WO2013066593A1 - Composition pour électrode - Google Patents

Composition pour électrode Download PDF

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Publication number
WO2013066593A1
WO2013066593A1 PCT/US2012/059825 US2012059825W WO2013066593A1 WO 2013066593 A1 WO2013066593 A1 WO 2013066593A1 US 2012059825 W US2012059825 W US 2012059825W WO 2013066593 A1 WO2013066593 A1 WO 2013066593A1
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Prior art keywords
electrode
composition
battery
material composition
carbon nanotubes
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PCT/US2012/059825
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English (en)
Inventor
Gang Xu
Jun Ma
Yan Zhang
Chunliang Qi
Dongmei Wei
Caihong Xing
Yunwang MEI
Haimei ZANG
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CNano Technology Limited
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Priority claimed from US13/285,243 external-priority patent/US9087626B2/en
Priority claimed from US13/437,205 external-priority patent/US20130004657A1/en
Application filed by CNano Technology Limited filed Critical CNano Technology Limited
Publication of WO2013066593A1 publication Critical patent/WO2013066593A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to carbon nanotube-based pastes, compositions of carbon nanotube-enhanced electrodes, and methods of making electrodes for a battery, optionally a Li ion battery.
  • the disclosure relates to an electrode composition for a Li ion battery.
  • Carbon nanotubes have many unique properties stemming from small sizes, cylindrical graphitic structure, and high aspect ratios.
  • a single-walled carbon nanotube (SWCNT) consists of a single graphite, or graphene, sheet wrapped around to form a cylindrical tube.
  • a multiwall carbon nanotube (MWCNT) includes a set of concentrically single layered nanotube placed along the fiber axis with interstitial distance of 0.34 nanometers.
  • Carbon nanotubes have extremely high tensile strength (-150 GPa), high modulus ( ⁇ 1 TPa), good chemical and environmental stability, and high thermal and electrical conductivity.
  • Carbon nanotubes have found many applications, including the preparation of conductive, electromagnetic and microwave absorbing and high-strength composites, fibers, sensors, field emission displays, inks, energy storage and energy conversion devices, radiation sources and nanometer-sized semiconductor devices, probes, and interconnects, etc.
  • Carbon nanotubes are often characterized according to tube diameters. Materials possessing smaller diameters exhibit more surface area and fiber strength; larger diameter nanotubes have a smaller surface area to volume ratio, and the surface area is more accessible than smaller nanotubes due to less entanglement.
  • large diameter nanotubes are often straighter compared to smaller ones; thus large diameter nanotubes extend through more space or volume in a composite matrix.
  • polymers such as poly(vinylpyrrolidone) (PVP), polystyrene sulfonate) (PSS), poly(phenylacetylene) (PAA), poly(meta-phenylenevinylene) (PmPV), polypyrrole (PPy).
  • PVP poly(vinylpyrrolidone)
  • PSS polystyrene sulfonate
  • PAA poly(phenylacetylene)
  • PmPV poly(meta-phenylenevinylene)
  • PPy polypyrrole
  • PBO poly(p-phenylene benzobisoxazole)
  • natural polymers have been used to wrap or coat carbon nanotubes and render them soluble in water or organic solvents.
  • SWCNTs single-walled carbon nanotubes
  • SDS sodium dodecyl sulfate
  • PVP polyvinylpyrrolidone
  • electro-conductive pastes or inks are comprised primarily of polymeric binders which contain or have mixed in lesser amounts of electro-conductive filler such as finely divided particles of metal such as silver, gold, copper, nickel, palladium or platinum and/or carbonaceous materials like carbon black or graphite, and a liquid vehicle.
  • a polymeric binder may attach the conductive filler to a substrate and/or hold the electro-conductive filler in a conductive pattern which serves as a conductive circuit.
  • the liquid vehicle includes solvents (e.g., liquids which dissolve the solid components) as well as non-solvents (e.g.. liquids which do not dissolve the solid components).
  • the liquid vehicle serves as a carrier to help apply or deposit the polymeric binder and electro-conductive filler onto certain substrates.
  • An electro- conductive paste with carbon nanotubes dispersed within is a versatile material wherein carbon nanotubes form low resistance conductive networks.
  • Electrodes for batteries comprising fiber agglomerates having micro-pores and an electrode active material included within the micro-pores; the agglomerates are tangled masses of vapor-grown carbon fibers. VGCF. The carbon fibers are compressed, heated and pulverized to form a battery electrode.
  • U.S.7, 608.362. granted to Samsung SDL discloses a composite cathode active material comprising a large diameter material selected from Li based compounds of Ni, Co, Mn, O, Al.
  • a small diameter active material selected from graphite, hard carbon, carbon black, carbon fiber and carbon nanotubes wherein the weight ratio of the large diameter material to the small diameter material is between about 60:40 to about 90: 10; in some embodiments the pressed density of the large diameter material is from 2.5 to 4.0 g/cm J and the pressed density of the small diameter material is from 1 .0 to 4.0 g/cnr ⁇ U .S.7, 781 , 103, granted to Samsung SDL and co-pending application U.S.2010/0273050 disclose a negative active material for a lithium secondary battery comprising mechanically pulverizing a carbon material and shaping the pulverized material into a spherical shape.
  • Samsung ' s U.S.2008/0038635 discloses an improved active material for a rechargeable lithium battery comprising an active material and a fiber shaped or tube shaped carbon conductive material attached to the surface of the active material wherein the carbon material is present in an amount from about 0.05 to 20 weight %.
  • Sheem and co-workers at Samsung disclosed a Li ion battery cathode wherein MWNT are used as a conducting agent with LiCoOi with a density up to 4 gm/cm J .
  • Liu, et al. disclosed a multiwalled carbon nanotube, WCNT, - LiMn 2 0 4 nanocomposite by a facile sol-gel method.
  • U .S.7.682.750. granted to Foxconn. discloses a lithium ion battery comprising an anode comprising a conductive substrate and at least one carbon nanotube array wherein the array comprises a plurality of MWCNT wherein the nanotubes are parallel to each other and perpendicular to the substrate.
  • Vapor grown carbon fibers have long been used as conductive additives for lithium ion batteries.
  • the required loading of this material in typical Lithium ion battery usually exceeds 3-4%.
  • the VGCF showed hardly any improvement.
  • Nanotek Instruments in U.S.201 0/021 819. 2010/0143798 and 2010/01 76337 disclosed the use of graphene platelets with a thickness less than 50 nm in combination with an electrode active material with a dimension less than 1 micron dispersed in a protective matrix.
  • lithium-cobalt oxide and lithium- manganese oxide are common cathode coatings.
  • lithium-iron phosphate (LFP) particles provide improved safety, longer cycles, and longer operating life. Iron and phosphate are also less expensive than other materials, and their high charge capacities make them a good match for plug-in hybrid applications.
  • PSD particle size distribution
  • Li-ion batteries are a type of rechargeable battery in which lithium ions move from the negative electrode (anode) to the positive electrode (cathode) during discharge, and from the cathode to the anode during charge.
  • the three primary functional components of a lithium-ion battery are the anode, cathode, and electrolyte, for which a variety of materials may be used.
  • the most popular material for the anode is graphite.
  • the cathode is generally one of three materials: a layered oxide (such as lithium cobalt oxide), one based on a polyanion (such as lithium iron phosphate), or a spinel (such as lithium manganese oxide), although materials such as T1S 2 (titanium disulfide) originally were also used.
  • a layered oxide such as lithium cobalt oxide
  • a polyanion such as lithium iron phosphate
  • a spinel such as lithium manganese oxide
  • T1S 2 titanium disulfide
  • the instant invention discloses the use of carbon nanotube-based conductive paste for both the cathode and the anode in a Lithium-ion battery.
  • the carbon nanotubes Once deposited inside the active materials, the carbon nanotubes create conductive networks within particulates, so as to enhance overall conductivity and reduce battery internal resistance.
  • a modified battery can have improved capacity and cycle life owing to the conductive network built by carbon nanotubes.
  • Carbon nanotubes are a new class of conductive materials that can provide much enhanced performance for Lithium ion batteries.
  • the conventional cathode composition can no longer satisfy the requirement due to the specialty of carbon nanotubes versus carbon black.
  • the preferred composition is active material/conductive filler/binder is.
  • this composition will result in poor adhesion of cathode material on its current collector; alternatively, broken coatings when folded or wrapped.
  • the instant invention discloses a carbon nanotube based composition for electrodes that overcomes the deficiencies of the prior art.
  • Carbon nanotube-based compositions and methods of making an electrode for a Li ion battery are disclosed. It is an objective of the instant invention to disclose a composition for preparing an electrode of a lithium ion battery with incorporation of carbon nanotubes with more active material by having less conductive filler loading and less binder loading such that battery performance is enhanced.
  • an enhanced electrode composition uses less binder, such as PVDF, thus allowing more electrode material, absolutely and proportionately, by weight, in the composition, which in-turn improves overall storage capacity.
  • the instant invention discloses that carbon nanotubes with a combination of large and small diameters are used to accommodate different cathode or anode materials of variable sizes. Generally, cathode and/or anode materials with smaller particle sizes tend to have less pore size under compression, while large particles have more pore volume. Small diameter carbon nanotubes fit in the smal l space between small cathode and/or anode particles.
  • a conductive paste based on carbon nanotubes is comprised of carbon nanotubes and preferred amount of liquid vehicle as dispersant and/or binder.
  • liquid vehicle as dispersant and/or binder.
  • PVP and PVDF may undergo strong interaction as shown by N. Chen in "Surface phase morphology and composition of the casting films of PVDF-PVP blend", Polymer, 43, 1429 (2002).
  • the addition of PVP altered the crystallization of PVDF and hence modified its mechanical and adhesion properties.
  • the decreased of PVDF or combined PVP-PVDF can further improve the battery performance by allowing more addition of cathode material, so that improve the total capacity.
  • Figure 1 A illustrates a schematic diagram of coating made of active materials, carbon nanotubes and binder on an aluminum film as an electrode of lithium battery.
  • FIG 1 C illustrate both large and small cathode and/or anode particles in an electrode layer.
  • Figure 2 illustrates a cycle performance of lithium ion battery comprising carbon nanotubes.
  • Figure 3 shows the conductive network formed by CNT coating on LiFeP0 4 observed under scanning electron microscope (SEM)
  • Figure 4 is a schematic of a Li-ion battery showing component parts.
  • Figure 5 is an electron micrograph of intrapenetrating large and small diameter carbon nanotubes.
  • agglomerate refers to microscopic particulate structures of carbon nanotubes; for example, an agglomerate is typically an entangled mass of nanotubes, the mass having diameters between about 0.5 ⁇ to about 5 mm.
  • carbon nanotube means a hollow carbon structure having a diameter of from about 2 to about 100 nm; for purposes herein we mean multi-walled nanotubes exhibiting little to no chirality.
  • CNT(I) refers more specifical ly to nanotubes with diameters between about 5-20 nm; the term “CNT(II) refers more specifically to nanotubes with diameters between about 40- 100 nm.
  • multi-wall carbon nanotube refers to carbon nanotubes wherein graphene layers form more than one concentric cylinders placed along the fiber axis.
  • carbon nanotube-based paste refers to an electro-conductive composite in which an electro-conductive filler is multi-wall carbon nanotubes.
  • composite means a material comprising at least one polymer and at least one multi-wall carbon nanotube and/or agglomerate.
  • dispenser refers to an agent assisting dispersing and stabilizing carbon nanotubes in a composite.
  • carbon nanotube network refers to a structure consisting of nanotubes with a "bi-modal" distribution, a mixture of two different uni-modal diameter distributions or distributions having only a narrow range of diameters.
  • Large diameter carbon nanotubes, CNT(II) serve as the backbone of various conductive paths, while small diameter nanotubes, CNT( l ). serve to connect individual particles.
  • CNT(l) is about 10- 1 5 nm; a range for large diameter nanotubes, CNT(II), is about 50-80 nm.
  • a range of diameters for small CNTs is about 5-20 nm; a range for large diameter nanotubes is about 40- 1 00 nm.
  • Electrode composition refers to the composition of the electrode active material plus any matrix or composite which may be surrounding the electrode active material .
  • Material of a specific "electrode composition” is coated or bonded to a metallic conductor plate which
  • Figure 1 A illustrates a schematic diagram of coating made of active materials 1 , carbon nanotubes, CNT(I) 2 and binder 3 on an aluminum film 4 as an electrode of lithium battery.
  • Figure I B illustrates both large and small cathode particles 1 in an electrode layer, and mixed, large.
  • CNT(II) 5 and small, CNT(l) 2, diameter carbon nanotubes, and binder 3 forming a carbon nanotube network to accommodate an unconventional packing structure and provide alternative conductive paths.
  • Figure 1 C illustrates schematically both large and small graphite anode particles in an electrode layer, and mixed with large, CNT(ll) 5 and small, CNT(l) 2, diameter carbon nanotubes, and binder 3 forming a carbon nanotube network to accommodate an unconventional packing structure and provide alternative conductive paths.
  • Figure 5 is a SEM at 5,000X showing exemplary of intrapenetrating CNT( I) 505 and CNT(II) 510.
  • a solid support wherein said plurality of metal nanoparticles and said support are combined to form a plurality of catalyst nano-agglomerates; and a plurality of multi-walled carbon nanotubes deposited on a plurality of catalyst nano-agglomerates.
  • the agglomerates have sizes from about 0.5 to 10,000 micrometers, wherein carbon nanotubes are in the form of multiwall nanotubes having diameters of about 4 to 100 nra.
  • the size of as-made agglomerates can be reduced by various means.
  • a representative characteristic of these agglomerates is their tap density; the tap density of as-made agglomerates can vary from 0.02 to 0.20 g/cnr' depending upon catalyst, growth condition, process design, etc. Rigid agglomerates tend to have high tap densities, while fluffy ones and single-walled nanotubes have low tap densities.
  • Dispersant serves as an aid for dispersing carbon nanotubes in a solvent. It can be a polar polymeric compound, a surfactant, or high viscosity liquid such as mineral oil or wax. Dispersants used in the current invention include poly(vinylpyrrolidone) (PVP). poly(styrene sulfonate) (PSS).
  • poly(phenylacetylene) PAA
  • poly(meta-phenylenevinylene) PmPV
  • polypyrrole PPy
  • poly(p-phenylene benzobisoxazole) PBO
  • natural polymers amphiphilic materials in aqueous solutions, anionic aliphatic surfactant, sodium dodecyl sulfate (SDS), cyclic lipopeptide biosurfactant.
  • surfactin water-soluble polymers, , poly(vinyl alcohol), PVA. sodium dodecyl sulfate, SDS, n-methylpyrrolidone. polyoxyethylene surfactant. poly(vinylidene fluoride). PVdF.
  • CMC carboxyl methyl cellulose
  • HEC hydroxyl ethyl cellulose
  • PAA polyacrylic acid
  • PVC polyvinyl chloride
  • Polymeric binder choices include the dispersants mentioned as well as polyethylene, polypropylene, polyamide. polyurethane, polyvinyl chloride, polyvinylidene fluoride, thermoplastic polyester resin and combinations thereof.
  • Polyvinylpyrrolidone binds polar molecules extremely well. Depending upon its molecular weight, PVP has different properties when used as a binder or as a dispersing agent such as a thickener. In some embodiments of the instant invention, molecular weights for dispersants and/or binders range between about 9,000 and 1 ,800,000 Daltons; in some embodiments, between about 50,000 to 1 .400,000 Daltons are preferred; in some embodiments between about 55,000 to 80,000 Daltons are preferred.
  • a liquid vehicle may serve as a carrier for carbon nanotubes.
  • Liquid vehicles may be a solvent or a non-solvent, depending upon whether or not a vehicle dissolves solids which are mixed therein.
  • the volatility of a liquid vehicle should not be so high that it vaporizes readily at relatively lo temperatures and pressures such as room temperature and pressure, for instance. 25°C and 1 atm. The volatility, however, should not be so low that a solvent does not vaporize somewhat during paste preparation.
  • drying ' " or removal of excess liquid vehicle refers to promoting the volatilization of those components which can be substantially removed by baking, or vacuum baking or centrifuging or some other de-liquefying process at temperatures below 100 to 200°C.
  • a l iquid vehicle is used to dissolve polymeric dispersant(s) and entrain carbon nanotubes in order to render a composition that is easily applied to a substrate.
  • liquid vehicles include, but are not limited to, water, alcohols, ethers, aromatic hydrocarbons, esters, ketones, n-methyl pyrrolidone and mixtures thereof.
  • water is used as a solvent to dissolve polymers and form liquid vehicles. When combined with specific polymers these aqueous systems can replace solvent based inks while maintaining designated thixotropic properties, as disclosed in U.S.4,427.820, incorporated herein in its entirety by reference.
  • one means of reducing the size of large agglomerates to acceptable size agglomerates is to apply a shear force to an agglomerate; a shear force is one technique to aid with dispersion.
  • Means to apply a shear force include, but are not limited to, milling, sand milling, sonication, grinding, cavitation, or others known to one knowledgeable in the art.
  • carbon nanotubes are first reduced in size by using a jet-miller.
  • the tap density can decrease after dispersion, optionally by milling, to around 0.06 g/cm3 in some embodiments, or 0.04 g/cmf in some embodiments, or 0.02 g/cnf in some embodiments.
  • a colloid mill or sand mill or other technique is then used to provide sufficient shear force to further break up nanotube agglomerates, as required by an application.
  • Carbon nanotubes with diameters of about 50 nm but less than about 100 nm, are known to be straighter than smaller nanotubes; smaller nanotubes are often in the form of entangled agglomerates.
  • small diameter nanotubes are first dispersed into individualized nanotubes in a liquid suspension, such as nMP or water; then large diameter nanotube materials are added directly to the liquid suspension at desired ratio to small diameter nanotubes followed by vigorous agitation and mixing.
  • the resultant paste then contains mixture of both large and small nanotubes crossing each other and forming the desired network in a new paste.
  • Exemplary lithium ion battery active materials comprise lithium based compounds and or mixtures comprising lithium and one or more elements chosen from a list consisting of oxygen, phosphorous, sulphur, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, aluminum, niobium and zirconium and iron.
  • Typical cathode materials include lithium-metal oxides, such as LiCoCb, LiM C ⁇ , and Li(Ni x Mn y Co )02], vanadium oxides, olivines, such as LiFePC>4, and rechargeable lithium oxides.
  • Layered oxides containing cobalt and nickel are materials for lithium-ion batteries also.
  • Exemplary anode materials are lithium, carbon, graphite, l ithium-alloying materials, intermetallics, and silicon and silicon based compounds such as silicon dioxide. Carbonaceous anodes comprising silicon and lithium are utilized anodic materials also. Methods of coating battery materials in combination with a carbon nanotube agglomerate onto anodic or cathodic backing plates such as aluminum or copper, for example, are disclosed as an alternative embodiment of the instant invention.
  • Example 1 Dispersion of carbon nanotubes [CNT(I)] in n-methyl pyrrolidone.
  • Viscosity was taken at 25°C using Brookfield viscometer for each sample and recorded; Hegman scale reading was taken simultaneously. Maximum dispersion was observed after milling for 90 minutes. The fineness of this paste reached better than 1 0 micrometer after 60 minutes of milling. This sample was named as Sample A.
  • a PVDF solution was prepared by placing 10 g of PVDF (HSV900) and 100 g n-methyl pyrrolidone in a 500-mL beaker under constant agitation. After all PVDF was dissolved, designated amount of paste (Sample A) from Example 1 and PVDF solution were mixed under strong agitation of 500- 1 000RPM for 30 minutes. The resultant mixture was named Sample B.
  • Clean aluminum foil was chosen as cathode current collector, and placed on a flat plexiglass. A doctor blade was applied to deposit a thin coating of Sample C of thickness of about 40 micrometer on the surface of aluminum foil. The coated foil was then placed in a dry oven at 1 00°C for 2 hours. The cathode plate was then roll-pressed to form a sheet. A round disk of coated foil was punched out of the foil and placed in a coin battery cell. Lithium metal was used as anode, and the coin cell was sealed after assemble the cathode/separator/anode and injecting electrolyte. The made battery was then tested for various charging and discharging performance.
  • Example 4 Composition comparison between commercial and disclosed electrodes.
  • Example 3 The coated aluminum. Al. foil from Example 3 was further tested for adhesion and anti- crease properties. The foil was folded several times until the coating cracked or peeled off the surface. Table 2 indicates how the coated Al foils can survive multiple folding action. The number represented the number of folding times before the failure occurred.
  • Example 6 Application of carbon nanotube paste on Li-ion battery cathode material
  • a CNT(I) paste comprising 2%CNT and 0.4% PVP k30 was selected to make a Lithium-ion coin battery.
  • LiFeP04 manufactured by Phostech/Sud Chemie was used as cathode material and Lithium foil was used as anode.
  • the cathode materials contains LiFeP04.
  • CNT, PVP, and PVDF was prepared by mixing appropriate amount of LiFePCM, CNT paste and PVDF together with n-methyl pyrrolidone in a warren blender. Coating of such paste was made on an Al foil using a doctor blade followed by drying and compression.
  • Example 7 Life Cycle Evaluation A battery assembled using the method described in Example 3 was tested for cycle life performance under different charging rate.
  • Figure 2 illustrates a carbon nanotube
  • the inventors have discovered, however, that the amount of polymeric binder needed in electro- conductive pastes can be eliminated or significantly reduced when using multiwall carbon nanotubes of the present invention as an electro-conductive filler and various polymers, for example, polyvinylpyrrolidone (PVP), as dispersant. As a result, the inventors have discovered that conductivity of electro-conductive pastes can be significantly improved.
  • PVP polyvinylpyrrolidone
  • an electrode composition comprises carbon nanotube agglomerates; a dispersant; and a liquid vehicle; wherein the carbon nanotube agglomerates are dispersed as defined by a Hegman scale reading of 7 or more; optionally, the carbon nanotubes are multiwall carbon nanotubes; optionally carbon nanotubes are in a spherical agglomerates; optionally, an electrode composition comprises a dispersant selected from a group consisting of poly(vinylpyrrolidone) (PVP), poly(styrene sulfonate) (PSS). poly(phenylacetylene) (PAA), poly(meta-phenylenevinylene) (PmPV).
  • PVP poly(vinylpyrrolidone)
  • PSS poly(styrene sulfonate)
  • PAA poly(phenylacetylene)
  • PmPV poly(meta-phenylenevinylene)
  • polypyrrole polypyrrole
  • PBO poly(p-phenylene benzobisoxazole)
  • natural polymers amphophilic materials in aqueous solutions, anionic aliphatic surfactant, sodium dodecyl sulfate (SDS), cyclic lipopeptide biosurfactant.
  • surfactin water- soluble polymers, carboxyl methyl cellulose, hydroxyl ethyl cellulose. alcohol), PVA, sodium dodecyl sulfate.
  • SDS polyoxyethylene surfactant.
  • an electrode composition comprises a solid state bulk electrical resistivity less than 1 0 " ' ⁇ -cm and a viscosity greater than 5,000 cps; optionally, an electrode composition comprises carbon nanotube agglomerates having a maximum dimension from about 0.5 to about 1000 micrometers; optionally, an electrode composition has carbon nanotubes with a diameter from about 4 to about 1 00 nm; optionally, an electrode composition comprises carbon nanotube agglomerates made in a fluid
  • a method for making an electrode composition comprises the steps: selecting carbon nanotube agglomerates; adding the carbon nanotubes agglomerates to a liquid vehicle to form a suspension; dispersing the carbon nanotubes agglomerates in the suspension; reducing the size of the carbon nanotube agglomerates to a Hegman scale of 7 or less; and removing a portion of the liquid vehicle from the suspension to form a concentrated electrode composition such that the electrode composition has carbon nanotubes present in the range of about 1 to 15% by weight, a bulk electrical resistivity of about 10 " ' ⁇ -cm or less and a viscosity greater than 5.000 cps; optionally, a method further comprises the step of mixing a dispersant with the liquid vehicle before adding the carbon nanotube agglomerates; optionally, a method wherein the dispersing step is performed by a means for dispersing chosen from a group consisting of jet mill, ultra-sonicator, ultrasonics, colloid-mill,
  • an electrode composition consists of multi-walled carbon nanotubes of diameter greater than 4nm; a dispersant chosen from a group consisting of poly(vinylpyrrolidone) (PVP), poly(styrene sulfonate) (PSS), poly(phenylacetylene) (PAA), poly(meta-phenylenevinylene) (PmPV).
  • a dispersant chosen from a group consisting of poly(vinylpyrrolidone) (PVP), poly(styrene sulfonate) (PSS), poly(phenylacetylene) (PAA), poly(meta-phenylenevinylene) (PmPV).
  • polypyrrole polypyrrole
  • PBO poly(p-phenylene benzobisoxazole)
  • natural polymers amphiphil ic materials in aqueous solutions, anionic aliphatic surfactant, sodium dodecyl sulfate (SDS), cyclic lipopeptide biosurfactant, surfactin, water- soluble polymers, carboxyl methyl cellulose, hydroxyl ethyl cellulose, poly(vinyl alcohol).
  • PVA sodium dodecyl sulfate
  • SDS polyoxyethylene surfactant
  • an electrode composition further consists of lithium ion battery electrode materials chosen from a group consisting of lithium, oxygen, phosphorous, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, aluminum, niobium and zirconium and iron wherein the electrode composition is present in a range from about 2% to about 50% by weight and the viscosity is greater than
  • a method of preparing an battery electrode coating using a paste composition as disclosed herein comprises the steps: mixing the paste composition with lithium ion oxide compound materials; coating the paste onto a metallic film to form an electrode for a lithium ion battery and removing excess or at least a portion of the liquid from the coating; optionally, a method further comprises the step of mixing a polymeric binder with a liquid vehicle before mixing the paste composition with lithium ion battery materials: optionally, a method uses a polymeric binder chosen from a group consisting of polyethylene, polypropylene, polyamide.
  • a method utilizes spherical carbon nanotube agglomerates fabricated in a fluidized bed reactor as described in Assignee ' s inventions U.S. 7.563,427, and U.S. Applications 2009/0208708. 2009/0286675, and U.S. 12/5 1 6.1 66.
  • a paste composition as disclosed herein utilizes spherical carbon nanotube agglomerates fabricated in a fluidized bed reactor as described in Assignee ' s inventions U .S. 7.563.427, and U.S. Applications 2009/0208708. 2009/0286675, and U.S. 1 2/5 1 6.166.
  • an electrode material composition, or electrode material, for coating to a metallic current collector or metal conductor for a lithium battery comprises multi- walled carbon nanotubes in an agglomerate; electrode active materials chosen from a group consisting of lithium, oxygen, phosphorous, sulphur, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, graphite, aluminum, niobium, titanium and zirconium and iron; a dispersant chosen from a group consisting of poly(vinylpyrrolidone) (PVP), poly(styrene sulfonate) (PSS).
  • PVP poly(vinylpyrrolidone)
  • PSS poly(styrene sulfonate)
  • poly(phenylacetylene) PAA
  • poly(meta-pheny!enevinylene) PmPV
  • polypyrrole PPy
  • poly(p-phenylene benzobisoxazole) PBO
  • natural polymers amphiphilic materials in aqueous solutions, anionic aliphatic surfactant, sodium dodecyl sulfate (SDS).
  • cycl ic lipopeptide biosurfactant surfactin, water-soluble polymers, carboxyl methyl cellulose, hydroxyl ethyl cellulose, poly(vinyl alcohol), PVA. sodium dodecyl sulfate, SDS. n- methylpyiTolidone.
  • an electrode material composition comprises carbon nanotube agglomerates made in a fluidized bed reactor;
  • a method of preparing an electrode material using the electrode material composition herein disclosed comprises the steps: forming a paste composition comprising carbon nanotube agglomerates, dispersant and polymeric binders; mixing the paste composition with a lithium ion battery active material composition wherein the paste composition is in a range from about 1 % to about 25.0% by weight of the mixed composition: coating the mixed paste composition and active material composition onto a metal conductor: and removing excess volatile components to form an electrode for a lithium ion battery such that after removal of the excess volatile components the active material composition is more than about 80% by weight of the coated paste and battery material composition: optionally, a method wherein the active material composition is more than about 90% by weight of the coated paste and battery material composition after removal of the excess volatile components: optionally, a method further comprising the step of mixing a polymeric binder with a l iquid vehicle before mixing the paste composition with lithium ion battery materials: optionally, a method wherein the polymeric binder is chosen from
  • the lithium ion battery electrode active materials are chosen from a group consisting of lithium, oxygen, phosphorous, sulphur, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, graphite, aluminum, niobium, titanium, and zirconium and iron; optionally, a method wherein the multi-walled carbon nanotube agglomerates, dispersant and polymeric binders are formed into a dry pellet prior to mixing with the lithium ion battery active material composition.
  • a dry pellet comprising carbon nanotube agglomerates, dispersant and polymeric binders is formed to facilitate shipment to a different location where mixing with a liquid vehicle or additional dispersant may be done prior to coating an electrode composition onto a metallic electrical conductor prior to redrying.
  • the catalyst was prepared via co-precipitation of Cu nitrate, Ni nitrate, and Al nitrate.
  • the three nitrates were weighed, and dissolved using deionized water at the molar ratio of Cu:Ni:Al of 3 :7: 1 .
  • a solution containing 20% ammonium bicarbonate was slowly added to the flask under continuous agitation. After the pH reached at 9. at which point the precipitation ceased, the resultant suspension was allowed to digest under constant stirring for l hour. The precipitates were then washed with deionized water followed by filtration, drying and calcination.
  • the resultant catalyst contained 50wt% Ni.
  • Nanotubes were prepared following the procedure described in Example 8 at 680°C using 1 gram of catalyst. A total of 30 g of nanotubes was isolated for a weight yield of 29 times the catalyst. Scan electron micrograph revealed the carbon nanotubes made from this process have average diameters of 80 nm.
  • Example 10 Mixing of large and small nanotubes and electrode preparation
  • CNT (II) were blended with conductive paste containing 5% small nanotubes CNT (I) made from Example 1 at a mass ratio of 3 : 1 40 in a Ross mixer for 5 hours; the ' ⁇ 40 , ' is the mass of the conductive paste comprising 5% CNT(I), resulting in a mixture of two distinct carbon nanotubes, (1) and (II), at a mass ratio of 1 : 11 is 7:3; the proportion of large diameter nanotubes to total nanotube content is 30% by weight.
  • An electrode coating composition was then prepared using paste containing mixed large and small nanotubes with graphite particles, with average diameter of 20 micrometers, together with other necessary binders, such as PVDF.
  • the coating formula was then applied to a Mylar sheet for resistivity measurement, and copper foil to be used as a battery anode.
  • the coated sheet was further subjected to compression under constant pressure, e.g. 10 kg/cm .
  • an electrode composition comprising a portion of large diameter carbon nanotubes and a portion of small diameter carbon nanotubes.
  • "large diameter" CNT. CNT(II) is defined as those nanotubes whose diameter is about 40 nm or greater;
  • small diameter " CNT. CNT(I) is defined as those nanotubes whose diameter is about 20 nm or less.
  • Large diameter nanotubes are typically much longer, at least 1 - 10 micrometers or longer than small diameter nanotubes, forming major conductive pathways.
  • Small diameter CNT ' s serve as "local pathways' " or networks.
  • the portion, by weight, of large diameter CNTs is between about 5% and 50% with small diameter nanotubes ranging from about 50% to about 95%.
  • an electrode material composition for a coating applied to a conductive electrode, one of a cathode or anode, for a battery comprises multi-w alled carbon nanotubes in an agglomerate comprising a first portion of large diameter carbon nanotubes, CNT(U), and a second portion of small diameter carbon nanotubes.
  • CNT(I) such that the weight ratio of the second portion to the combined weight of the first portion and the second portion is between about 0.05 to about 0.50; electrode active materials; dispersant; and polymeric binder such that the polymeric binder is less than about 0.5% to about 5 % by weight of the electrode material composition wherein the electrode active material is in a range of about 30-60% by weight, the total carbon nanotubes are in a range from about 0.2 to about 5% by weight and the dispersant is in a range from about 0.1 to 2% by weight before applying the coating to the electrode; optionally the carbon nanotube agglomerates are made in a fluidized bed reactor; optionally the carbon nanotube agglomerates have a maximum dimension from about 0.5 to about 1 .000 microns; optionally the large diameter carbon nanotubes have a diameter in a range from about 40 nm to about 1 00 nm and the small diameter carbon nanotubes have a diameter in a range from about 5 nm to about 20 nm; optionally
  • a method of preparing an electrode coating material using the electrode material composition of Claim 1 comprises the steps: forming a paste composition comprising carbon nanotube agglomerates, dispersant and polymeric binders; mixing the paste composition with a battery active material composition wherein the paste composition is in a range from about 1 % to about 25% by weight of the mixed composition; coating the mixed paste composition and active material composition onto an electrical conductor; and removing excess volatile components to form an electrode for a battery such that after removal of the excess volatile components the active material composition is more than about 80% by weight of the coated paste and battery material composition and the bulk resistivity of the coating is less than about 10 Ohm-cm for a cathode or 1 Ohm.
  • the active material composition is more than about 90% by weight of the coated paste and battery material composition after removal of the excess volatile components; ; optionally the method further comprises the step of mixing a polymeric binder with a liquid vehicle before mixing the paste composition with lithium ion battery materials; optionally the polymeric binder is chosen from a group consisting of polyethylene, polypropylene, polyamide, polyurethane, polyvinyl chloride, polyvinylidene fluoride, thermoplastic polyester resins, and mixtures thereof and is less than about 5% by weight of the paste composition; optionally the battery electrode active materials are chosen from a group consisting of lithium, oxygen, phosphorous, sulphur, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, graphite, aluminum, niobium, titanium, and zirconium and iron; optionally the multi-walled carbon nanotube agglomerates, dispersant and polymeric binders are formed into a dry pellet prior to mixing with the battery active
  • Carbon nanotube-based compositions and methods of making an electrode for a Li ion battery are disclosed.
  • a composition for preparing an electrode of battery, optionally a lithium ion battery with incorporation of a bi-modal diameter distributed carbon nanotubes with more active material by having less total conductive filler loading, less binder loading , and better electrical contact between conductive filler with active battery materials such that battery performance is enhanced.
  • An electrode material composition for a coating applied to a conductive electrode, one of a cathode or anode, for a battery comprising;
  • multi-walled carbon nanotubes in an agglomerate comprising a first portion of large diameter carbon nanotubes.
  • CNT(ll) and a second portion of small diameter carbon nanotubes, CNT(I), such that the weight ratio of the second portion to the combined weight of the first portion and the second portion is between about 0.05 to about 0.50;
  • the polymeric binder such that the polymeric binder is less than about 0.5% to about 5 % by weight of the electrode material composition wherein the electrode active material is in a range of about 30-60% by weight, the total carbon nanotubes are in a range from about 0.2 to about 5% by weight and the dispersant is in a range from about 0.1 to 2% by weight before applying the coating to the electrode.
  • the paste composition is in a range from about 1 % to about 25% by weight of the mixed composition
  • Concept 1 The method of Concept 9 wherein the polymeric binder is chosen from a group consisting of polyethylene, polypropylene, polyamide, polyurethane, polyvinyl chloride, polyvinylidene fluoride, thermoplastic polyester resins, and mixtures thereof and is less than about 5% by weight of the paste composition.
  • the polymeric binder is chosen from a group consisting of polyethylene, polypropylene, polyamide, polyurethane, polyvinyl chloride, polyvinylidene fluoride, thermoplastic polyester resins, and mixtures thereof and is less than about 5% by weight of the paste composition.

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  • 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

L'invention concerne des compositions à base de nanotubes de carbone et des procédés de fabrication d'une électrode pour batterie au lithium-ion. L'invention concerne une composition permettant de fabriquer une électrode de batterie, éventuellement une batterie au lithium-ion, dans laquelle sont incorporés des nanotubes de carbone à distribution par diamètre bimodale possédant davantage de matériau actif compte tenu de la charge de remplissage conductrice inférieure totale, de la moindre charge de liant et du meilleur contact électrique entre la charge de remplissage et les matériaux actifs de la batterie, d'où meilleur fonctionnement de cette dernière.
PCT/US2012/059825 2011-10-31 2012-10-11 Composition pour électrode WO2013066593A1 (fr)

Applications Claiming Priority (4)

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US13/285,243 US9087626B2 (en) 2011-10-31 2011-10-31 Measuring moisture in a CNT based fluid or paste
US13/285,243 2011-10-31
US13/437,205 US20130004657A1 (en) 2011-01-13 2012-04-02 Enhanced Electrode Composition For Li ion Battery
US13/437,205 2012-04-02

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CN116315455A (zh) * 2023-05-04 2023-06-23 合肥长阳新能源科技有限公司 一种高离子电导率耐高温锂电池隔膜及其制备方法
CN116315455B (zh) * 2023-05-04 2023-08-08 合肥长阳新能源科技有限公司 一种高离子电导率耐高温锂电池隔膜及其制备方法

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