaken and stored at room temperature (21 °C-23°C) , ambient atmosphere, for one week. After storage, the slurry was filtered to remove the LFP particles. The filtrate was examined for the Fe cation concentration (corrosion study) .
  • a Perkin Elmer OPTIMA 5300DV was used for the measurement of Fe cation concentration in each filtrate, as follows.
  • the filtrate (1 g) was added to a 50 ml volumetric flask and dilute with “5 wt%HNO3 in water, ” up to the “50 ml” mark, to form a test solution.
  • the test solution was weighed, mixed well, and analyzed for Fe cation concentration using the following instrument conditions: a) RF power: 1.3 Kw; b) gas flows: Plasma gas -15 L/min.
  • each cathode composition is shown in Figure 1.
  • the cathode composition containing the AMP (CE2) had a relatively low viscosity, and lower than the control cathode composition CE1.
  • the viscosity of LFP slurry has increased 35.9%and 13.9%, respectively, relative to the viscosity of CE1. This indicates that the cathode compositions CE3 and CE4 do not have a good dispersion of the LFP particles, as compared to CE2.
  • Cathode composition IE1 containing Di-HEP, has a drop in viscosity of 12.2%, relative to the viscosity of CE1, and a drop in viscosity of 8.4%, relative to the viscosity of CE2. These results indicate that cathode composition IE1 has a better dispersing performance than that of CE2.
  • Corrosion is another important issue, because the degradation of the LFP will lead to a performance decrease in the cathode of a battery.
  • LFP will corrode under an acid environment, and release Fe cations into an electrolyte within a battery.
  • the active hydrogen (s) (N-H) on the ring structure may also contribute to an acidic environment.
  • the Fe cation concentration is used to demonstrate the corrosion performance of each dispersant. As seen in Table 3, the piperazine resulted in the highest amount of corrosion (4.4 ppm Fe) as compared to HEP and Di-HEP.
  • cathode compositions containing Di-HEP can be used to form cathodes that will exhibit negligible corrosion. Also, such cathode compositions will have reduced viscosity compared to cathode compositions containing AMP, piperazine or HEP.

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Abstract

A cathode composition comprising at least the following components: a) at least one lithium phosphate compound, and b) at least one dispersant selected from the following Structure 1 as described herein.

Description

CATHODE COMPOSITIONS CONTAINING PIPERAZINE DERIVATIVES BACKGROUND OF THE INVENTION
The fast development of a new energy vehicle (NEV) has brought great opportunity to the lithium-ion battery (LiB) market. Among the various types of cathode materials used in these batteries, lithium iron phosphate (LFP) is the most popular one, because of its lower cost, longer cycle stability and higher safety performance. The first step to prepare the LFP cathode is to make a LFP cathode slurry. This procedure is typically carried out by mixing the LFP, with a binder and a conductive agent, in N-methyl-2-pyrrolidone (NMP) as solvent. Subsequently, the mixture is homogenized until a uniform slurry results.
Due to their high specific surface area, the LFP particles tend to aggregate, and this aggregation makes it difficult to disperse these particles in the solvent. Furthermore, LFP particles may also interact with the conductive agent and the binder to form an aggregation. Because of the aggregation, the viscosity of the cathode slurry increases dramatically. During the cathode manufacturing, the LFP slurry will be coated onto an aluminum foil. Subsequently, the NMP will evaporate, leaving only the active materials, binder and conductive agent on the foil surface. Regarding this process, the high viscosity of the LFP slurry will lead to two problems, a low coating rate and a prolonged evaporation rate, each as discussed below.
A low coating rate. The high viscosity of the slurry will hinder the coating of the slurry on the foil, and thus decrease the manufacturing efficiency of the cathode. Furthermore, the high viscosity will increase the risk of generating defects on the electrode, which will significantly increase the amount of defective cathodes and reduce the manufacturing efficiency.
A prolonged evaporation rate. To mitigate the risk of defects on the electrode, manufacturers tend to add more of the NMP solvent to lower the viscosity of the LFP slurry. However, this will lower the solid content of the slurry and will increase the time needed to remove the NMP.
Thus, there is a need for cathode compositions that help to prevent the aggregation of the LFP particles. This reduction in aggregation will, in turn, reduce the viscosity of an LFP slurry. The reduced viscosity will increase the coating rate on the metal foil, decrease the risk of generating defects on the cathode, and allow for an increase in the solid content of the slurry, which will decrease the evaporation time of the solvent. Thus, the overall manufacturing efficiency will increase.
International Publication WO2018/156330 discloses a cathode active material layer for a lithium battery. The cathode active material layer comprises multiple cathode active material particles and an optional conductive additive that are bonded together by a binder comprising a  high-elasticity polymer (see abstract) . The cathode active material may contain an organic material or a polymeric material selected from poly (anthraquinonyl sulfide) (PAQS) ; a lithium oxocarbon; 3, 4, 9, 10-perylenetetracarboxylic dianhydride (PTCDA) ; poly (anthraquinonyl sulfide) ; pyrene-4, 5, 9, 10-tetraone (PYT) ; polymer-bound PYT; quino (triazene) ; a redox-active organic material; tetracyanoquinodimethane (TCNQ) ; tetracyanoethylene (TCNE) ; 2, 3, 6, 7, 10, 11-hexamethoxytriphenylene (HMTP) ; poly (5-amino-l, 4-dyhydroxy anthraquinone) (PADAQ) ; phosphazene disulfide polymer ( [ (NPS2) 3] n) , lithiated 1, 4, 5, 8-naphthalenetetraol formaldehyde polymer; hexaaza-trinaphtylene (HATN) ; hexaazatriphenylene hexacarbonitrile (HAT (CN) 6) ; 5-benzylidene hydantoin; isatine lithium salt; pyromellitic diimide lithium salt; tetrahydroxy-p-benzo-quinone derivatives (THQLi4) ; N, N′-diphenyl-2, 3, 5, 6-tetraketopiperazine (PHP) ; N, N′-diallyl-2, 3, 5, 6-tetraketopiperazine (AP) ; N, N′-dipropyl-2, 3, 5, 6-tetraketopiperazine (PRP) ; a thioetherpolymer; a quinone compound; 1, 4-benzoquinone; 5, 7, 12, 14-pentacenetetrone (PT) ; 5-amino-2, 3-dihydro-l, 4-dyhydroxy anthraquinone (ADDAQ) ; 5-amino-l, 4-dy-hydroxyanthraquinone (ADAQ) ; calixquinone; Li4C6O6; Li2C6O6; Li6C6O6; or a combination thereof. See claims 4 and 14.
U.S. Patent 10,388,990 discloses an electrolyte for a lithium secondary battery, and where the electrolyte includes the following: a lithium salt; a non-aqueous organic solvent; and a piperazine derivative represented by Formula 1, as described therein, having an oxidation potential lower than an oxidation potential of the non-aqueous organic solvent by about 2 V to about 4 V. See the abstract. See also U.S. Patent 9,819,054.
International Publication WO2018/222348 discloses a method of preparing an alkali metal cell, the method comprising: (a) combining a quantity of an active material, a quantity of an electrolyte, and a conductive additive to form a deformable and conductive electrode material; (b) forming the electrode material into a quasi-solid polymer electrode; (c) forming a second electrode; and (d) forming an alkali metal cell by combining the quasi-solid electrode and the second electrode. See abstract. The cathode active material may contain an organic material or a polymeric material selected from poly (anthraquinonyl sulfide) (PAQS) ; a lithium oxocarbon; 3, 4, 9, 10-perylenetetracarboxylic dianhydride (PTCDA) ; poly (anthraquinonyl sulfide) ; pyrene-4, 5, 9, 10-tetraone (PYT) ; polymer-bound PYT; quino (triazene) ; a redox-active organic material; tetracyanoquinodimethane (TCNQ) ; tetracyanoethylene (TCNE) ; 2, 3, 6, 7, 10, 11-hexamethoxytriphenylene (HMTP) ; poly (5-amino-l, 4-dyhydroxy anthraquinone) (PADAQ) ; phosphazene disulfide polymer ( [ (NPS2) 3] n) , lithiated 1, 4, 5, 8-naphthalenetetraol formaldehyde polymer; hexaazatrinaphtylene (HATN) ; hexaazatriphenylene hexacarbonitrile (HAT (CN) 6) ; 5-benzylidene hydantoin; isatine lithium salt; pyromellitic diimide lithium salt; tetrahydroxy-p-benzoquinone derivatives (THQLi4) ; N, N′-diphenyl-2, 3, 5, 6-tetraketopiperazine  (PHP) ; N, N′-diallyl-2, 3, 5, 6-tetraketopiperazine (AP) ; N, N′-dipropyl-2, 3, 5, 6-tetraketopiperazine (PRP) ; a thioetherpolymer; a quinone compound; 1, 4-benzoquinone; 5, 7, 12, 14-penta-cenetetrone (PT) ; 5-amino-2, 3-dihydro-l, 4-dyhydroxy anthraquinone (ADDAQ) ; 5-amino-1, 4-dyhydroxyanthraquinone (ADAQ) ; calixquinone; Li4C6O6; Li2C6O6; Li6C6O6; or a combination thereof. See claims 28 and 35.
International Publication WO2019/009242 discloses a binder cathode composition which has a reduced viscosity, while keeping the bonding performance thereof during the production of an electrode. The binder cathode composition can be used for bonding an electrode active material to a current collector, and is characterized by containing an adhesive resin and a dispersant, wherein the dispersant is a compound represented by formula (I) or formula (II) , each as described therein. See English abstract.
U.S. Publication 2011/0206979 discloses a lithium ion rechargeable accumulator or secondary battery comprising a negative electrode, the active material of which is graphite carbon; a positive electrode, the active material of which is LiFePO4; and an ionic liquid electrolyte comprising at least one ionic liquid of formula C+A- wherein C+ represents a cation and A- represents an anion; and at least one conducting salt. The ionic liquid electrolyte further comprising an organic additive which is vinyl ethylene carbonate (VEC) . See abstract. The cation C+ of the ionic liquid may be selected from hydroxonium, oxonium, ammonium, amidinium, phosphonium, uronium, thiouronium, guanidinium, sulfonium, phospholium, phosphorolium, iodonium, carbonium cations; heterocyclic cations such as pyridinium, quinolinium, isoquinolinium, imidazolium, pyrazolium, imidazolinium, triazolium, pyridazinium, pyrimidinium, pyrrolidinium, thiazolium, oxazolium, pyrazinium, piperazinium, piperidinium, pyrrolium, pyrizinium, indolium, quinoxalinium, thiomorpholinium, morpholinium, and indolinium cations; and the tautomeric forms of the latter (see paragraph [0078] ) .
CN102491304B (machine translation) discloses a method for preparing lithium iron phosphate, which serves as a lithium ion battery cathode material in an ionic eutectic mixture. In the method, an ionic eutectic mixture is obtained by compounding urea/carboxylic acid/alcohols with a quaternary ammonium salt, and an organic amine or an organic alkali serving as a regulating agent. The mixture is taken as a reaction solvent as well as a template agent, and a pure-phase lithium iron phosphate with high crystallizing performance is directly obtained with an ionic thermosynthesis method. See abstract. The organic amine may be thanomin, trolamine, hexahydroaniline, hexanediamine. Organic bases may be piperazine anhydrous (see claim 3) .
CN103943825A (machine translation) discloses a method for supplementing the lithium element in a new lithium ion battery. A liquid solution method is used for supplementing  lithium for an electrode. The method comprises the following steps: a) preparing a solvent which can dissolve the metal lithium, and dissolving the metal lithium to form a lithium solution; b) enabling an electrode sheet to be in full contact with the lithium solution and enabling the lithium solution to infiltrate into the electrode; c) removing the solvent in the electrode sheet to obtain the electrode sheet after lithium supplementation. See abstract. The solvent may contain polyamine compounds such as ethylenediamine, N, N′-dimethyl-ethylenediamine, piperazine, diaminopropanes, diaminobutane, dimethyl diaminobutane, triamido ethylamine, tertiary benzyl amine, tertiary sulfo group amine, N-benzyl, N-methyl capric acid amine (see claim 3) .
CN115579460A (machine translation) discloses a water-based positive electrode slurry of a lithium iron phosphate battery, a preparation method of the water-based positive electrode slurry, the lithium iron phosphate battery and a positive electrode plate. The preparation method comprises the following steps: (1) mixing the lithium iron phosphate powder with the conductive agent and the first part of the thickening agent in a dry mixing manner to obtain a mixed material; (2) adding water and a surfactant to the mixture obtained in the step (1) , to obtain a first mixed slurry with a solid content of 80-90 wt%; (3) dispersing water into the first mixed slurry obtained in the step (2) , to obtain a second mixed slurry with the solid content of 75-80 wt%; (4) dispersing a second portion of the thickener and water into the second mixed slurry from step (3) ; (5) dispersing the aqueous binder and water into the third mixed slurry. According to the preparation method, the surfactant and the thickening agent are added, and the aqueous positive slurry of the lithium iron phosphate battery is prepared by a multi-step high-viscosity and high-temperature stirring preparation method, so that the aqueous positive slurry of the lithium iron phosphate battery is uniformly dispersed and has good stability. See abstract. The surfactant is at least one selected from 2-amino-2-methyl-1-propanol, styrene-acrylate copolymer and polyvinylpyrrolidone (see claim 2) .
Batteries, electrodes and/or compositions are also discloses in U.S. Patent 10,741,832; US Publication 2019/0296360; CN102130338A (machine translation) and CN106663802B (machine translation) .
However, as discussed above, there remains a need for cathode compositions that help to prevent the aggregation of LFP particles. This need has been met as discussed below.
SUMMARY OF THE INVENTION
A cathode composition comprising at least the following components a) and b) :
a) at least one lithium phosphate compound,
b) at least one dispersant selected from the following Structure 1:
wherein R1 and R2 are each independently a C1-C6 alkylene.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a bar graph showing the viscosity of the noted cathode compositions.
DETAILED DRESCRIPTION OF THE INVENTION
Compositions have been discovered that reduce the aggregation of LFP particles, leading to a decrease in the viscosity of the composition. Such compositions also have negligible corrosion, and can be prepared in water, providing a greener impact on the environment.
As discussed, a cathode composition is provided, comprising at least the following components a) and b) :
a) at least one lithium phosphate compound,
b) at least one dispersant selected from the following Structure 1:
wherein R1 and R2 are each independently a C1-C6 alkylene.
The above cathode composition may comprise a combination of two or more embodiments, as described herein. Each component may independently comprise a combination of two or more embodiments, as described herein. Structure 1 may, comprise a combination of two or more embodiments, as described herein. As used herein, in regard to Structure 1, R1 = R1 and R2 = R2. An “alkylene” group may be linear, branched, cyclic, or any combination thereof.
In one embodiment, or a combination of two or more embodiments, each described herein, the cathode composition is a slurry.
In one embodiment, or a combination of two or more embodiments, each described herein, for component b, Structure 1, R1 = R2.
In one embodiment, or a combination of two or more embodiments, each described herein, component b is selected from Structures 1b) , as shown below:
1b) wherein n is an integer from 1 to 6, or from 1 to 5, or from 1 to 4, or from 2 to 4, or from 2 to 3, or 2; and m is an integer from 1 to 6, or from 1 to 5, or from 1 to 4, or from 2 to 4, or from 2 to 3, or 2.
In one embodiment, or a combination of two or more embodiments, each described herein, component b is selected from Structure 1b) , as shown above, and or n = m, or n = m = 2 or 3, orn=m=2.
In one embodiment, or a combination of two or more embodiments, each described herein, component a is selected from lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, or a combination thereof. In one embodiment, or a combination of two or more embodiments, each described herein, component a is lithium iron phosphate.
In one embodiment, or a combination of two or more embodiments, each described herein, component a is in particle form. In one embodiment, or a combination of two or more embodiments, each described herein, the cathode composition further comprises a carbon coating over the particles of component a, to form carbon coated particles.
In one embodiment, or a combination of two or more embodiments, each described herein, component b is present in an amount ≥ 0.05 wt%, or ≥ 0.06 wt%, or ≥ 0.08 wt%, or ≥ 0.10 wt%, or ≥ 0.12 wt%, or ≥ 0.14 wt%, or ≥ 0.16 wt%, or ≥ 0.18 wt%, or ≥ 0.20 wt%, based on the weight of the cathode composition. In one embodiment, or a combination of two or more embodiments, each described herein, component b is present in an amount ≤ 1.00 wt%, or ≤ 0.90 wt%, or ≤ 0.80 wt%, or ≤ 0.70 wt%, or ≤ 0.60 wt%, or ≤ 0.50 wt%, or ≤ 0.40 wt%, or ≤ 0.30 wt%, based on the weight of the cathode composition.
In one embodiment, or a combination of two or more embodiments, each described herein, the weight ratio of component a to component b is ≥ 150, or ≥ 200, or ≥ 250, or ≥ 300, or ≥ 350, or ≥ 400, or ≥ 450. In one embodiment, or a combination of two or more embodiments, each described herein, the weight ratio of component a to component b is ≤ 700, or ≤ 650, or ≤600, or ≤ 550, or ≤ 500.
In one embodiment, or a combination of two or more embodiments, each described herein, component a is present in an amount ≥ 35%, or ≥ 40 wt%, or ≥ 45 wt%, or ≥ 50 wt%, or ≥ 52 wt%, or ≥ 54 wt%, or ≥ 55 wt%, or ≥ 56 wt%, or ≥ 58 wt%, or ≥ 60 wt%, based on the weight of the cathode composition. In one embodiment, or a combination of two or more embodiments, each described herein, component a is present in an amount ≤ 80 wt%, or ≤ 75 wt%, or≤ 70 wt%, or≤ 68 wt%, or≤ 66 wt%, or≤ 65 wt%, or≤ 64 wt%, or≤ 62 wt%, based on the weight of the cathode composition.
In one embodiment, or a combination of two or more embodiments, each described herein, the cathode composition further comprises a solvent as component c. In one embodiment, or a combination of two or more embodiments, each described herein, the solvent (component c) is N-methyl-2-pyrrolidone (NMP) .
In one embodiment, or a combination of two or more embodiments, each described herein, component c is present in an amount ≥ 20.0 wt%, or ≥ 22.0 wt%, or ≥ 25.0 wt%, ≥ 28.0 wt%, or ≥ 30.0 wt%, or ≥ 32.0 wt%, or ≥ 34.0 wt%, or ≥ 66.0 wt%, based on the weight of the cathode composition. In one embodiment, or a combination of two or more embodiments, each described herein, the component c is present in an amount ≤ 60.0 wt%, or ≤ 58.0 wt%, or ≤ 56.0 wt%, or ≤ 54.0 wt%, or ≤ 52.0 wt%, or ≤ 50.0 wt%, or ≤ 48.0 wt%, or ≤ 46.0 wt%, or ≤ 44.0 wt%, or ≤ 42.0 wt%, or ≤ 40.0 wt%, or ≤ 38.0 wt%, based on the weight of the cathode composition.
In one embodiment, or a combination of two or more embodiments, each described herein, the weight ratio of component a to component c is ≥ 1.30, or ≥ 1.35, or ≥ 1.40, or ≥ 1.45, or ≥, or 1.50, or ≥ 1.52, or ≥ 1.54, or ≥ 1.56, or ≥ 1.58, or ≥ 1.60. In one embodiment, or a combination of two or more embodiments, each described herein, the weight ratio of component a to component c is ≤ 2.00, or ≤ 1.95, or ≤ 1.90, or ≤ 1.85, or ≤ 1.80, or ≤ 1.78, or ≤ 1.76, or ≤1.74, or ≤ 1.72, or ≤ 1.70, or ≤ 1.65.
In one embodiment, or a combination of two or more embodiments, each described herein, the cathode composition further comprises at least one conductive agent as component d.
In one embodiment, or a combination of two or more embodiments, each described herein, the cathode composition further comprises at least one binder as component e.
In one embodiment, or a combination of two or more embodiments, each described herein, the sum of components a and b is present in an amount ≥ 40.0 wt%, or ≥ 45.0 wt%, or ≥50.0 wt%, or ≥ 52.0 wt%, or ≥ 54.0 wt%, ≥ 56.0 wt%, or ≥ 58.0 wt%, or ≥ 60.0 wt%and/or ≤80.0 wt%, or ≤ 78.0 wt%, or ≤ 76.0 wt%, or ≤ 74.0 wt%, or ≤ 72.0 wt%, or ≤ 70.0 wt%, based on the weight of the cathode composition.
In one embodiment, or a combination of two or more embodiments, each described herein, the sum of components a, b and c is present in an amount ≥ 80.0 wt%, or ≥ 82.0 wt%, or ≥ 84.0 wt%, or ≥ 86.0 wt%, or ≥ 88.0 wt%, ≥ 90.0 wt%, or ≥ 92.0 wt%, or ≥ 94.0 wt%, or ≥ 96.0 wt%and/or ≤ 100.0 wt%, or ≤ 99.5 wt%, or ≤ 99.0 wt%, or ≤ 98.5 wt%, or ≤ 98.0 wt%, based on the weight of the cathode composition.
In one embodiment, or a combination of two or more embodiments, each described herein, the sum of components a, b, c and d is present in an amount ≥ 85.00 wt%, or ≥ 88.00 wt%, or ≥ 90.00 wt%, or ≥ 92.00 wt%, or ≥ 94.00 wt%, ≥ 96.00 wt%, or ≥ 97.00 wt%, or ≥  98.00 wt%and/or ≤ 100.00 wt%, or ≤ 99.50 wt%, or ≤ 99.00 wt%, or ≤ 98.50 wt%, based on the weight of the cathode composition.
Also provided is a cathode comprising an active layer formed from the cathode composition of any one embodiment, or a combination of two or more embodiments, each described herein. In one embodiment, or a combination of two or more embodiments, each described herein, the cathode further comprises a metal foil (or a metal foil current collector) . In one embodiment, or a combination of two or more embodiments, each described herein, the metal of the metal foil is selected from aluminum, aluminum alloy, copper, copper alloy, further from aluminum or copper, and further aluminum.
Also provided is a cathode assembly comprising at least one cathode of any one embodiment, or a combination of two or more embodiments, each described herein.
Also provided is a battery comprising the cathode assembly of any one embodiment, or a combination of two or more embodiments, each described herein.
In one embodiment, or a combination of two or more embodiments, each described herein, the battery is a lithium battery.
Also provided is a process to form a cathode composition of any one embodiment, or a combination of two or more embodiments, each described herein, the process comprising mixing at least components a and b. In one embodiment, or a combination of two or more embodiments, each described herein, the process further comprising mixing at least components a, b and c. In one embodiment, or a combination of two or more embodiments, each described herein, the process further comprising mixing at least components a, b, c and d. In one embodiment, or a combination of two or more embodiments, each described herein, the process further comprising mixing at least components a, b, c, d and e.
Also provided is a process to form a cathode, the process comprising applying to one planar surface of a metal foil, the cathode composition of any one embodiment, or a combination of two or more embodiments, each described herein. In one embodiment, or a combination of two or more embodiments, each described herein, the metal of the metal foil is selected from aluminum, aluminum alloy, copper, copper alloy, further from aluminum or copper and further aluminum.
Also provided is a process to form a cathode assembly, the process comprising compacting at least one cathode of any one embodiment, or a combination of two or more embodiments, each described herein. In one embodiment, or a combination of two or more embodiments, each described herein, the process comprises compacting at least two cathodes.
Also provided is a process to form a battery, the process comprising inserting the cathode assembly of any one embodiment, or a combination of two or more embodiments, each described herein, into an electrolyte.
Component b -N, N'-Substituted Piperazine
Component b is described herein. Syntheses of N, N'-substituted piperazines are known in the art, and various ether amines are also commercially available. For example, the N, N'-substituted piperazines can be generated by reacting the oxides with the piperazine. Further as an example, 1, 4-bis- (2-hydroxyethyl) piperazine can be synthesized by reacting the EO (ethylene oxide) and the piperazine at the targeted ratio of 2∶1. This N, N'-substituted piperazine can be recovered using conventional technologies.
Component b can be in the form of a liquid cathode composition that is added to an aqueous cathode composition. The N, N'-substituted piperazine per se can be in the form of a liquid at room temperature (22℃) , and therefore a "stock" cathode composition can be one where the N, N'-substituted piperazine is in neat form (100 wt%) . A stock cathode composition can also be prepared with the N, N'-substituted piperazine in one or more compatible solvents, such as, for example, where the N, N'-substituted piperazine is present in an amount in the range of about 30% (wt) to about 99% (wt) . The solvent may be water. The N, N'-substituted piperazine may be in the form of a solid cathode composition, such as in powder or granule form that can be added to an aqueous cathode composition.
DEFINITIONS
Unless stated to the contrary, implicit from the context, or customary in the art, parts and percents are based on weight, and all test methods are current as of the filing date of this disclosure.
The term "composition, " as used herein, includes a mixture of materials, which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition. Any reaction product or decomposition product is typically present in trace or residual amounts.
The term "cathode composition, " as used herein, includes a mixture of materials, which comprise the cathode composition, as well as reaction products and decomposition products formed from the materials of the cathode composition. Any reaction product or decomposition product is typically present in trace or residual amounts.
The term "polymer, " as used herein, refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus includes the term homopolymer (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure) , and the term interpolymer as defined hereinafter. Trace amounts of impurities, such as catalyst residues, can be incorporated into and/or within the polymer. Typically, a polymer is stabilized with very low amounts ( “ppm” amounts) of one or more stabilizers.
The term "interpolymer, " as used herein, refers to a polymer prepared by the polymerization of at least two different types of monomers. The term interpolymer thus includes the term copolymer (employed to refer to polymers prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.
The term “lithium phosphate compound, ” as used herein, refers to a compound comprising at least one lithium cation (Li+1) and at least one phosphate anion (PO4 -3) . Typically such a compound also comprises at least one other cation, such as a metal cation.
The term “slurry, ” as used herein, refers to a mixture comprising one or more insoluble materials, such as particles, suspended in a solvent, such as water. The mixture may also comprise one or more soluble materials, such as glucose, dissolved in the solvent, such as water.
The term “solvent, ” as used herein, refers to a liquid substance of one or more compounds capable of dissolving and/or dispersing one or more other substances.
The term “carbon coated particles, ” as used herein, refers to particles coated with a layer of carbon. Typically, 50%or more of the surface area of the particles is coated with carbon. Preferably, 90%or more of the surface area of the particles is coated with carbon.
The term “cathode, ” as used herein in reference to a battery, refers to an electrode through which current flows out, in a polarized electrical device.
The term “anode, ” as used herein in reference to a battery, refers to an electrode in a polarized electrical device, through which current flows in, from an outside circuit.
The term “active layer, ” in reference to an electrode, refers to a layer that adheres to the current collector, thus enabling the transport of electrons.
The term “conductive agent, ” as used herein in reference to a cathode composition, refers to a material (for example, a carbon material) added to the composition to increase the ability of the active layer to charge and discharge electrons.
The term “binder, ” as used herein in reference to a cathode composition, refers to a material (for example, a polymer) added to the composition to provide adhesion of the components within the active layer and with the metal foil.
The term “dispersant, ” as used herein in reference to a cathode composition, refers to a substance, that is typically added to a suspension of solid or liquid particles, in a liquid (such as a slurry or an emulsion) , to improve the separation of the particles and to prevent their settling or clumping.
The term “dispersant for conductive agent in reference to a cathode composition, ” as used herein in reference to a cathode composition, refers to a substance, used improve the separation of a conductive agent within the composition and to prevent the settling or clumping of the conductive agent.
The phrase “the cathode composition is coated onto one planar surface of the metal foil” and similar phrases, used herein in reference to the process of preparing a cathode, refer to the act of contacting the metal surface with the cathode composition. This contact may occur by wetting the metal surface with the cathode composition using a brush, a spray, a roller, or by any other means known in the art.
The term “planar surface, 'in reference to a metal foil of certain width, length and thickness, or of certain diameter and thickness, or other dimensions, refers to the surface area formed by the width and length, or the surface area formed by the diameter, or the surface area formed from the larger dimensions of the foil.
The term, “cathode assembly, ” as used herein, refers to battery component that comprises one or more cathodes.
The term “electrolyte, ” as used herein, in reference to a battery, refers to a solution capable of carrying ions back and forth between a cathode and an anode of a battery.
The term “electrochemical cell, ” as used herein, refers to a device that generates electrical energy from chemical energy. Electrical energy can also be applied to these cells to cause one or more chemical reactions to occur.
The term “battery, ” as used herein, refers to a container containing one or more electrochemical cells, in which chemical energy is converted to electrical energy.
The term “lithium battery, ” as used herein, refers to a battery that uses a lithium source in one or more electrochemical cells. Examples of lithium batteries include, but are not limited to, a lithium-ion battery, a lithium metal battery, a lithium-sulfur battery, a lithium-selenium battery, or a lithium-air battery.
The term “water, ” as used herein, refers to H2O. Such a water (H2O) is virtually pure water, and as such, may or may not contain one or more impurities, such as, for example, dissolved inorganic ions. Typically, the impurities are present in an amount ≤ 1000 ppm, preferably ≤ 100 ppm, more preferably ≤ 10 ppm, more preferably ≤ 1 ppm, based on the weight of a sample of the water.
The terms “thermally treating, ” “thermally treated, ” “thermal treatment, ” and similar terms, as used herein, in reference to a cathode composition or a compound or a coated foil, each as discussed herein, refer to increasing the temperature of the “material at issue” by application of heat. As an example, heat may be applied, for example, by electrical means (for example, a heating coil in an oven) . Note, the temperature at which the thermal treatment takes place, refers to the temperature of the “heat-applying” device, or, if the device contains an enclosed or semi-enclosed atmosphere, the temperature of the atmosphere within the device, such as, for example, the atmosphere within an oven or a tunnel (for example, the air temperature in an hot air oven or a hot air tunnel) .
The terms "comprising, " "including, " "having, " and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether the same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, "consisting essentially of” excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability. The term "consisting of” excludes any component, step or procedure, not specifically delineated or listed.
Listing of Some Cathode composition and Process Features
A] A cathode composition comprising at least the following components a) and b) :
a) at least one lithium phosphate compound,
b) at least one dispersant selected from the following Structure 1:
wherein R1 and R2 are each independently a C1-C6 alkylene.
B] The cathode composition of A] above, wherein the cathode composition is a slurry.
C] The cathode composition of A] or B] above, wherein, for component b, Structure 1, R1 = R2.
D] The cathode composition of any one ofA] -C] (A] through C] ) above, wherein, for component b, Structure 1, R1 is a C1-C5 alkylene, or a C1-C4 alkylene, or a C1-C3 alkylene, or a C1-C2 alkylene, or a C2 alkylene.
E] The cathode composition of any one of A] -D] above, wherein, for component b, Structure 1, R2 is a C1-C5 alkylene, or a C1-C4 alkylene, or a C1-C3 alkylene, or a C1-C2 alkylene, or a C2 alkylene.
F] The cathode composition of any one of A] -E] above, wherein component b is selected from Structures lb) , as shown below:
1b) wherein n is an integer from 1 to 6, or from 1 to 5, or from 1 to 4, or from 2 to 4, or from 2 to 3, or 2; and m is an integer from 1 to 6, or from 1 to 5, or from 1 to 4, or from 2 to 4, or from 2 to 3, or 2.
G] The cathode composition of F] above, wherein component b is selected from Structure 1b) , as shown above, and or n = m, or n = m = 2 or 3, or n= m= 2.
H] The cathode composition of any one of A] -G] above, wherein component a is selected from lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, or a combination thereof.
I] The cathode composition of H] above, wherein component a is lithium iron phosphate.
J] The cathode composition of any one of A] -I] above, wherein component a is in particle form.
K] The cathode composition of J] above, wherein the cathode composition further comprises a carbon coating over the particles of component a, to form carbon coated particles.
L] The cathode composition of K] above, wherein the carbon coated particles comprise ≥ 80 wt%, or ≥ 85 wt%, or ≥ 90 wt%, or ≥ 92 wt%, or ≥ 94 wt%, or ≥ 96 wt%, or ≥ 97 wt%, or ≥ 98 wt%and/or ≤ 100 wt%, or ≤ 99 wt%of lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, or a combination thereof, based on the weight of the carbon coated particles.
M] The cathode composition of K] or L] above, wherein the carbon coated particles comprise ≥ 80 wt%, or ≥ 85 wt%, or ≥ 90 wt%, or ≥ 92 wt%, or ≥ 94 wt%, or ≥ 96 wt%, or ≥ 98 wt%, and/or ≤ 100 wt%, or ≤ 99 wt%of lithium iron phosphate, based on the weight of the carbon coated particles.
N] The cathode composition of any one of K] -M] above, wherein the carbon coated particles are present in an amount ≥ 40 wt%, or ≥ 45 wt%, or ≥ 50 wt%, or ≥ 55 wt%and/or ≤ 90 wt%, or≤ 85 wt%, or≤ 80 wt%, or≤ 75 wt%. or≤ 70 wt%, or≤ 65 wt%, based on the weight of the cathode composition.
O] The cathode composition of any one of K] -N] above, wherein the weight ratio of the carbon coated particles to component b is ≥ 100, or ≥ 150, or ≥ 200, or ≥ 250, or ≥ 300, or ≥ 350, or ≥ 400, or ≥ 450, or ≥ 500 and/or ≤ 700, or ≤ 650, or ≤ 600, or ≤ 550.
P1 The cathode composition of any one of A] -O] above, wherein the component b is present in an amount ≥ 0.05 wt%, or ≥ 0.06 wt%, or ≥ 0.08 wt%, or ≥ 0.10 wt%, or ≥ 0.12 wt%, or ≥  0.14 wt%, or ≥ 0.16 wt%, or ≥ 0.18 wt%, or ≥ 0.20 wt%, based on the weight of the cathode composition.
Q] The cathode composition of any one of A] -P] above, wherein the component b is present in an amount ≤ 1.00 wt%, or ≤ 0.90 wt%, or ≤ 0.80 wt%, or ≤ 0.70 wt%, or ≤ 0.60 wt%, or ≤ 0.50 wt%, or ≤ 0.40 wt%, or ≤ 0.30 wt%, based on the weight of the cathode composition.
R] The cathode composition of any one of A] -Q] above, wherein the weight ratio of component a to component b is ≥ 150, or ≥ 200, or ≥ 250, or ≥ 300, or ≥ 350, or ≥ 400, or ≥ 450, or ≥ 500.
S] The cathode composition of any one of A] -R] above, wherein the weight ratio of component a to component b is ≤ 700, or ≤ 650, or ≤ 600, or ≤ 550.
T] The cathode composition of any one of A] -S] above, wherein the component a is present in an amount ≥ 35%, or ≥ 40 wt%, or ≥ 45 wt%, or ≥ 50 wt%, or ≥ 52 wt%, or ≥ 54 wt%, or ≥ 55 wt%, or ≥ 56 wt%, or ≥ 58 wt%, or ≥ 60 wt%, based on the weight of the cathode composition.
U] The cathode composition of any one of A] -T] above, wherein the component a is present in an amount ≤ 80 wt%, or ≤ 75 wt%, or ≤ 70 wt%, or ≤ 68 wt%, or ≤ 66 wt%, or ≤ 65 wt%, or ≤64 wt%, or ≤ 62 wt%, based on the weight of the cathode composition.
V] The cathode composition of any one of A] -U] above, wherein the cathode composition comprises only one lithium phosphate compound as component a.
W] The cathode composition of any one of A] -V] above, wherein the cathode composition comprises only one dispersant, selected from Structure 1, as component b.
X] The cathode composition of any one of A] -W] above, wherein the cathode composition further comprises a solvent as component c.
Y] The cathode composition of X] above, wherein the solvent (component c) is N-methyl-2-pyrrolidone (NMP) .
Z] The cathode composition of X] or Y] above, wherein the component c is present in an amount ≥ 20.0 wt%, or ≥ 22.0 wt%, or ≥ 25.0 wt%, ≥ 28.0 wt%, or ≥ 30.0 wt%, or ≥ 32.0 wt%, or ≥ 34.0 wt%, or ≥ 36.0 wt%, based on the weight of the cathode composition.
A2] The cathode composition of any one of X] -S] above, wherein the component c is present in an amount ≤ 60.0 wt%, or ≤ 58.0 wt%, or ≤ 56.0 wt%, or ≤ 54.0 wt%, or ≤ 52.0 wt%, or ≤ 50.0 wt%, or ≤ 48.0 wt%, or ≤ 46.0 wt%, or ≤ 44.0 wt%, or ≤ 42.0 wt%, or ≤ 40.0 wt%, or ≤ 38.0 wt%based on the weight of the cathode composition.
B2] The cathode composition of any one of X] -A2] above, wherein the weight ratio of component a to component c is ≥ 1.30, or ≥ 1.35, or ≥ 1.40, or ≥ 1.45, or ≥ 1.50, or ≥ 1.52, or ≥ 1.54, or ≥ 1.56, or ≥ 1.58, or ≥ 1.60.
C2] The cathode composition of any one of X] -B2] above, wherein the weight ratio of component a to component c is ≤ 2.00, or ≤ 1.95, or ≤ 1.90, or ≤ 1.85, or ≤ 1.80, or ≤ 1.78, or ≤1.76, or ≤ 1.74, or ≤ 1.72, or ≤ 1.70, or ≤ 1.68, or ≤ 1.66, or ≤ 1.64, or ≤ 1.62.
D2] The cathode composition of any one of A] -C2] , wherein the cathode composition further comprises at least one conductive agent as component d.
E2] The cathode composition of D2] , wherein component d is carbon black, and further conductive carbon black.
F2] The cathode composition of D2] or E2] above, wherein component d is present in an amount ≥ 0.20 wt%, or ≥ 0.25 wt%, or ≥ 0.30 wt%, ≥ 0.35 wt%, or ≥ 0.40 wt%, or ≥ 0.45 wt%, or ≥ 0.50 wt%, or ≥ 0.55 wt%, or ≥ 0.60 wt%and/or ≤ 1.00 wt%, or ≤ 0.95 wt%, or ≤ 0.90 wt%, or ≤ 0.85 wt%, or ≤ 0.80 wt%, or ≤ 0.75 wt%, or ≤ 0.70 wt%, or ≤ 0.65 wt%, based on the weight of the cathode composition.
G2] The cathode composition of any one of D2] -F2] above, wherein the cathode composition comprises only one conductive agent as component d.
H2] The cathode composition of any one of A] -G2] , wherein the cathode composition further comprises at least one binder as component e.
I2] The cathode composition of H2] , wherein component e is polyvinylidene difluoride.
J2] The cathode composition of H2] or I2] above, wherein component e is present in an amount ≥ 0.50 wt%, or ≥ 0.70 wt%, or ≥ 1.00 wt%, ≥ 1.20 wt%, or ≥ 1.40 wt%, or ≥ 1.60 wt%, or ≥ 1.70 wt%, or ≥ 1.80 wt%and/or ≤ 5.00 wt%, or ≤ 4.50 wt%, or ≤ 4.00 wt%, or ≤ 3.50 wt%, or ≤ 3.00 wt%, or ≤ 2.50 wt%, or ≤ 2.00 wt%, based on the weight of the cathode composition.
K2] The cathode composition of any one of H2] -J2] above, wherein the cathode composition comprises only one binder as component e.
L2] The cathode composition of any one of A] -K2] , wherein the cathode composition further comprises a “dispersant for the conductive agent” as componentf.
M2] The cathode composition of L2] , wherein the component fis polyvinyl pyrrolidone, and further PVP K30.
N2] The cathode composition of L2] or M2] above, wherein component fis present in an amount ≥ 0.020 wt%, or ≥ 0.025 wt%, or ≥ 0.030 wt%, ≥ 0.035 wt%, or ≥ 0.040 wt%, or ≥ 0.045 wt%, or ≥ 0.050 wt%, or ≥ 0.055 wt%, or ≥ 0.060 wt%and/or ≤ 0.100 wt%, or ≤ 0.095 wt%, or ≤ 0.090 wt%, or ≤ 0.085 wt%, or ≤ 0.080 wt%, or ≤ 0.075 wt%, or ≤ 0.070 wt%, or ≤ 0.065 wt%, based on the weight of the cathode composition.
O2] The cathode composition of any one of L2] -N2] above, wherein the cathode composition comprises only one “dispersant for the conductive agent” as componentf
P2] The cathode composition of any one of L2] -O2] above, wherein the weight ratio of component d to component f is ≥ 7.0, or ≥ 7.5, or ≥ 8.0, or ≥ 8.5, or ≥, or 9.0, or ≥ 9.5, or ≥ 10 and/or ≤20, or≤ 18, or≤ 16, or≤ 14, or≤ 12, or≤ 11.
Q2] The cathode composition of any one of A] -P2] above, wherein the sum of components a and b is present in an amount ≥ 40.0 wt%, or ≥ 45.0 wt%, or ≥ 50.0 wt%, or ≥ 52.0 wt%, or ≥ 54.0 wt%, ≥ 56.0 wt%, or ≥ 58.0 wt%, or ≥ 60.0 wt%and/or ≤ 80.0 wt%, or ≤ 78.0 wt%, or ≤76.0 wt%, or ≤ 74.0 wt%, or ≤ 72.0 wt%, or ≤ 70.0 wt%, or ≤ 68.0 wt%, or ≤ 66.0 wt%, based on the weight of the cathode composition.
R2] The cathode composition of any one of X] -Q2] above, wherein the sum of components a, b and c is present in an amount ≥ 80.0 wt%, or ≥ 82.0 wt%, or ≥ 84.0 wt%, or ≥ 86.0 wt%, or ≥88.0 wt%, ≥ 90.0 wt%, or ≥ 92.0 wt%, or ≥ 94.0 wt%, or ≥ 96.0 wt%, or ≥ 97.0 wt%and/or ≤100.0 wt%, or ≤ 99.5 wt%, or ≤ 99.0 wt%, or ≤ 98.5 wt%, or ≤ 98.0 wt%, based on the weight of the cathode composition.
S2] The cathode composition of any one of D2] -R2] above, wherein the sum of components a, b, c and d is present in an amount ≥ 85.00 wt%, or ≥ 88.00 wt%, or ≥ 90.00 wt%, or ≥ 92.00 wt%, or ≥ 94.00 wt%, ≥ 96.00 wt%, or ≥ 97.00 wt%, or ≥ 98.00 wt%and/or ≤ 100.00 wt%, or ≤ 99.50 wt%, or ≤ 99.00 wt%, or ≤ 98.50 wt%, based on the weight of the cathode composition.
T2] The cathode composition of any one of H2] -S2] above, wherein the sum of components a, b, c, d and e is present in an amount ≥ 90.00 wt%, or ≥ 91.00 wt%, or ≥ 92.00 wt%, or ≥ 93.00 wt%, or ≥ 94.00 wt%, ≥ 95.00 wt%, or ≥ 96.00 wt%, or ≥ 97.00 wt%, or ≥ 97.50 wt%, or ≥ 98.00 wt or ≥ 98.50 wt%, ≥ 99.00 wt%and/or ≤ 100.00 wt%, or ≤ 99.98 wt%, based on the weight of the cathode composition.
U2] The cathode composition of any one of A] -T2] above, wherein the cathode composition comprises ≤ 1.0 ppm, or ≤ 0.50 ppm, or ≤ 0.20 ppm, or ≤ 0.10 ppm, or ≤ 0.05 ppm, or ≤ 0.02 ppm, or ≤ 0.01 ppm of an amino alcohol, based on the weight of the cathode composition, and further the cathode composition does not comprise an amino alcohol.
V2] The cathode composition of any one of A] -U2] above, wherein the cathode composition comprises ≤ 1.0 ppm, or ≤ 0.50 ppm, or ≤ 0.20 ppm, or ≤ 0.10 ppm, or ≤ 0.05 ppm, or ≤ 0.02 ppm, or ≤ 0.01 ppm of “2-amino-2-methyl-1-propanol, ” based on the weight of the cathode composition, and further the cathode composition does not comprise a “2-amino-2-methyl-1-propanol. ”
A3] A cathode comprising an active layer formed from the cathode composition of any one of A] -V2] above.
B3] The cathode of A3] , wherein the cathode further comprises a metal foil.
C3] The cathode of B3] above, wherein the metal of the metal foil is selected from, aluminum, aluminum alloy, copper, copper alloy, further from aluminum or copper and further aluminum.
D3] The cathode of B3] or C3] above, wherein the metal has a thickness ≥ 10, or ≥ 12, or ≥ 14 μm and/or ≤ 25, or ≤ 22, or ≤ 20, or ≤ 18, ≤ 16 μm.
E3] The cathode of any one of B3] -D3] above, wherein the cathode composition is coated onto one planar surface of the metal foil, to form a coated foil.
F3] The cathode of E3] above, wherein the coated foil is thermally treated, and further thermally treated to evaporate the solvent to form the active layer over the metal foil.
G3] The cathode of F3] above, wherein the coated foil is thermally treated at a temperature ≥ 50℃, or ≥ 55℃, or ≥ 60℃, or ≥ 65℃, or ≥ 70℃, or ≥ 75℃, or ≥ 80℃ and/or ≤ 120℃ or ≤ 115℃, or ≤ 110℃ or ≤ 105℃, or ≤ 100℃, or ≤ 95℃, or ≤ 90℃, or ≤ 85℃.
H3] The cathode of any one of A3] -G3] above, wherein the cathode is compressed under a pressure.
I3] The cathode of H3] above, wherein the pressure is ≥ 5.0 MT, or ≥ 10 MT, or ≥ 15 MT, or ≥ 20 MT, or ≥ 22 MT, or ≥ 24 MT, or ≥ 26 MT (Millitorr) and/or ≤ 40 MT, or ≤ 38 MT or ≤ 36 MT, or ≤ 34 MT, or ≤ 32 MT, or ≤ 30 MT, or ≤ 28 MT (Millitorr) .
J3] A cathode assembly comprising at least one cathode of any one of A3] -I3] above.
K3] The cathode assembly of J3] above, wherein the assembly comprises at least two cathodes.
L3] A battery comprising the cathode assembly of J3] or K3] above.
M3] The battery of L3] above, wherein the battery is a lithium battery.
A4] A process to form the cathode composition of any one of A] -V2] above, the process comprising mixing at least components a and b.
B4] The process of A4] above, further comprising mixing at least components a, b and c.
C4] The process of B4] , further comprising mixing at least components a, b, c and d.
D4] The process of C4] , further comprising mixing at least components a, b, c, d and e.
E4] The process of any one of A4] -D4] above, wherein the mixing takes place at a rate ≥ 1000, or ≥ 1200, or ≥ 1400, or ≥ 1600, or ≥ 1800, or ≥ 2000, and/or ≤ 5000, or ≤ 4500, or ≤ 4000, or ≤ 3500, or ≤ 3000 rpm.
F4] A process to form a cathode, the process comprising applying to one planar surface of a metal foil, the cathode composition of any one of A] -V2] above, to form a coated foil.
G4] The process of F4] above, wherein the metal of the metal foil is selected from aluminum, aluminum alloy, copper, copper alloy, further from aluminum or copper and further aluminum.
H4] The process of F4] or G4] above, wherein the metal has a thickness ≥ 10, or ≥ 12, or ≥ 14 μm and/or ≤ 25, or ≤ 22, or ≤ 20, or ≤ 18, ≤ 16 μm.
I4] The process of any one of F4] oH4] above, wherein the coated foil is thermally treated, and further thermally treated to evaporate the solvent to form an active layer over the metal foil.
J4] The process of I4] above, wherein the coated foil is thermally treated at a temperature ≥50℃, or ≥ 55℃, or ≥ 60℃, or ≥ 65℃, or ≥ 70℃, or ≥ 75℃, or ≥ 80℃ and/or ≤ 120℃ or ≤ 115℃, or ≤ 110℃ or ≤ 105℃, or ≤ 100℃, or ≤ 95℃, or ≤ 90℃, or ≤ 85℃.
K4] A process to form a cathode assembly, the process comprising compacting under a pressure at least one cathode of any one of A3] -I3] above.
L4] The process of K4] above, wherein the process comprises compacting at least two cathodes.
M4] The process of K4] or L4] above, wherein the pressure is ≥ 5.0 MT, or ≥ 10 MT, or ≥ 15 MT, or ≥ 20 MT, or ≥ 22 MT, or ≥ 24 MT, or ≥ 26 MT (Millitorr) and/or ≤ 40 MT, or ≤ 38 MT or ≤ 36 MT, or ≤ 34 MT, or ≤ 32 MT, or ≤ 30 MT, or ≤ 28 MT (Millitorr) .
N4] A process to form a battery, the process comprising inserting the cathode assembly of J3] or K3] into an electrolyte.
O4] The process of N4] above, wherein the battery is a lithium battery.
EXPERIMENTAL
Reagents are listed in Table 1, and cathode compositions are shown in Table 2.
Table 1: Commercial Reagents
Table 2: Cathode Compositions (LFP slurry formulations)
Preparation of the Cathode compositions (LFP Slurries)
The viscosity of LFP slurry is very sensitive to moisture. Therefore, before the preparation of the cathode composition (slurry) , each component, except for the NMP, was dried in an oven, at 80℃, for 24 hours, under circulating air. The NMP was dried, at room temp, with 5A molecular sieve, to remove the trace amount of water.
The slurry preparation is described in the following steps: 1) the PVDF (2.0 g) was added to NMP (18 g) , and the resulting mixture was thermally treated in an oven set at 50℃, until complete dissolution of the PVDF, to form a “PVDF/NMP” solution; 2) the Super P (SP, 0.060 g) , PVP K30 (PVP, 0.006 g) and NMP (1.194 g) were mixed in a high speed mixer (SPEEDMIXER DAC 150) , at 3000 rpm for three minutes, to form a “SP/PVP/NMP” mixture; 3) the LFP (6.000 g) and NMP (0.940 g) were added to the above “SP/PVP/NMP” mixture, and the resulting mixture was mixed in the high speed mixer, at 3000 rpm, for three minutes, to form a “LFP/SP/PVP/NMP” mixture; 4) the “PVDF/NMP” solution (1.800 g) was added to the above “LFP/SP/PVP/NMP” mixture, and the resulting mixture was mixed in the high speed mixer, at 2000 rpm for two minutes, and then for an additional two minutes, to form a pre-cathode composition; 5) the corresponding amount of dispersant (0.012 g) was added to the above pre-cathode composition according to the Table 2 above, and the slurry was mixed at 2000 rpm for three minutes to form the cathode composition. Note, as a comparison-control, 0.012 g of NMP was added to the pre-cathode composition, and the slurry was mixed at 2000 rpm for three minutes to form the control cathode composition (see CE1) . The viscosity of each cathode composition was examined.
Viscosity of the Cathode composition
The viscosity of each cathode composition (LFP slurry) was measured using a BROOKFIELD CAP 2000+ viscometer. To be specific, 0.5 mL of the cathode composition was put under the spindle (#10) , maintained at 22℃, under ambient atmosphere. The spindle was  rotated at 50 rpm during the determination of the viscosity. The cathode composition was maintained at 22℃ for 30 seconds, and then the motor to the spindle was started. As the spindle rotated, the viscosity data was displayed after of 30 seconds. For each cathode composition, one viscosity measurement was taken. The results are shown in Figure 1.
Corrosion Study
Each dispersant (0.2 g, Piperazine, HEP or Di-HEP) was added to water (19.8 g) , and the resulting mixture was mixed in the high speed mixer at 2000 rpm for three minutes, for complete dissolution of the dispersant. The resulting dispersant solution was “1 wt%dispersant, ” based on the weight of the solution. Next, the LFP particles (0.2 g) were added to the dispersant solution, and the resulting slurry was shaken and stored at room temperature (21 ℃-23℃) , ambient atmosphere, for one week. After storage, the slurry was filtered to remove the LFP particles. The filtrate was examined for the Fe cation concentration (corrosion study) .
For the corrosion study, a Perkin Elmer OPTIMA 5300DV was used for the measurement of Fe cation concentration in each filtrate, as follows. The filtrate (1 g) was added to a 50 ml volumetric flask and dilute with “5 wt%HNO3 in water, ” up to the “50 ml” mark, to form a test solution. The test solution was weighed, mixed well, and analyzed for Fe cation concentration using the following instrument conditions: a) RF power: 1.3 Kw; b) gas flows: Plasma gas -15 L/min. Auxiliary gas -0.2 L/min, Nebulizer gas -0.80 L/min; c) sample delivery -Pump Flow; d) Flow rate of 1.50 ml/min; e) view distance -15.0mm; and f) plasma view -axial. The results are shown in Table 3 below.
Table 3: Corrosion Results
Summary of Results
The viscosity of each cathode composition is shown in Figure 1. The cathode composition containing the AMP (CE2) had a relatively low viscosity, and lower than the control cathode composition CE1. For the cathode compositions containing piperazine (CE3) and HEP (CE4) , the viscosity of LFP slurry has increased 35.9%and 13.9%, respectively, relative to the viscosity of CE1. This indicates that the cathode compositions CE3 and CE4 do not have a good dispersion of the LFP particles, as compared to CE2. Cathode composition IE1, containing Di-HEP, has a drop in viscosity of 12.2%, relative to the viscosity of CE1, and a drop in viscosity of 8.4%, relative to the viscosity of CE2. These results indicate that cathode composition IE1 has a better dispersing performance than that of CE2.
Corrosion is another important issue, because the degradation of the LFP will lead to a performance decrease in the cathode of a battery. According to literature studies, LFP will corrode under an acid environment, and release Fe cations into an electrolyte within a battery. For piperazine and its derivatives, the active hydrogen (s) (N-H) on the ring structure may also contribute to an acidic environment. Herein, the Fe cation concentration is used to demonstrate the corrosion performance of each dispersant. As seen in Table 3, the piperazine resulted in the highest amount of corrosion (4.4 ppm Fe) as compared to HEP and Di-HEP. Both the HEP and Di-HEP showed a significantly lower amount of corrosion, at 1.7 ppm Fe and 1.6 ppm Fe, respectively. These values indicate that the overall corrosion is negligible. Thus, cathode compositions containing Di-HEP can be used to form cathodes that will exhibit negligible corrosion. Also, such cathode compositions will have reduced viscosity compared to cathode compositions containing AMP, piperazine or HEP.

Claims (20)

  1. A cathode composition comprising at least the following components a) and b) :
    a) at least one lithium phosphate compound,
    b) at least one dispersant selected from the following Structure 1:
    wherein R1 and R2 are each independently a C1-C6 alkylene.
  2. The cathode composition of clam 1, wherein the cathode composition is a slurry.
  3. The cathode composition of claim 1 or claim 2, wherein component b is selected from Structures 1b) , as shown below:
    1b) wherein n is an integer from 1 to 6.
  4. The cathode composition of any one of claims 1-3, wherein component a is selected from lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, or a combination thereof.
  5. The cathode composition of claim 4, wherein component a is lithium iron phosphate.
  6. The cathode composition of any one of claims 1-5, wherein the component b is present in an amount from 0.05 wt%to 1.00 wt%, based on the weight of the cathode composition.
  7. The cathode composition of any one of claims 1-6, wherein the weight ratio of component a to component b is from 150 to 700.
  8. The cathode composition of any one of claims 1-7, wherein the cathode composition further comprises a solvent as component c.
  9. The cathode composition of claim 8, wherein the solvent (component c) is N-methyl-2-pyrrolidone (NMP) .
  10. The cathode composition of claim 8 or claim 9, wherein the weight ratio of component a to component c is from 1.30 to 2.00.
  11. The cathode composition of any one of claims 1-10, wherein the cathode composition further comprises at least one conductive agent as component d.
  12. The cathode composition of any one of claims 1-11, wherein the cathode composition further comprises at least one binder as component e.
  13. The cathode composition of any one of claims 1-12, wherein the sum of components a and b is present in an amount from 40.0 wt%to 80.0 wt%, based on the weight of the cathode composition.
  14. The cathode composition of any one of claims 1-13, wherein the sum of components a, b and c is present in an amount from 80.0 wt%to 100.0 wt%, based on the weight of the cathode composition.
  15. The cathode composition of any one of claims 1-14, wherein the sum of components a, b, c and d is present in an amount from 85.00 wt%to 99.50 wt%, based on the weight of the cathode composition.
  16. A cathode comprising an active layer formed from the cathode composition of any one of claims 1-15.
  17. The cathode of claim 16, wherein the cathode further comprises a metal foil.
  18. A cathode assembly comprising at least one cathode of claim 16 or claim 17.
  19. A battery comprising the cathode assembly of claim 18.
  20. A process to form a cathode composition of any one of claims 1-15, the process comprising mixing at least components a and b.
PCT/CN2023/130144 2023-11-07 2023-11-07 Cathode compositions containing piperazine derivatives Pending WO2025097293A1 (en)

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