WO2013085509A1 - Composition d'électrode pour pile ion-lithium - Google Patents

Composition d'électrode pour pile ion-lithium Download PDF

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Publication number
WO2013085509A1
WO2013085509A1 PCT/US2011/063826 US2011063826W WO2013085509A1 WO 2013085509 A1 WO2013085509 A1 WO 2013085509A1 US 2011063826 W US2011063826 W US 2011063826W WO 2013085509 A1 WO2013085509 A1 WO 2013085509A1
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WIPO (PCT)
Prior art keywords
composition
material composition
electrode
poly
weight
Prior art date
Application number
PCT/US2011/063826
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English (en)
Inventor
Qi Li
Caihong Xing
Zhaojie Wei
Jun Ma
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CNano Technology Limited
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Priority to PCT/US2011/063826 priority Critical patent/WO2013085509A1/fr
Publication of WO2013085509A1 publication Critical patent/WO2013085509A1/fr

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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
    • H01M4/04—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
    • 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
    • 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 and methods of making an electrode 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.
  • polymers such as poly(vinylpyrrolidone) (PVP), poly(styrene sulfonate) (PSS), poly(phenylacetylene) (PAA), poly(meta-phenylenevinylene) (PmPV), polypyrrole (PPy), poly(p-phenylene benzobisoxazole) (PBO) and 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.
  • U. S.6,528,21 granted to Showa Denko, discloses electrode materials 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 SDI discloses a composite cathode active material comprising a large diameter material selected from Li based compounds of Ni, Co, Mn, O, Al, and a small diameter active material selected from graphite, hard carbon, carbon black, carbon fiber, 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/cm3 and the pressed density of the small diameter material is from 1.0 to 4.0 g/cm3.
  • U.S.7,781,103 granted to Samsung SDI, 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 disclose a Li ion battery cathode wherein MWNT are used as a conducting agent with LiCo02 with a density up to 4 gm/cm3.
  • Sheem and co-workers at Samsung disclose a Li ion battery cathode wherein nanotubes are coated on the surface of active LiCo02 particles using electrostatic heterocaoagulation.
  • Liu, et al. disclose a multiwalled carbon nanotube, MWCNT, - LiMn204 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 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 battery.
  • 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.2010/021819, 2010/0143798 and 2010/0176337 discloses 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-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 TiS 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
  • TiS 2 titanium disulfide
  • Li-ion batteries also contain polymeric binders, conductive additives, separator, and current collectors. Carbon black such as Super- PTM made by Timcal Corporation is usually used as conductive additives.
  • 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 a desire in this writing 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.
  • compositions for preparing a cathode or anode of lithium ion battery with incorporation of carbon nanotubes such that enhanced battery performance by having less conductive filler loading, less binder loading and more active material.
  • the 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 illustrates a schematic diagram of coating made of active materials, 1, carbon nanotubes, 2, and binder, 3, on an aluminum film, 4, as an electrode of lithium battery. Carbon nanotubes, as shown, acted as conductive filler to form electronica conductive path throughout the active material particles, so as to enhance the overall conductivity.
  • Figure 2 illustrates a cycle performance of lithium ion battery comprising carbon nanotubes. Carbon nanotube embedded electrode was shown to have excellent cycle life performance at various charge rate.
  • Figure 3 is Figure 6c from U.S. Application 2009/0286675, showing spherical agglomerates of carbon nanotubes.
  • Figure 4 is a schematic of a Li-ion battery showing component parts.
  • 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.
  • 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.
  • 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 collects or dispenses electrons, or "current”, when a battery is in an active, discharging, or (re)charging state as shown schematically in Figure 4.
  • Concept 9 The method of Concept 6 further comprising the step of mixing a polymeric binder with a liquid vehicle before mixing the paste composition with lithium ion battery materials.
  • Concept 10 The method of Concept 8 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.

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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 porte sur des compositions à base de nanotubes de carbone et sur des procédés permettant de fabriquer une électrode pour pile ion-lithium. L'invention se rapporte également à une composition qui permet de préparer une électrode de pile ion-lithium comprenant des nanotubes de carbone et, par une teneur réduite en charge conductrice et en liant, une matière plus active, de sorte que la performance de la pile s'en trouve améliorée.
PCT/US2011/063826 2011-12-07 2011-12-07 Composition d'électrode pour pile ion-lithium WO2013085509A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US2011/063826 WO2013085509A1 (fr) 2011-12-07 2011-12-07 Composition d'électrode pour pile ion-lithium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2011/063826 WO2013085509A1 (fr) 2011-12-07 2011-12-07 Composition d'électrode pour pile ion-lithium

Publications (1)

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WO2013085509A1 true WO2013085509A1 (fr) 2013-06-13

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107146886A (zh) * 2017-05-08 2017-09-08 喻思皓 一种钒电池结构及电极处理工艺
CN109346683A (zh) * 2018-08-29 2019-02-15 中南大学 一种包含空心球状颗粒的锂离子电池负极材料的制备方法
CN109494360A (zh) * 2018-10-26 2019-03-19 合肥国轩高科动力能源有限公司 一种氧化亚硅复合材料及其制备方法
CN109860538A (zh) * 2018-12-20 2019-06-07 天津市捷威动力工业有限公司 一种锂电池硅碳负极浆料及其制备方法、锂离子电池
CN109935792A (zh) * 2017-12-15 2019-06-25 东莞市凯金新能源科技股份有限公司 低成本锂离子电池负极材料复合表面改性方法
CN111313005A (zh) * 2020-02-29 2020-06-19 江西远东电池有限公司 一种硅碳负极合浆方法
CN112909250A (zh) * 2019-11-19 2021-06-04 中能中科（天津）新能源科技有限公司 碳材料微球、锂碳粉及其制备方法和应用
WO2021198853A1 (fr) * 2020-03-31 2021-10-07 Tvs Motor Company Limited Anode métallique pour batteries au lithium-ion
CN113937292A (zh) * 2021-09-02 2022-01-14 深圳市拓邦锂电池有限公司 电极抑制剂及其应用、电池极片的制备方法
US20220352523A1 (en) * 2021-04-28 2022-11-03 GM Global Technology Operations LLC Method and apparatus for fabricating an electrode for a battery
EP3959765A4 (fr) * 2019-04-26 2023-03-08 Dow Global Technologies LLC Polyvinylpyrrolidone en tant que dispersant pour production de cathode de batterie au lithium-ion

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US20090098457A1 (en) * 2007-10-15 2009-04-16 Samsung Electronics Co., Ltd. Electrode for secondary battery, manufacturing method thereof and secondary battery employing the same
US20090181309A1 (en) * 2008-01-15 2009-07-16 Samsung Electronics Co., Ltd. Electrode, lithium battery, method of manufacturing electrode, and composition for coating electrode
US20110171364A1 (en) * 2010-01-13 2011-07-14 CNano Technology Limited Carbon Nanotube Based Pastes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090098457A1 (en) * 2007-10-15 2009-04-16 Samsung Electronics Co., Ltd. Electrode for secondary battery, manufacturing method thereof and secondary battery employing the same
US20090181309A1 (en) * 2008-01-15 2009-07-16 Samsung Electronics Co., Ltd. Electrode, lithium battery, method of manufacturing electrode, and composition for coating electrode
US20110171364A1 (en) * 2010-01-13 2011-07-14 CNano Technology Limited Carbon Nanotube Based Pastes
US20110171371A1 (en) * 2010-01-13 2011-07-14 CNano Technology Limited Enhanced Electrode Composition for Li ion Battery

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107146886A (zh) * 2017-05-08 2017-09-08 喻思皓 一种钒电池结构及电极处理工艺
CN109935792B (zh) * 2017-12-15 2021-08-06 广东凯金新能源科技股份有限公司 锂离子电池负极材料复合表面改性方法
CN109935792A (zh) * 2017-12-15 2019-06-25 东莞市凯金新能源科技股份有限公司 低成本锂离子电池负极材料复合表面改性方法
CN109346683A (zh) * 2018-08-29 2019-02-15 中南大学 一种包含空心球状颗粒的锂离子电池负极材料的制备方法
CN109494360A (zh) * 2018-10-26 2019-03-19 合肥国轩高科动力能源有限公司 一种氧化亚硅复合材料及其制备方法
CN109494360B (zh) * 2018-10-26 2021-12-14 合肥国轩高科动力能源有限公司 一种氧化亚硅复合材料及其制备方法
CN109860538B (zh) * 2018-12-20 2022-07-29 天津市捷威动力工业有限公司 一种锂电池硅碳负极浆料及其制备方法、锂离子电池
CN109860538A (zh) * 2018-12-20 2019-06-07 天津市捷威动力工业有限公司 一种锂电池硅碳负极浆料及其制备方法、锂离子电池
EP3959765A4 (fr) * 2019-04-26 2023-03-08 Dow Global Technologies LLC Polyvinylpyrrolidone en tant que dispersant pour production de cathode de batterie au lithium-ion
CN112909250A (zh) * 2019-11-19 2021-06-04 中能中科（天津）新能源科技有限公司 碳材料微球、锂碳粉及其制备方法和应用
CN112909250B (zh) * 2019-11-19 2022-04-26 中能中科（天津）新能源科技有限公司 碳材料微球、锂碳粉及其制备方法和应用
CN111313005A (zh) * 2020-02-29 2020-06-19 江西远东电池有限公司 一种硅碳负极合浆方法
WO2021198853A1 (fr) * 2020-03-31 2021-10-07 Tvs Motor Company Limited Anode métallique pour batteries au lithium-ion
US20220352523A1 (en) * 2021-04-28 2022-11-03 GM Global Technology Operations LLC Method and apparatus for fabricating an electrode for a battery
US11735744B2 (en) * 2021-04-28 2023-08-22 GM Global Technology Operations LLC Method and apparatus for fabricating an electrode for a battery
CN113937292A (zh) * 2021-09-02 2022-01-14 深圳市拓邦锂电池有限公司 电极抑制剂及其应用、电池极片的制备方法
CN113937292B (zh) * 2021-09-02 2024-03-08 深圳市拓邦锂电池有限公司 电极抑制剂及其应用、电池极片的制备方法

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