US20110086268A1 - Electrodes including polyacrylate binders and methods of making and using the same - Google Patents

Electrodes including polyacrylate binders and methods of making and using the same Download PDF

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US20110086268A1
US20110086268A1 US12/968,738 US96873810A US2011086268A1 US 20110086268 A1 US20110086268 A1 US 20110086268A1 US 96873810 A US96873810 A US 96873810A US 2011086268 A1 US2011086268 A1 US 2011086268A1
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lithium
electrochemical cell
electrode
active material
powdered
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Dinh Ba Le
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Amperex Technology Ltd
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3M Innovative Properties Co
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621Binders
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0402Methods of deposition of the material
    • H01M4/0404Methods of deposition of the material by coating on electrode collectors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134Electrodes based on metals, Si or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1395Processes of manufacture of electrodes based on metals, Si or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386Silicon or alloys based on silicon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387Tin or alloys based on tin
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621Binders
    • H01M4/622Binders being polymers
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00Metal working
    • Y10T29/49Method of mechanical manufacture
    • Y10T29/49002Electrical device making
    • Y10T29/49108Electric battery cell making
    • Y10T29/49115Electric battery cell making including coating or impregnating

Definitions

  • This invention relates to electrode binders for electrochemical cells and to electrodes containing such binders.
  • Powdered alloys of main group elements and conductive powders such as carbon black have been used to make electrodes for lithium-ion cells in a process that involves mixing the powdered active ingredients with a polymeric binder such as polyvinylidene fluoride.
  • the mixed ingredients are prepared as a dispersion in a solvent for the polymeric binder, and coated onto a metal foil substrate, or current collector.
  • the resulting composite electrode contains the powdered active ingredient in the binder, adhered to the metal substrate.
  • the first cycle irreversible capacity loss in the resulting cells can be unacceptably large, e.g., as large as 300 mAh/g or more for an electrode based on a powdered metal material.
  • Secondary electrochemical cells such as lithium-ion cells, are capable of being reversibly charged and discharged multiple times.
  • the charging and the discharging of the lithium-ion electrochemical cells are accomplished by lithiating and delithiating the cell electrodes.
  • lithium-ion cells When lithium-ion cells are constructed, they usually contain excess lithium-ions in the positive electrode and no lithium-ions in the negative electrode.
  • lithium-ion cells When lithium-ion cells are constructed, they usually contain excess lithium-ions in the positive electrode and no lithium-ions in the negative electrode.
  • lithium-ion cells When the initial cycling reaction of the cells (charging), lithium transfers from the positive electrode to the negative electrode until the negative electrode has reached its capacity of absorbing lithium-ions.
  • the lithium-ions migrate from the lithiated negative electrode back to the positive electrode.
  • a desirable lithium-ion cell is one that has low irreversible capacity loss after the initial cycling, and has low capacity loss (fade) after multiple cycles.
  • this invention provides an electrode composition that comprises a powdered material capable of undergoing lithiation and delithiation.
  • the electrode composition includes a non-elastomeric binder that includes lithium polyacrylate.
  • this invention provides an electrochemical cell that comprises a positive electrode, a negative electrode, and an electrolyte.
  • the negative electrode, the positive electrode, or both electrodes include a powdered material capable of undergoing lithiation and delithiation and a non-elastomeric binder that includes lithium polyacrylate.
  • this invention provides a method of making an electrochemical cell electrode that includes providing a current collector, providing a powdered material capable of undergoing lithiation and delithiation, and applying to the current collector a coating that includes the powdered material and lithium polyacrylate.
  • lithium polyacrylate as a binder provides reduced irreversible capacity and fade.
  • the irreversible first cycle capacity loss in these electrodes can be significantly decreased by forming the electrode using a lithium polyacrylate binder.
  • a binder which can be prepared by neutralizing poly(acrylic acid) with lithium hydroxide
  • Such a binder can be used to prepare electrodes and cells that experience decreased first cycle irreversible capacity loss compared to electrodes or cells made with conventional polymeric binders.
  • the disclosed electrodes containing lithium polyacrylate binders can improve cycle life in rechargeable lithium-ion cells employing electrodes based on small particle alloy powders.
  • the disclosed binders can also allow fabrication of rechargeable lithium-ion cells having improved capacities or employing novel alloy powders.
  • metal refers to both metals and to metalloids such as silicon and germanium, whether in an elemental or ionic state;
  • alloy refers to a mixture of two or more metals
  • lithiumate and “lithiation” refer to a process for adding lithium to an electrode material
  • delivery and “delithiation” refer to a process for removing lithium from an electrode material
  • active refers to a material that can undergo lithiation and delithiation
  • charge and “charging” refer to a process for providing electrochemical energy to a cell
  • discharge and “discharging” refer to a process for removing electrochemical energy from a cell, e.g., when using the cell to perform desired work;
  • positive electrode refers to an electrode (often called a cathode) where electrochemical reduction and lithiation occurs during a discharging process
  • negative electrode refers to an electrode (often called an anode) where electrochemical oxidation and delithiation occurs during a discharging process.
  • aliphatic cycloaliphatic and “aromatic” include substituted and unsubstituted moieties containing only carbon and hydrogen, moieties that contain carbon, hydrogen and other atoms (e.g., nitrogen or oxygen ring atoms), and moieties that are substituted with atoms or groups that may contain carbon, hydrogen or other atoms (e.g., halogen atoms, alkyl groups, ester groups, ether groups, amide groups, hydroxyl groups or amine groups).
  • Electrode compositions according to the present invention may be used in negative or positive electrodes.
  • a variety of powdered materials can be employed to make the electrode compositions.
  • Exemplary powdered materials can for example contain silicon, silver, lithium, tin, bismuth, lead, antimony, germanium, zinc, gold, platinum, palladium, arsenic, aluminum, gallium, indium, thallium, molybdenum, niobium, tungsten, tantalum, iron, copper, titanium, vanadium, chromium, nickel, cobalt, zirconium, yttrium, a lanthanide, an actinide or an alloy containing any of the foregoing metals or metalloids and other powdered active metals and metalloids that will be familiar to those skilled in the art.
  • Graphitic carbon powder can also be used to make the disclosed electrode compositions.
  • Exemplary powders can have a maximum length in one dimension that is no greater than 60 ⁇ m, no greater than 40 ⁇ m, or no greater than 20 ⁇ m, or even smaller.
  • the powders can, for example, have a maximum particle diameter that is submicron, at least 1 ⁇ m, at least 2 ⁇ m, at least 5 ⁇ m, or at least 10 ⁇ m or even larger.
  • suitable powders often have a maximum dimension of 1 to 60 ⁇ m, 10 to 60 ⁇ m, 20 to 60 ⁇ m, 40 to 60 ⁇ m, 1 to 40 ⁇ m, 2 to 40 ⁇ m, 10 to 40 ⁇ m, 5 to 20 ⁇ m, or 10 to 20 ⁇ m.
  • the powdered materials can contain optional matrix formers within powder particles.
  • Each phase originally present in the particle can be in contact with the other phases in the particle.
  • a silicon phase can be in contact with both a copper silicide phase and a silver or silver alloy phase.
  • Each phase in a particle can for example have a grain size less than 500 ⁇ , less than 400 ⁇ , less than 300 ⁇ , less than 200 ⁇ , less than 150 ⁇ , or even smaller.
  • Exemplary silicon-containing powdered materials useful in this invention include the silicon alloys wherein the powdered material comprises from about 65 to about 85 mole percent silicon, from about 5 to about 12 mole percent iron, from about to about 12 mole percent titanium, and from about 5 to about 12 mole percent carbon. Additional examples of useful silicon alloys include compositions that include silicon, copper, and silver or silver alloy such as those discussed in U.S. Pat. Appl. Publ. No. 2006/0046144 A1 (Obrovac et al); multiphase, silicon-containing electrodes such as those discussed in U.S. Pat. No.
  • lithium alloys such as Li 4/3 Ti 5/3 O 4 , LiV 3 O 8 , LiV 2 O 5 , LiCo 0.2 Ni 0.8 O 2 , LiNiO 2 , LiFePO 4 , LiMnPO 4 , LiCoPO 4 , LiMn 2 O 4 , and LiCoO 2 ; lithium atoms intercalated within a lithium transition metal oxide such as lithium cobalt dioxide, lithium nickel dioxide, and lithium manganese dioxide; the lithium alloy compositions that include mixed metal oxides of cobalt, manganese, and nickel such as those described in U.S. Pat. Nos. 6,964,828 and 7,078128 (Lu et al); 6,203,944 (Turner); and 6,680,145 B2 (Obrovac et al.).
  • Exemplary powdered materials useful for making negative electrodes of his invention include U.S. Pat. No. 6,699,336 B2 (Turner et al.); U.S. Pat. Appl. Publ. No. 2003/0211390 A1 (Dahn et al.); U.S. Pat. Nos. 6,255,017 B1 (Turner) and 6,436,578 B2 (Turner et al.); graphitic carbon that exists in forms such as powders, flakes, fibers or spheres (e.g., mesocarbon microbeads (MCMB)); combinations thereof and other powdered materials that will be familiar to those skilled in the art.
  • MCMB mesocarbon microbeads
  • Powdered alloy particles may include a conductive coating.
  • a particle that contains silicon, copper, and silver or a silver alloy can be coated with a layer of conducting material (e.g., with the alloy composition in the particle core and the conductive material in the particle shell).
  • Suitable conductive materials include, for example, carbon, copper, silver, or nickel.
  • Exemplary powdered alloy materials can be prepared by any known means, for example, by physically mixing and then milling the various precursor components to the alloys.
  • the mixing can be by simple blending or by using a melt spinning process.
  • ingots containing the alloy composition can be melted in a radio frequency field and then ejected through a nozzle onto a surface of a rotating wheel (e.g., a copper wheel). Because the surface temperature of the rotating wheel is substantially lower than the temperature of the melted alloy, contact with the surface of the rotating wheel quenches the melt. Quenching minimizes the formation of large crystallites that can be detrimental to electrode performance.
  • conductive coatings When conductive coatings are employed, they can be formed using techniques such as electroplating, chemical vapor deposition, vacuum evaporation or sputtering. Suitable milling can be done by using various techniques such as vertical ball milling, horizontal ball milling or other milling techniques known to those skilled in the art.
  • the electrode composition can contain additives such as will be familiar to those skilled in the art.
  • the electrode composition can include an electrically conductive diluent to facilitate electron transfer from the powdered material to a current collector.
  • Electrically conductive diluents include, but are not limited to, carbon (e.g., carbon black for negative electrodes and carbon black, flake graphite and the like for positive electrodes), metal, metal nitrides, metal carbides, metal silicides, and metal borides.
  • Representative electrically conductive carbon diluents include carbon blacks such as SUPER P and SUPER S carbon blacks (both from MMM Carbon, Belgium), SHAWANIGAN BLACK (Chevron Chemical Co., Houston, Tex.), acetylene black, furnace black, lamp black, graphite, carbon fibers and combinations thereof.
  • carbon blacks such as SUPER P and SUPER S carbon blacks (both from MMM Carbon, Belgium), SHAWANIGAN BLACK (Chevron Chemical Co., Houston, Tex.), acetylene black, furnace black, lamp black, graphite, carbon fibers and combinations thereof.
  • the electrode composition can include an adhesion promoter that promotes adhesion of the powdered material or electrically conductive diluent to the binder.
  • the combination of an adhesion promoter and binder can help the electrode composition better accommodate volume changes that can occur in the powdered material during repeated lithiation/delithiation cycles.
  • the disclosed binders can offer sufficiently good adhesion to metals and alloys so that addition of an adhesion promoter may not be needed.
  • an adhesion promoter can be made a part of the lithium polyacrylate binder (e.g., in the form of an added functional group), can be a coating on the powdered material, can be added to the electrically conductive diluent, or can be a combination of such measures.
  • adhesion promoters include silanes, titanates, and phosphonates as described in U.S. Pat. Appl. Publ. No. 2004/0058240 A1 (Christensen), the disclosure of which is incorporated herein by reference.
  • the binders of this invention contain lithium polyacrylate.
  • Lithium polyacrylate can be made from poly(acrylic acid) that is neutralized with lithium hydroxide.
  • poly(acrylic acid) includes any polymer or copolymer of acrylic acid or methacrylic acid or their derivatives where at least about 50 mole %, at least about 60 mole %, at least about 70 mole %, at least about 80 mole %, or at least about 90 mole % of the copolymer is made using acrylic acid or methacrylic acid.
  • Useful monomers that can be used to form these copolymers include, for example, alkyl esters of acrylic or methacrylic acid that have alkyl groups with 1-12 carbon atoms (branched or unbranched), acrylonitriles, acrylamides, N-alkyl acrylamides, N,N-dialkylacrylamides, hydroxyalkylacrylates, and the like.
  • alkyl esters of acrylic or methacrylic acid that have alkyl groups with 1-12 carbon atoms (branched or unbranched), acrylonitriles, acrylamides, N-alkyl acrylamides, N,N-dialkylacrylamides, hydroxyalkylacrylates, and the like.
  • polymers or copolymers of acrylic acid or methacrylic acid that are water soluble—especially after neutralization or partial neutralization. Water solubility is typically a function of the molecular weight of the polymer or copolymer and/or the composition.
  • Poly(acrylic acid) is very water
  • Homopolymers and copolymers of acrylic and methacrylic acid that are useful in this invention can have a molecular weight (M W ) of greater than about 10,000 grams/mole, greater than about 75,000 grams/mole, or even greater than about 450,000 grams/mole or even higher.
  • the homopolymers and copolymer that are useful in this invention have a molecular weight (M W )) of less than about 3,000,000 grams/mole, less than about 500,000 grams/mole, less than about 450,000 grams/mole or even lower.
  • Carboxylic acidic groups on the polymers or copolymers can be neutralized by dissolving the polymers or copolymers in water or another suitable solvent such as tetrahydrofuran, dimethylsulfoxide, N, N-dimethylformamide, or one or more other dipolar aprotic solvents that are miscible with water.
  • the carboxylic acid groups (acrylic acid or methacrylic acid) on the polymers or copolymers can be titrated with an aqueous solution of lithium hydroxide. For example, a solution of 34% poly(acrylic acid) in water can be neutralized by titration with a 20% by weight solution of aqueous lithium hydroxide.
  • the carboxylic acid groups are lithiated (neutralized with lithium hydroxide) on a molar basis.
  • lithiated neutralized with lithium hydroxide
  • the binders of this invention may be blended with other polymeric materials to make a blend of materials. This may be done, for example, to increase the adhesion, to provide enhanced conductivity, to change the thermal properties or to affect other physical properties of the binder.
  • the binders of this invention are non-elastomeric. By non-elastomeric it is meant that the binders do not contain substantial amounts of natural or synthetic rubber. Synthetic rubbers include styrene-butadiene rubbers and latexes of styrene-butadiene rubbers.
  • the binders of this invention contain less than 20% by weight, less than 10% by weight, less than 5% by weight, less than 2% by weight, or even less of natural or synthetic rubber.
  • any selected additives such as binders, conductive diluents, fillers, adhesion promoters, thickening agents for coating viscosity modification such as carboxymethylcellulose and other additives known by those skilled in the art are mixed in a suitable coating solvent such as water or N-methylpyrrolidinone (NMP) to form a coating dispersion or coating mixture.
  • a suitable coating solvent such as water or N-methylpyrrolidinone (NMP)
  • NMP N-methylpyrrolidinone
  • the dispersion is mixed thoroughly and then applied to a foil current collector by any appropriate dispersion coating technique such as knife coating, notched bar coating, dip coating, spray coating, electrospray coating, or gravure coating.
  • the current collectors are typically thin foils of conductive metals such as, for example, copper, aluminum, stainless steel, or nickel foil.
  • the slurry is coated onto the current collector foil and then allowed to dry in air followed usually by drying in a heated oven, typically at about 80° C. to about 300° C. for about an hour to remove all of the solvent.
  • electrolytes can be employed in the disclosed lithium-ion cell.
  • Representative electrolytes contain one or more lithium salts and a charge-carrying medium in the form of a solid, liquid or gel.
  • Exemplary lithium salts are stable in the electrochemical window and temperature range (e.g. from about ⁇ 30° C. to about 70° C.) within which the cell electrodes can operate, are soluble in the chosen charge-carrying media, and perform well in the chosen lithium-ion cell.
  • Exemplary lithium salts include LiPF 6 , LiBF 4 , LiClO 4 , lithium bis(oxalato)borate, LiN(CF 3 SO 2 ) 2 , LiN(C 2 F 5 SO 2 ) 2 , LiAsF 6 , LiC(CF 3 SO 2 ) 3 , and combinations thereof.
  • Exemplary charge-carrying media are stable without freezing or boiling in the electrochemical window and temperature range within which the cell electrodes can operate, are capable of solubilizing sufficient quantities of the lithium salt so that a suitable quantity of charge can be transported from the positive electrode to the negative electrode, and perform well in the chosen lithium-ion cell.
  • Exemplary solid charge carrying media include polymeric media such as polyethylene oxide, polytetrafluoroethylene, polyvinylidene fluoride, fluorine-containing copolymers, polyacrylonitrile, combinations thereof and other solid media that will be familiar to those skilled in the art.
  • Exemplary liquid charge carrying media include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl-methyl carbonate, butylene carbonate, vinylene carbonate, fluoroethylene carbonate, fluoropropylene carbonate, y-butylrolactone, methyl difluoroacetate, ethyl difluoroacetate, dimethoxyethane, diglyme (bis(2-methoxyethyl) ether), tetrahydrofuran, dioxolane, combinations thereof and other media that will be familiar to those skilled in the art.
  • Exemplary charge carrying media gels include those described in U.S. Pat. Nos.
  • the charge carrying media solubilizing power can be improved through addition of a suitable cosolvent.
  • exemplary cosolvents include aromatic materials compatible with Li-ion cells containing the chosen electrolyte.
  • Representative cosolvents include toluene, sulfolane, dimethoxyethane, combinations thereof and other cosolvents that will be familiar to those skilled in the art.
  • the electrolyte can include other additives that will familiar to those skilled in the art.
  • the electrolyte can contain a redox chemical shuttle such as those described in U.S. Pat. Nos.
  • Electrochemical cells of this invention are made by taking at least one each of a positive electrode and a negative electrode as described above and placing them in an electrolyte.
  • a microporous separator such as CELGARD 2400 microporous material, available from Hoechst Celanese, Corp., Charlotte, N.C., is used to prevent the contact of the negative electrode directly with the positive electrode. This is especially important in coin cells such as, for example, 2325 coin cells as known in the art.
  • Electrochemical cells made with the negative electrodes of this invention showed reduced irreversible capacity loss and less fade than similar cells containing negative electrodes with conventional binders.
  • the disclosed cells can be used in a variety of devices, including portable computers, tablet displays, personal digital assistants, mobile telephones, motorized devices (e.g., personal or household appliances and vehicles), instruments, illumination devices (e.g., flashlights) and heating devices.
  • One or more electrochemical cells of this invention can be combined to provide battery pack. Further details regarding the construction and use of rechargeable lithium-ion cells and battery packs will be familiar to those skilled in the art.
  • Si 70 Fe 10 Ti 10 was prepared by melting silicon lumps (65.461 grams)(Alfa Aesar/99.999%, Ward Hill, Mo.), iron pieces (18.596 grams) (Alfa Aesar/99.97%) and titanium sponge (15.943 grams) (Alfa Aesar/99.7%) in an ARC furnace.
  • the alloy ingot of Si 70 Fe 10 Ti 10 was broken into small chinks and was treated in a hammer mill to produce alloy powder particles of approximately 150 micrometers.
  • Si 70 Fe 10 Ti 10 C 10 alloy was made from Si 70 Fe 10 Ti 10 alloy powder (described above) and graphite (TIMREX SFG44, TimCal Ltd., Bodio, Switzerland) by reactive ball milling in a high kinetic ball mill (SIMOLOYER, CM20-201m, Zoz GmbH, Wenden, Germany).
  • SIMOLOYER high kinetic ball mill
  • a sample of 1.4423 kg of Si 70 Fe 10 Ti 10 alloy powder, 0.0577 kg graphite and 25 kg of 4.76 millimeter diameter chromium-steel balls were charged to the mill.
  • the mill was operated for 180 cycles where each cycle consisted of 45 seconds at 550 revolutions per minutes (rpm) and then 15 seconds at 300 rpm.
  • the total milling time was 3 hours.
  • the mill was cooled by chilled water during the milling.
  • Lithium polyacrylate was made by adding an aqueous solution of lithium hydroxide solution to an aqueous poly(acrylic acid) solution. Different molar ratios of lithium hydroxide and carboxylic acid groups were used. Typically a 20 wt % aqueous solution of lithium hydroxide and a 34 wt % aqueous solution of poly (acrylic acid) were used. De-ionized water was added to bring the final solution of lithium polyacrylate to 10 wt % solids. Poly(acrylic acid) of 100,000 (M W ) and 250,000 (M W ) were obtained as aqueous solutions from Aldrich Chemicals, Milwaukee, Wis..
  • KETJEN Black conductive carbon (0.024g) (Akzo Nobel Polymer Chemical LLC, Chicago, Ill.) and PAA100k-64% Li salt (1.36 g of a 10% solids solution in water, were mixed in a 45-mL stainless steel vessel using four 13 micrometer diameter tungsten carbide balls. The mixing was carried out in a planetary micro mill (PULVERSETTE 7 Model; Fritsch, Germany) at a speed setting of 1 for 30 minutes. Then Si 70 Fe 10 Ti 10 C 10 powder (1.20 g), MCMB-1028 graphite (0.64 g) (MMM Carbon, Belgium) and de-ionized water (0.1 g) were added to the mill and the mixing was continued at a speed setting of 2 for 30 minutes. The resulting solution was coated onto a 13-micron thick Cu foil using a die with a 125 ⁇ m gap. The sample was then dried in a vacuum oven at 120° C. for 2 hours.
  • Example 2 in Table 1 An electrode based on the composition of Example 2 in Table 1 was prepared by the procedure used for Example 1 except that only 1.84 grams of Si 70 Fe 10 Ti 10 C 10 powder was added to the milled conductive carbon and polymer mixture. The milled coating solution was coated onto copper foil using a 75 ⁇ m gap.
  • Example 3 An electrode based on the composition of Example 3 in Table 1 was prepared by the procedure used for Example 1 except that Si 70 Fe 10 Ti 10 C 10 powder (1.20 g), SLP30-Graphite (0.64 g) (TIMREX SLP30, TimCal Ltd., CH-6743 Bodio, Switzerland), de-ionized water (1.0 g) and PAA100k-107% Li salt (1.6 g of a 10% solids solution in water) were milled in a single step at a speed setting of 2 for 30 minutes. The milled solution was spread onto the copper foil using a 3 ⁇ m gap.
  • Example 4 of Table l An electrode based on the composition of Example 4 of Table l was prepared by the same procedure used for Example 3, except that only 0.2 grams of de-ionized water was added. The milled solution was spread onto the copper foil using a 3 mil gap.
  • Example 5 of Table 1 An electrode based on the composition of Example 5 of Table 1 was prepared by the same procedure used for Example 3, except that 2.5 grams of de-ionized water was used with the graphite and the poly(acrylic acid) in the milling step. The milled solution was spread onto the copper foil using a 3 mil gap.
  • Electrodes based on the compositions of Example 6 and Example 7 of Table 1 were prepared by the same procedure used for Example 4.
  • Example 8 An electrode based on the composition of Example 8 in Table 1 was prepared by the same procedure used for Example 5.
  • Example 1 Graphite (1.00 gram) (MCMB, Grade 6-28, Osaka Gas Co. Osaka-Shi, Japan), Si 70 Fe 10 Ti 10 C 10 (0.1 gram), polyvinylidene fluoride (KYNAR 741) solution (1.0 gram of a 10% by weight solution in N-methyl pyrrolidinone (NMP)), and NMP (2.5 grams) were mixed in planetary micro mill as described for Example 1. The mixture was coated and dried as in Example 1.
  • Example 1 This mixture (1.90 grams), polyvinylidene fluoride (KYNAR 741) solution (1.0 grams) and NMP (3.0 grams) were mixed in the micro mill of Example 1 at a speed setting of 2 for one hour. The mixture was coated and dried as in Example 1.
  • KYNAR 741 polyvinylidene fluoride
  • Disks (16-mm diameter) were cut from the electrode coatings for use in 2325-button cells.
  • Each 2325 cell contains a 18 mm diameter disk of Cu as a spacer (36-mil (900 ⁇ m) thick), an 18 mm diameter disk of the alloy electrode, one 20 mm diameter microporous separator (CELGARD 2400; Separation Products, Hoechst Celanese Corp., Charlotte, N.C. 28273)), 18 mm diameter lithium (0.38 mm thick lithium ribbon; Aldrich Chemicals, Milwaukee, Wis.) and an 18 mm diameter copper spacer (600 ⁇ m thick).
  • electrolyte solution 1M LiPF 6 in 90wt % ethylene carbonate (EC): diethylene carbonate (DEC) (1:2 v/v) (Ferro Chemicals (Zachary, La.); 10 wt % fluoroethylene carbonate (FEC) (Fujian Chuangxin Science and Technology Development, LTP, Fujian, China)) were mixed and used as the electrolyte.
  • the electrolyte mixture was dried over molecular sieves (3A type) over 12 hrs.
  • the coin cells were charged and discharged from 0.005V to 0.90V with a constant current of 250 mA/g for alloy and alloy/graphite electrodes and with a constant current of 100 mA/g for graphite electrodes.
  • the cell voltage was held constant and the charging continued until the current reached 10 mA/g.
  • the cell was allowed to remain at open circuit for fifteen minutes at the end of every half cycle.
  • the initial charge capacity of each cell was calculated from the measured total milliamp-hours charged until the cell voltage reached 0.005V. The cell was then discharged as described above.
  • the irreversible capacity loss (shown in Table 2) was calculated from the difference between the initial charge capacity and the first discharge capacity divided by the initial capacity times 100.
  • the data in Table 2 show that negative electrodes made using the binders of this invention have less irreversible capacity loss compared with electrodes made with polyvinylidene fluoride binders.
  • the discharge capacity after cycle 5 and after cycle 50 for each cell is provided in Table 3.
  • the data show that cells containing negative electrodes with binders of this invention have less fade after 50 cycles than those made with polyvinylene fluoride binders.

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Abstract

Provided is an electrode composition comprising a powdered material capable of undergoing lithiation and delithiation, and a non-elastomeric binder comprising lithium polyacrylate, along with methods of making and using the same, as well as electrochemical cells incorporating the same.

Description

    CROSS REFERENCE TO RELATED APPLICATIONS
  • This application is a divisional of U.S. Ser. No. 11/671,601, filed Feb. 6, 2007, now allowed, the disclosure of which is incorporated by reference in its entirety herein.
  • FIELD OF THE INVENTION
  • This invention relates to electrode binders for electrochemical cells and to electrodes containing such binders.
  • BACKGROUND
  • Powdered alloys of main group elements and conductive powders such as carbon black have been used to make electrodes for lithium-ion cells in a process that involves mixing the powdered active ingredients with a polymeric binder such as polyvinylidene fluoride. The mixed ingredients are prepared as a dispersion in a solvent for the polymeric binder, and coated onto a metal foil substrate, or current collector. The resulting composite electrode contains the powdered active ingredient in the binder, adhered to the metal substrate.
  • Many polymers such as polyvinylidene fluoride, aromatic and aliphatic polyimides and polyacrylates have been used as binders for metal and graphite based lithium-ion cell electrodes. However, the first cycle irreversible capacity loss in the resulting cells can be unacceptably large, e.g., as large as 300 mAh/g or more for an electrode based on a powdered metal material.
  • Secondary electrochemical cells, such as lithium-ion cells, are capable of being reversibly charged and discharged multiple times. In the case of lithium-ion batteries, the charging and the discharging of the lithium-ion electrochemical cells are accomplished by lithiating and delithiating the cell electrodes. When lithium-ion cells are constructed, they usually contain excess lithium-ions in the positive electrode and no lithium-ions in the negative electrode. During the initial cycling reaction of the cells (charging), lithium transfers from the positive electrode to the negative electrode until the negative electrode has reached its capacity of absorbing lithium-ions. Upon the first discharge, the lithium-ions migrate from the lithiated negative electrode back to the positive electrode. Typically, after the first charging not all of the lithium-ions in the negative electrode are able to migrate out of the negative electrode. This results in what is known as irreversible loss in the capacity of the cell. Loss in the capacity of a cell from additional cycling (after the first cycle) is called capacity fade. This can be for a variety of reasons including changes in the morphology of the active electrode material upon repeated cycling, a buildup of insulating layers on the active electrode material upon repeated cycling or other reasons. A desirable lithium-ion cell is one that has low irreversible capacity loss after the initial cycling, and has low capacity loss (fade) after multiple cycles.
  • SUMMARY
  • In view of the foregoing, we recognize that there is a need for electrodes that undergo reduced first cycle capacity loss (irreversible capacity loss) and reduced capacity fade.
  • In one aspect, this invention provides an electrode composition that comprises a powdered material capable of undergoing lithiation and delithiation. In addition, the electrode composition includes a non-elastomeric binder that includes lithium polyacrylate.
  • In another aspect, this invention provides an electrochemical cell that comprises a positive electrode, a negative electrode, and an electrolyte. The negative electrode, the positive electrode, or both electrodes include a powdered material capable of undergoing lithiation and delithiation and a non-elastomeric binder that includes lithium polyacrylate.
  • In yet a further aspect, this invention provides a method of making an electrochemical cell electrode that includes providing a current collector, providing a powdered material capable of undergoing lithiation and delithiation, and applying to the current collector a coating that includes the powdered material and lithium polyacrylate.
  • The use of lithium polyacrylate as a binder provides reduced irreversible capacity and fade. The irreversible first cycle capacity loss in these electrodes can be significantly decreased by forming the electrode using a lithium polyacrylate binder. Such a binder (which can be prepared by neutralizing poly(acrylic acid) with lithium hydroxide) can be used to prepare electrodes and cells that experience decreased first cycle irreversible capacity loss compared to electrodes or cells made with conventional polymeric binders.
  • The disclosed electrodes containing lithium polyacrylate binders can improve cycle life in rechargeable lithium-ion cells employing electrodes based on small particle alloy powders. The disclosed binders can also allow fabrication of rechargeable lithium-ion cells having improved capacities or employing novel alloy powders.
  • In this application:
  • the terms “a”, “an”, and “the” are used interchangeably with “at least one” to mean one or more of the elements being described;
  • the term “metal” refers to both metals and to metalloids such as silicon and germanium, whether in an elemental or ionic state;
  • the term “alloy” refers to a mixture of two or more metals;
  • the terms “lithiate” and “lithiation” refer to a process for adding lithium to an electrode material;
  • the terms “delithiate” and “delithiation” refer to a process for removing lithium from an electrode material;
  • the term “active” refers to a material that can undergo lithiation and delithiation;
  • the terms “charge” and “charging” refer to a process for providing electrochemical energy to a cell;
  • the terms “discharge” and “discharging” refer to a process for removing electrochemical energy from a cell, e.g., when using the cell to perform desired work;
  • the phrase “positive electrode” refers to an electrode (often called a cathode) where electrochemical reduction and lithiation occurs during a discharging process; and
  • the phrase “negative electrode” refers to an electrode (often called an anode) where electrochemical oxidation and delithiation occurs during a discharging process.
  • Unless the context clearly requires otherwise, the terms “aliphatic”, “cycloaliphatic” and “aromatic” include substituted and unsubstituted moieties containing only carbon and hydrogen, moieties that contain carbon, hydrogen and other atoms (e.g., nitrogen or oxygen ring atoms), and moieties that are substituted with atoms or groups that may contain carbon, hydrogen or other atoms (e.g., halogen atoms, alkyl groups, ester groups, ether groups, amide groups, hydroxyl groups or amine groups).
  • DETAILED DESCRIPTION
  • All numbers are herein assumed to be modified by the term “about”. The recitation of numerical ranges by endpoints includes all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).
  • Electrode compositions according to the present invention may be used in negative or positive electrodes. A variety of powdered materials can be employed to make the electrode compositions. Exemplary powdered materials can for example contain silicon, silver, lithium, tin, bismuth, lead, antimony, germanium, zinc, gold, platinum, palladium, arsenic, aluminum, gallium, indium, thallium, molybdenum, niobium, tungsten, tantalum, iron, copper, titanium, vanadium, chromium, nickel, cobalt, zirconium, yttrium, a lanthanide, an actinide or an alloy containing any of the foregoing metals or metalloids and other powdered active metals and metalloids that will be familiar to those skilled in the art. Graphitic carbon powder can also be used to make the disclosed electrode compositions.
  • Exemplary powders can have a maximum length in one dimension that is no greater than 60 μm, no greater than 40 μm, or no greater than 20 μm, or even smaller. The powders can, for example, have a maximum particle diameter that is submicron, at least 1 μm, at least 2 μm, at least 5 μm, or at least 10 μm or even larger. For example, suitable powders often have a maximum dimension of 1 to 60 μm, 10 to 60 μm, 20 to 60 μm, 40 to 60 μm, 1 to 40 μm, 2 to 40 μm, 10 to 40 μm, 5 to 20 μm, or 10 to 20 μm. The powdered materials can contain optional matrix formers within powder particles. Each phase originally present in the particle (i.e., before a first lithiation) can be in contact with the other phases in the particle. For example, in particles based on a silicon:copper:silver alloy, a silicon phase can be in contact with both a copper silicide phase and a silver or silver alloy phase.
  • Each phase in a particle can for example have a grain size less than 500 Å, less than 400 Å, less than 300 Å, less than 200 Å, less than 150 Å, or even smaller.
  • Exemplary silicon-containing powdered materials useful in this invention include the silicon alloys wherein the powdered material comprises from about 65 to about 85 mole percent silicon, from about 5 to about 12 mole percent iron, from about to about 12 mole percent titanium, and from about 5 to about 12 mole percent carbon. Additional examples of useful silicon alloys include compositions that include silicon, copper, and silver or silver alloy such as those discussed in U.S. Pat. Appl. Publ. No. 2006/0046144 A1 (Obrovac et al); multiphase, silicon-containing electrodes such as those discussed in U.S. Pat. No. 7,498,100 (Christensen et al); silicon alloys that contain tin, indium and a lanthanide, actinide element or yttrium such as those described in U.S. Pat. Publ. Nos. 2007/0020521, 2007/0020522, and 2007/0020528 (all to Obrovac et al.) filed Mar. 23, 2006; amorphous alloys having a high silicon content such as those discussed in U.S. Pat. No. 7,732,955 (Christensen et al.); and other powdered materials used for negative electrodes such as those discussed in U.S. Pat. Publ. No. 2007/0269718 (Krause et al.) and PCT Publ. No. WO 2007/044315 (Krause et al.). Each of the foregoing references is incorporated herein in its entirety.
  • Other useful exemplary powdered materials for making positive electrodes of the invention include lithium alloys such as Li4/3Ti5/3O4, LiV3O8, LiV2O5, LiCo0.2Ni0.8O2, LiNiO2, LiFePO4, LiMnPO4, LiCoPO4, LiMn2O4, and LiCoO2; lithium atoms intercalated within a lithium transition metal oxide such as lithium cobalt dioxide, lithium nickel dioxide, and lithium manganese dioxide; the lithium alloy compositions that include mixed metal oxides of cobalt, manganese, and nickel such as those described in U.S. Pat. Nos. 6,964,828 and 7,078128 (Lu et al); 6,203,944 (Turner); and 6,680,145 B2 (Obrovac et al.).
  • Exemplary powdered materials useful for making negative electrodes of his invention include U.S. Pat. No. 6,699,336 B2 (Turner et al.); U.S. Pat. Appl. Publ. No. 2003/0211390 A1 (Dahn et al.); U.S. Pat. Nos. 6,255,017 B1 (Turner) and 6,436,578 B2 (Turner et al.); graphitic carbon that exists in forms such as powders, flakes, fibers or spheres (e.g., mesocarbon microbeads (MCMB)); combinations thereof and other powdered materials that will be familiar to those skilled in the art. Each of the foregoing references is incorporated herein in its entirety.
  • Powdered alloy particles may include a conductive coating. For example, a particle that contains silicon, copper, and silver or a silver alloy can be coated with a layer of conducting material (e.g., with the alloy composition in the particle core and the conductive material in the particle shell). Suitable conductive materials include, for example, carbon, copper, silver, or nickel.
  • Exemplary powdered alloy materials can be prepared by any known means, for example, by physically mixing and then milling the various precursor components to the alloys. The mixing can be by simple blending or by using a melt spinning process. According to this process, ingots containing the alloy composition can be melted in a radio frequency field and then ejected through a nozzle onto a surface of a rotating wheel (e.g., a copper wheel). Because the surface temperature of the rotating wheel is substantially lower than the temperature of the melted alloy, contact with the surface of the rotating wheel quenches the melt. Quenching minimizes the formation of large crystallites that can be detrimental to electrode performance. When conductive coatings are employed, they can be formed using techniques such as electroplating, chemical vapor deposition, vacuum evaporation or sputtering. Suitable milling can be done by using various techniques such as vertical ball milling, horizontal ball milling or other milling techniques known to those skilled in the art.
  • The electrode composition can contain additives such as will be familiar to those skilled in the art. The electrode composition can include an electrically conductive diluent to facilitate electron transfer from the powdered material to a current collector. Electrically conductive diluents include, but are not limited to, carbon (e.g., carbon black for negative electrodes and carbon black, flake graphite and the like for positive electrodes), metal, metal nitrides, metal carbides, metal silicides, and metal borides. Representative electrically conductive carbon diluents include carbon blacks such as SUPER P and SUPER S carbon blacks (both from MMM Carbon, Belgium), SHAWANIGAN BLACK (Chevron Chemical Co., Houston, Tex.), acetylene black, furnace black, lamp black, graphite, carbon fibers and combinations thereof.
  • The electrode composition can include an adhesion promoter that promotes adhesion of the powdered material or electrically conductive diluent to the binder. The combination of an adhesion promoter and binder can help the electrode composition better accommodate volume changes that can occur in the powdered material during repeated lithiation/delithiation cycles. The disclosed binders can offer sufficiently good adhesion to metals and alloys so that addition of an adhesion promoter may not be needed. If used, an adhesion promoter can be made a part of the lithium polyacrylate binder (e.g., in the form of an added functional group), can be a coating on the powdered material, can be added to the electrically conductive diluent, or can be a combination of such measures. Examples of adhesion promoters include silanes, titanates, and phosphonates as described in U.S. Pat. Appl. Publ. No. 2004/0058240 A1 (Christensen), the disclosure of which is incorporated herein by reference.
  • The binders of this invention contain lithium polyacrylate. Lithium polyacrylate can be made from poly(acrylic acid) that is neutralized with lithium hydroxide. In this application, poly(acrylic acid) includes any polymer or copolymer of acrylic acid or methacrylic acid or their derivatives where at least about 50 mole %, at least about 60 mole %, at least about 70 mole %, at least about 80 mole %, or at least about 90 mole % of the copolymer is made using acrylic acid or methacrylic acid. Useful monomers that can be used to form these copolymers include, for example, alkyl esters of acrylic or methacrylic acid that have alkyl groups with 1-12 carbon atoms (branched or unbranched), acrylonitriles, acrylamides, N-alkyl acrylamides, N,N-dialkylacrylamides, hydroxyalkylacrylates, and the like. Of particular interest are polymers or copolymers of acrylic acid or methacrylic acid that are water soluble—especially after neutralization or partial neutralization. Water solubility is typically a function of the molecular weight of the polymer or copolymer and/or the composition. Poly(acrylic acid) is very water soluble and is preferred along with copolymers that contain significant mole fractions of acrylic acid. Poly(methacrylic) acid is less water soluble—particularly at larger molecular weights.
  • Homopolymers and copolymers of acrylic and methacrylic acid that are useful in this invention can have a molecular weight (MW) of greater than about 10,000 grams/mole, greater than about 75,000 grams/mole, or even greater than about 450,000 grams/mole or even higher. The homopolymers and copolymer that are useful in this invention have a molecular weight (MW)) of less than about 3,000,000 grams/mole, less than about 500,000 grams/mole, less than about 450,000 grams/mole or even lower. Carboxylic acidic groups on the polymers or copolymers can be neutralized by dissolving the polymers or copolymers in water or another suitable solvent such as tetrahydrofuran, dimethylsulfoxide, N, N-dimethylformamide, or one or more other dipolar aprotic solvents that are miscible with water. The carboxylic acid groups (acrylic acid or methacrylic acid) on the polymers or copolymers can be titrated with an aqueous solution of lithium hydroxide. For example, a solution of 34% poly(acrylic acid) in water can be neutralized by titration with a 20% by weight solution of aqueous lithium hydroxide. Typically, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 100% or more, 107% or more of the carboxylic acid groups are lithiated (neutralized with lithium hydroxide) on a molar basis. When more than 100% of the carboxylic acid groups have been neutralized this means that enough lithium hydroxide has been added to the polymer or copolymer to neutralize all of the groups with an excess of lithium hydroxide present.
  • The binders of this invention may be blended with other polymeric materials to make a blend of materials. This may be done, for example, to increase the adhesion, to provide enhanced conductivity, to change the thermal properties or to affect other physical properties of the binder. The binders of this invention, however, are non-elastomeric. By non-elastomeric it is meant that the binders do not contain substantial amounts of natural or synthetic rubber. Synthetic rubbers include styrene-butadiene rubbers and latexes of styrene-butadiene rubbers. For example, the binders of this invention contain less than 20% by weight, less than 10% by weight, less than 5% by weight, less than 2% by weight, or even less of natural or synthetic rubber.
  • To make a positive or a negative electrode, the active powdered material, any selected additives such as binders, conductive diluents, fillers, adhesion promoters, thickening agents for coating viscosity modification such as carboxymethylcellulose and other additives known by those skilled in the art are mixed in a suitable coating solvent such as water or N-methylpyrrolidinone (NMP) to form a coating dispersion or coating mixture. The dispersion is mixed thoroughly and then applied to a foil current collector by any appropriate dispersion coating technique such as knife coating, notched bar coating, dip coating, spray coating, electrospray coating, or gravure coating. The current collectors are typically thin foils of conductive metals such as, for example, copper, aluminum, stainless steel, or nickel foil. The slurry is coated onto the current collector foil and then allowed to dry in air followed usually by drying in a heated oven, typically at about 80° C. to about 300° C. for about an hour to remove all of the solvent.
  • A variety of electrolytes can be employed in the disclosed lithium-ion cell. Representative electrolytes contain one or more lithium salts and a charge-carrying medium in the form of a solid, liquid or gel. Exemplary lithium salts are stable in the electrochemical window and temperature range (e.g. from about −30° C. to about 70° C.) within which the cell electrodes can operate, are soluble in the chosen charge-carrying media, and perform well in the chosen lithium-ion cell. Exemplary lithium salts include LiPF6, LiBF4, LiClO4, lithium bis(oxalato)borate, LiN(CF3SO2)2, LiN(C2F5SO2)2, LiAsF6, LiC(CF3SO2)3, and combinations thereof. Exemplary charge-carrying media are stable without freezing or boiling in the electrochemical window and temperature range within which the cell electrodes can operate, are capable of solubilizing sufficient quantities of the lithium salt so that a suitable quantity of charge can be transported from the positive electrode to the negative electrode, and perform well in the chosen lithium-ion cell. Exemplary solid charge carrying media include polymeric media such as polyethylene oxide, polytetrafluoroethylene, polyvinylidene fluoride, fluorine-containing copolymers, polyacrylonitrile, combinations thereof and other solid media that will be familiar to those skilled in the art. Exemplary liquid charge carrying media include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl-methyl carbonate, butylene carbonate, vinylene carbonate, fluoroethylene carbonate, fluoropropylene carbonate, y-butylrolactone, methyl difluoroacetate, ethyl difluoroacetate, dimethoxyethane, diglyme (bis(2-methoxyethyl) ether), tetrahydrofuran, dioxolane, combinations thereof and other media that will be familiar to those skilled in the art. Exemplary charge carrying media gels include those described in U.S. Pat. Nos. 6,387,570 (Nakamura et al.) and 6,780,544 (Noh). The charge carrying media solubilizing power can be improved through addition of a suitable cosolvent. Exemplary cosolvents include aromatic materials compatible with Li-ion cells containing the chosen electrolyte. Representative cosolvents include toluene, sulfolane, dimethoxyethane, combinations thereof and other cosolvents that will be familiar to those skilled in the art. The electrolyte can include other additives that will familiar to those skilled in the art. For example, the electrolyte can contain a redox chemical shuttle such as those described in U.S. Pat. Nos. 5,709,968 (Shimizu), 5,763,119 (Adachi), 5,536,599 (Alamgir et al.), 5,858,573 (Abraham et al.), 5,882,812 (Visco et al.), 6,004,698 (Richardson et al.), 6,045,952 (Kerr et al.), and 6,387,571 B1 (Lain et al.); and in U.S. Pat. Appl. Publ. Nos. 2005/0221168 A1, 2005/0221196 A1, 2006/0263696 A1, and 2006/0263697 A1 (all to Dahn et al.).
  • Electrochemical cells of this invention are made by taking at least one each of a positive electrode and a negative electrode as described above and placing them in an electrolyte. Typically, a microporous separator, such as CELGARD 2400 microporous material, available from Hoechst Celanese, Corp., Charlotte, N.C., is used to prevent the contact of the negative electrode directly with the positive electrode. This is especially important in coin cells such as, for example, 2325 coin cells as known in the art.
  • Electrochemical cells made with the negative electrodes of this invention showed reduced irreversible capacity loss and less fade than similar cells containing negative electrodes with conventional binders.
  • The disclosed cells can be used in a variety of devices, including portable computers, tablet displays, personal digital assistants, mobile telephones, motorized devices (e.g., personal or household appliances and vehicles), instruments, illumination devices (e.g., flashlights) and heating devices. One or more electrochemical cells of this invention can be combined to provide battery pack. Further details regarding the construction and use of rechargeable lithium-ion cells and battery packs will be familiar to those skilled in the art.
  • The invention is further illustrated in the following illustrative examples, in which all parts and percentages are by weight percent (wt %) unless otherwise indicated.
  • EXAMPLES
  • Preparatory Example 1
  • Preparation of Si70Fe10Ti10C10 Alloy
  • Si70Fe10Ti10 was prepared by melting silicon lumps (65.461 grams)(Alfa Aesar/99.999%, Ward Hill, Mo.), iron pieces (18.596 grams) (Alfa Aesar/99.97%) and titanium sponge (15.943 grams) (Alfa Aesar/99.7%) in an ARC furnace. The alloy ingot of Si70Fe10Ti10 was broken into small chinks and was treated in a hammer mill to produce alloy powder particles of approximately 150 micrometers.
  • Si70Fe10Ti10C10 alloy was made from Si70Fe10Ti10 alloy powder (described above) and graphite (TIMREX SFG44, TimCal Ltd., Bodio, Switzerland) by reactive ball milling in a high kinetic ball mill (SIMOLOYER, CM20-201m, Zoz GmbH, Wenden, Germany). A sample of 1.4423 kg of Si70Fe10Ti10 alloy powder, 0.0577 kg graphite and 25 kg of 4.76 millimeter diameter chromium-steel balls were charged to the mill. The mill was operated for 180 cycles where each cycle consisted of 45 seconds at 550 revolutions per minutes (rpm) and then 15 seconds at 300 rpm. The total milling time was 3 hours. The mill was cooled by chilled water during the milling.
  • Preparatory Example 2 Preparation of Lithium Polyacrylate
  • Lithium polyacrylate was made by adding an aqueous solution of lithium hydroxide solution to an aqueous poly(acrylic acid) solution. Different molar ratios of lithium hydroxide and carboxylic acid groups were used. Typically a 20 wt % aqueous solution of lithium hydroxide and a 34 wt % aqueous solution of poly (acrylic acid) were used. De-ionized water was added to bring the final solution of lithium polyacrylate to 10 wt % solids. Poly(acrylic acid) of 100,000 (MW) and 250,000 (MW) were obtained as aqueous solutions from Aldrich Chemicals, Milwaukee, Wis.. Samples of 65% LiOH neutralized lithium polyacrylate, of both 100,000 MW and 250,000 MW , were prepared by adding 185.56 grams of de-ionized water and 60.41 grams of 20% lithium hydroxide solution and 100 grams poly(acrylic acid) (PAA) solution (34 wt % in water). The results were 10% solids solutions of lithium polyacrylate which had been 64% neutralized. The two samples were designated lithium (64%) polyacrylate PAA100k-64% Li salt and lithium (64%) polyacrylate PAA250k-64% Li salt.
  • Additional samples of 107% of neutralized lithium polyacrylate were prepared using both the 100,000 MW and the 250,000 MW polymer by adding 149.01 grams of de-ionized water and 106.01 grams of 20% lithium hydroxide solution to 100 grams poly(acrylic acid) solution (34 wt % in water). The results were 10% solids solutions of lithium polyacrylate with a 7 mole % excess of lithium hydroxide. The two samples were designated lithium (107%) polyacrylate PAA100k-107% Li Salt and lithium (107%) polyacrylate PAA250k-107% LI salt.
  • TABLE 1
    Calculated Weight % of total, dried coating
    Example
    1 2 3 4 5 6 7 8 9 10
    Si70Fe10Ti10C10 60 92 60 92 92 5 47.5
    65 wt % Si70Fe10Ti10C10: 92
    35 wt % SLP30
    MCMB 1028 32
    MCMB 6-28 90
    SFG44 47.5
    KETJEN Black 1.2 1.2
    PAA100k-64% Li salt 6.8 6.8
    SLP30 32 95 95
    PAA100k-107% Li salt 8 8 5
    PAA250k-107% Li salt 8 8 5
    KYNAR 741 5 5
    Die Gap for coating (μm) 125 75 125 75 125 75 75 75 250 250
  • Electrode Fabrication Example 1
  • KETJEN Black conductive carbon (0.024g) (Akzo Nobel Polymer Chemical LLC, Chicago, Ill.) and PAA100k-64% Li salt (1.36 g of a 10% solids solution in water, were mixed in a 45-mL stainless steel vessel using four 13 micrometer diameter tungsten carbide balls. The mixing was carried out in a planetary micro mill (PULVERSETTE 7 Model; Fritsch, Germany) at a speed setting of 1 for 30 minutes. Then Si70Fe10Ti10C10 powder (1.20 g), MCMB-1028 graphite (0.64 g) (MMM Carbon, Belgium) and de-ionized water (0.1 g) were added to the mill and the mixing was continued at a speed setting of 2 for 30 minutes. The resulting solution was coated onto a 13-micron thick Cu foil using a die with a 125 μm gap. The sample was then dried in a vacuum oven at 120° C. for 2 hours.
  • Example 2
  • An electrode based on the composition of Example 2 in Table 1 was prepared by the procedure used for Example 1 except that only 1.84 grams of Si70Fe10Ti10C10 powder was added to the milled conductive carbon and polymer mixture. The milled coating solution was coated onto copper foil using a 75 μm gap.
  • Example 3
  • An electrode based on the composition of Example 3 in Table 1 was prepared by the procedure used for Example 1 except that Si70Fe10Ti10C10 powder (1.20 g), SLP30-Graphite (0.64 g) (TIMREX SLP30, TimCal Ltd., CH-6743 Bodio, Switzerland), de-ionized water (1.0 g) and PAA100k-107% Li salt (1.6 g of a 10% solids solution in water) were milled in a single step at a speed setting of 2 for 30 minutes. The milled solution was spread onto the copper foil using a 3 μm gap.
  • Example 4
  • An electrode based on the composition of Example 4 of Table lwas prepared by the same procedure used for Example 3, except that only 0.2 grams of de-ionized water was added. The milled solution was spread onto the copper foil using a 3 mil gap.
  • Example 5
  • An electrode based on the composition of Example 5 of Table 1 was prepared by the same procedure used for Example 3, except that 2.5 grams of de-ionized water was used with the graphite and the poly(acrylic acid) in the milling step. The milled solution was spread onto the copper foil using a 3 mil gap.
  • Examples 6 and 7
  • Electrodes based on the compositions of Example 6 and Example 7 of Table 1 were prepared by the same procedure used for Example 4.
  • Example 8
  • An electrode based on the composition of Example 8 in Table 1 was prepared by the same procedure used for Example 5.
  • Comparative Example 1
  • Graphite (1.00 gram) (MCMB, Grade 6-28, Osaka Gas Co. Osaka-Shi, Japan), Si70Fe10Ti10C10 (0.1 gram), polyvinylidene fluoride (KYNAR 741) solution (1.0 gram of a 10% by weight solution in N-methyl pyrrolidinone (NMP)), and NMP (2.5 grams) were mixed in planetary micro mill as described for Example 1. The mixture was coated and dried as in Example 1.
  • Comparative Example 2
  • Si70Fe10Ti10C10 powder (2.0 grams) and TIMREX SFG44 graphite (2.0 grams) were mixed in the micro mill used for Example 1 at a speed setting of 7 for 30 minutes.
  • This mixture (1.90 grams), polyvinylidene fluoride (KYNAR 741) solution (1.0 grams) and NMP (3.0 grams) were mixed in the micro mill of Example 1 at a speed setting of 2 for one hour. The mixture was coated and dried as in Example 1.
  • Test Cell Assembly
  • Disks (16-mm diameter) were cut from the electrode coatings for use in 2325-button cells. Each 2325 cell contains a 18 mm diameter disk of Cu as a spacer (36-mil (900 μm) thick), an 18 mm diameter disk of the alloy electrode, one 20 mm diameter microporous separator (CELGARD 2400; Separation Products, Hoechst Celanese Corp., Charlotte, N.C. 28273)), 18 mm diameter lithium (0.38 mm thick lithium ribbon; Aldrich Chemicals, Milwaukee, Wis.) and an 18 mm diameter copper spacer (600 μm thick). One hundred microliters of electrolyte solution (1M LiPF6 in 90wt % ethylene carbonate (EC): diethylene carbonate (DEC) (1:2 v/v) (Ferro Chemicals (Zachary, La.); 10 wt % fluoroethylene carbonate (FEC) (Fujian Chuangxin Science and Technology Development, LTP, Fujian, China)) were mixed and used as the electrolyte. The electrolyte mixture was dried over molecular sieves (3A type) over 12 hrs. The coin cells were charged and discharged from 0.005V to 0.90V with a constant current of 250 mA/g for alloy and alloy/graphite electrodes and with a constant current of 100 mA/g for graphite electrodes. During charging, when the cell reached 0.90V, the cell voltage was held constant and the charging continued until the current reached 10 mA/g. The cell was allowed to remain at open circuit for fifteen minutes at the end of every half cycle.
  • The initial charge capacity of each cell was calculated from the measured total milliamp-hours charged until the cell voltage reached 0.005V. The cell was then discharged as described above. The irreversible capacity loss (shown in Table 2) was calculated from the difference between the initial charge capacity and the first discharge capacity divided by the initial capacity times 100. The data in Table 2 show that negative electrodes made using the binders of this invention have less irreversible capacity loss compared with electrodes made with polyvinylidene fluoride binders.
  • TABLE 2
    Initial Charge Capacity and Irreversible Capacity of Examples 1-8
    Initital Charge Capacity Irreversible Capacity
    (mAh/g Active Material) Loss (%)
    Example 1 No Data No Data
    Example 2 No Data No Data
    Example 3 982 10.0
    Example 4 1339 10.4
    Example 5 392 8.7
    Example 6 987 9.8
    Example 7 1339 9.6
    Example 8 397 8.3
    Comparative 388 15.7
    Example 1
    Comparative 819 19.3
    Example 2
  • The discharge capacity after cycle 5 and after cycle 50 for each cell is provided in Table 3. The data show that cells containing negative electrodes with binders of this invention have less fade after 50 cycles than those made with polyvinylene fluoride binders.
  • TABLE 3
    Discharge Capacity at Cycle 5 and at Cycle 50 for Examples 1-8
    Discharge
    Capacity Discharge Capacity
    at Cycle 5 at Cycle 50
    (mAh/g Alloy and (mAh/g Alloy and % Capacity Loss/
    graphite) graphite) Cycle
    Example 1 864  854 0.026
    Example 2 1219 1179 0.073
    Example 3 891  862 1.072
    Example 4 1190 1134 0.105
    Example 5 363  362 0.006
    Example 6 897  847 0.012
    Example 7 1219 1138 0.144
    Example 8 365  366
    Comparative 311  289* 0.157
    Example 1
    Comparative 451  136 1.550
    Example 2
    *Comparative Example 1 Discharge Capacity at Cycle 19
  • A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications can be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.

Claims (19)

1. An electrode composition comprising:
a powdered active material capable of undergoing lithiation and delithiation; and
a non-elastomeric binder comprising lithium polyacrylate,
wherein the powdered active material comprises a lithium metal oxide comprising at least one of cobalt, manganese, and nickel.
2. An electrode composition according to claim 1, wherein the lithium metal oxide comprises cobalt, manganese and nickel.
3. An electrode composition according to claim 1, wherein the amount of lithium polyacrylate is 5 or more weight percent of the weight of the total composition.
4. An electrode composition according to claim 1, wherein the powdered material further comprises iron, titanium, or vanadium.
5. An electrode composition according to claim 1, wherein the powdered material comprises lithium cobalt oxide.
6. An electrochemical cell comprising:
a positive electrode;
a negative electrode; and
an electrolyte,
wherein the positive electrode comprises a non-elastomeric binder comprising lithium polyacrylate, and
wherein the powdered active material comprises a lithium metal oxide comprising at least one of cobalt, manganese, and nickel.
7. An electrochemical cell according to claim 6, wherein powdered active material comprises a lithium metal oxide comprising at least one of cobalt, manganese, and nickel.
8. An electrochemical cell according to claim 6, wherein the amount of lithium polyacrylate in the non-elastomeric binder is 5 or more weight percent of the weight of the total composition.
9. An electrochemical cell according to claim 6, wherein the powdered active material further comprises a material selected from iron, titanium, vanadium, and combinations thereof.
10. An electrochemical cell according to claim 6, wherein the cell further comprises a secondary electrochemical cell.
11. An electrochemical cell according to claim 6, wherein the negative electrode comprises a silicon alloy.
12. An electrochemical cell according to claim 6, wherein the alloy further comprises iron, titanium, or vanadium.
13. An electrochemical cell according to claim 6, wherein the negative electrode comprises graphitic carbon.
14. A battery pack comprising at least electrochemical cell according to claim 6.
15. A method of making an electrochemical cell electrode comprising:
providing a current collector;
providing a powdered active material capable of undergoing lithiation and delithiation; and
applying to the current collector a coating that comprises the powdered active material and lithium polyacrylate,
wherein the powdered active material comprises a lithium metal oxide comprising at least one of cobalt, manganese, and nickel.
16. A method of making an electrochemical cell electrode according to claim 15, wherein powdered active material comprises a lithium metal oxide comprising at least one of cobalt, manganese, and nickel.
17. A method of making an electrochemical cell electrode according to claim 15, wherein the amount of lithium polyacrylate in the non-elastomeric binder is 5 or more weight percent of the weight of the total composition.
18. A method of making an electrochemical cell electrode according to claim 15, wherein the powdered active material further comprises a material selected from iron, titanium, vanadium, and combinations thereof
19. A method of making an electrochemical cell electrode according to claim 15, wherein applying the coating further comprises:
mixing the powdered material with a solution of lithium polyacrylate to form a dispersion;
milling the dispersion to form a coatable mixture;
coating the mixture onto the current collector; and
drying the coated current collector.
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