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    • 专利摘要:
    BINDERS, ELECTROLYTES AND FILM OFSEPARATION FOR SOLAR ENERGY COLLECTION AND STORAGE DEVICESUSING DISCRETE CARBON NANOTUBES. The present invention refers, in various embodiments, to an improved binder composition,electrolyte composition and a separation film compositionusing discrete carbon nanotubes. Its methods ofproduction and utility for energy storage and energy devices.such as batteries, capacitors and photovoltaics. the composition ofbinder, electrolyte or separation may also comprisepolymers. Discrete carbon nanotubes also comprise theat least a part of the tubes being open ended and/orfunctionalized. The utility of binder, electrolyte orof separation film includes better capacity, power or durability in energy storage and collection devices. The usefulness ofelectrolyte and/or separating film compositions include betterion transport in energy storage and collection devices.
    公开号:BR112014032138A2
    申请号:R112014032138-8
    申请日:2013-06-21
    公开日:2021-08-03
    发明作者:Kurt W. Swogger；Clive P. Bosnyak；Milos Marinkovic
    申请人:Molecular Rebar Design, Llc；
    IPC主号:
    专利说明:

    [001] [001]This patent application claims priority from USSN 61/662393 filed June 21, 2012 and USSN 61/663513 filed June 22, 2012; and is related to USSN 13/164456 filed June 20, 2011; USSN 12/968151 filed December 14, 2010; USSN 13/140029 filed December 18, 2009; USSN 61/500561 filed June 23, 2011; USSN 61/500560 filed June 23, 2011; and USSN 61/638454 filed April 25, 2012; which disclosures are incorporated herein by reference. STATEMENT ON GOVERNMENT SPONSORED RESEARCH FEDERAL NOT APPLICABLE BACKGROUND
    [002] [002]Many energy storage devices such as batteries, capacitors and photovoltaics can use a binder and/or an electrolyte and separating film to provide better performances in mechanical stabilization, better electrical conduction of powder used in cathodes or electrodes and ion transport in electro or photoactive material and electrolytes.
    [003] [003] Lithium ion batteries are used extensively for portable electronic equipment and batteries, such as lithium ion and lead acid, are increasingly being used to provide electrical back-up for wind and solar energy. The salts for the cathode materials in lithium ion batteries are generally known to have low electrical conductivity and low electrochemical stability, which results in poor cycling (charge/discharge) capacity. Both the cathode and anode materials in many battery types, such as lithium-ion batteries, exhibit swelling and disswelling as the battery is charged and discharged. This spatial movement leads to a greater separation of some of the particles and an increase in electrical resistance. The high internal resistance of batteries, particularly in large lithium-ion battery packs as used in electric vehicles, can result in excessive heat generation, leading to leakage of chemical reactions and fires due to the organic liquid electrolyte.
    [004] [004] Primary lithium batteries consist, for example, of lithium, poly(carbon monofluoride) and lithium tetrafluoroborate together with a solvent such as gamma-butyrolactone as an electrolyte. These lithium primary batteries have excellent storage times, but they suffer from being only capable of delivering low current and the capacity is about a tenth of what is theoretically possible. This is attributed to the low electrical conductivity of poly(carbon monofluoride). In some cases, a portion of manganese dioxide is added to aid in the electrical and energy conductivity of the lithium battery.
    [005] [005] Attempts to overcome the deficiencies of poor adherence to current collectors and to avoid microcracks during expansion and contraction of rechargeable batteries have included the development of binders. Binders such as polyacrylic acid (PAA) for cathodes, poly(styrene-butadiene), carboxymethylcellulose (CMC), styrene-butadiene (SBR) for anodes, and particularly polyvinylidene fluoride (PVDF) for cathodes and anodes, are used in batteries Lithium-based to hold active material particles together and to maintain contact with current collectors, ie aluminum (Al) or copper (Cu) foil. PAA and SBR are used as aqueous suspensions or solutions and are considered to be more environmentally benign than organic solvent based systems such as n-methyl-2-pyrrolidone (NMP) with PVDF.
    [006] [006] A lithium ion battery cathode electrode is typically made by mixing active material powder such as lithium iron phosphate, powder binder, ie high molecular weight PVDF, solvent such as NMP using PVDF, and additives such as carbon black, into a slurry (slurry) and pumping this suspension into a coating machine. An anode electrode for a lithium ion battery is similarly made by typically mixing graphite, or other materials, such as silicon, as the active material, together with the binder, solvent and additives. Coating machines spread the mixed slurry (slurry) on both sides of the Al sheet to the cathode and Cu sheet to the anode. The coated sheet is subsequently calendered to make the thickness of the electrode more uniform, followed by a cutting operation for proper sizing and drying of the electrode.
    [007] [007]For zinc-carbon batteries, the positive electrode may consist of a mixture of wet manganese dioxide powder, a powdered carbon black and electrolyte such as ammonium chloride and water. Carbon black can add electrical conductivity to manganese dioxide particles, but is required at high weight percentages in the range of about 10 to 50% by weight of manganese dioxide. These high amounts of carbon black required for higher electrical conductivity, or reduced battery impedance, decrease the capacity per unit volume of the battery, as less manganese dioxide can be used per unit volume of the positive pulp mixture.
    [008] [008]For a lead-acid battery, the anode can be made from carbon particles together with a binder to provide greater specific capacity (capacity per unit weight). The anode of a zinc-carbon battery is often a carbon rod, typically made of compacted carbon particles, graphite and a binder such as pitch. Carbon particle anodes tend to have low mechanical strength, leading to fracture under conditions of vibration and mechanical shock.
    [009] [009] The characteristics of the binding material are important for both the manufacture and performance of the battery. Some of these characteristics of relevance are electrical and ionic conductivity, tensile strength and extensibility, adhesion to particles as well as sheets, and electrolyte swelling. Increased electrical and ionic conductivity is necessary to increase battery capacity and power.
    [010] [010]Impurities such as non-lithium, iron and manganese salts, to name a few,
    [011] [011]For photovoltaics, conductive paste ink lines, made from solvents, binders, metal powder and glass frits, are screen-printed on a screen on solar panel modules. Binders are generally polymer base for improved printability, such as ETHOCEL™ (Dow Chemical Company).
    [012] [012]Efforts to improve the safety of lithium ion batteries have included the use of non-flammable liquids such as ionic liquids eg ethyl-methyl-imidazolium bis(trifluoromethanesulfonyl)-imide (EMI-TFSI) and polymer solid, sometimes with additional additives, eg polyethylene oxide with titanium dioxide nanoparticles, or solid inorganic electrolytes such as a ceramic or glass from glass ceramics, Li1 + x + yTi2 - xAlxSiyP3 - yO12 (LTAP). The electrical conductivity values of organic liquid electrolytes are generally in the range 10-2 to 10-1 S / cm. Polymeric electrolytes have electrical conductivity values in the range of about 10-7 to 10-4 S / cm, as a function of temperature, whereas solid inorganic electrolytes generally have values in the range of 10-8 to 10-5 S / cm . At room temperature, most polymeric electrolytes have electrical conductivity values around 10-5 S / cm. The low ionic conductivities of solid inorganic polymers and electrolytes are currently a limitation to their general use in energy storage and collection devices. It is, therefore, highly desirable to improve the conductivity of electrolytes, and particularly with inorganic polymer and electrolytes because of their better flammability characteristics relative to biological liquids. Furthermore, it is desirable to improve the mechanical strength of solid electrolytes in battery applications that require durability in environments of high vibration or mechanical shock, as well as in their ease of fabrication of the device.
    [013] [013]In alkaline batteries, the electrolyte is typically potassium hydroxide. Alkaline batteries are known to have significantly poorer capacity at high discharge current than at low discharge current. Limitations of electrolyte ion transport as well as zinc anode polarization are known reasons for this. An increase in electrolyte ion transport is highly desirable.
    [014] [014]Among the new generation thin-film photovoltaic technologies, dye-sensitive solar cells (DSSCs) have one of the most promising potentials in terms of cost-performance ratio. One of the most serious disadvantages of current DSSCs technology is the use of corrosive electrolytes and liquids which severely limit their commercial development. An example of an electrolyte currently used for DSSCs is potassium iodide/iodine. Substitution of currently used electrolytes is desirable, but candidate electrolytes have low ion transport.
    [015] [015] Typical electrolytic capacitors are made of tantalum, aluminum or ceramic with electrolyte systems such as boric acid, sulfuric acid or solid electrolytes,
    [016] [016] A separation film is often added to batteries or capacitors with liquid electrolytes to perform the function of electrical isolation between the electrodes, further allowing the transport of ions. Typically, in lithium batteries, the separating film is a porous polymeric film, the polymer being, for example, a polyethylene, polypropylene or polyvinylidene fluoride. Porosity can be introduced, for example, using a spun fiber mat or by film and/or solvent stretching techniques. In lead-acid batteries, where the separate film is conventionally a fiberglass matte. The polymer separation film comprising discrete carbon nanotubes of the present invention can improve ion transport and still provide the necessary electrical isolation between electrodes.
    [017] [017] The present invention comprises binders, electrolytes and improved separation films for energy storage and collection devices such as batteries, capacitors and photovoltaics comprising discrete carbon nanotubes, methods for their production and products obtained from them. SUMMARY
    [018] [018] In one embodiment, the invention is a composition comprising a plurality of discrete carbon nanotube fibers, said fibers having an aspect ratio of from about 10 to about 500, and wherein at least a portion of discrete carbon nanotube fibers is open ended, wherein the composition comprises a binding material, an electrolyte material or an energy storage separation film or collection device.
    [019] [019] In another embodiment, the composition comprises a plurality of discrete carbon nanotube fibers with a portion of discrete carbon nanotubes that is open-ended and ion-conductive. The composition can further comprise at least one polymer. The polymer is selected from the group consisting of vinyl polymers, preferably poly(styrene-butadiene), copolymers containing partially or fully hydrogenated poly(styrene-butadiene), copolymers of poly(styrene-butadiene) functionalized as poly(styrene) -carboxylated butadiene and the like, poly(styrene-isoprene), poly(methacrylic acid), poly(acrylic acid), poly(vinyl alcohols) and poly(vinyl cetates), fluorinated polymers, preferably poly(difluoride) copolymers. vinylidine) and poly(vinylidene difluoride), conductive polymers, preferably poly(acetylene), poly(phenylene), poly(pyrrole) and poly(acrylonitrile), polymers derived from natural sources, preferably alginates, polysaccharides, lignosulfonates, and materials based on cellulose, polyethers, polyolefins, polyesters, polyurethanes and polyamides; block or random homopolymers, grafts, co- or terpolymers, and mixtures thereof.
    [020] [020] In yet another embodiment of the present invention, the plurality of discrete carbon nanotube fibers is further functionalized, preferably the functional group comprises a molecule of mass greater than 50 g / mol, and more preferably the functional group comprises carboxylate, hydroxyl, ester, ether or amide moieties, or mixtures thereof.
    [021] [021] Another embodiment of the present invention comprising a plurality of discrete carbon nanotube fibers further comprising at least one dispersion aid.
    [022] [022] In another embodiment of the present invention, the plurality of carbon nanotubes further comprises additional inorganic structures comprising elements from groups two to fourteen of the Periodic Table of Elements.
    [023] [023] Another embodiment of the present invention comprises a plurality of carbon, wherein the composition has a flexural strength of at least about ten percent greater than a comparative composition made without the plurality of discrete carbon nanotubes.
    [024] [024] Yet another embodiment of this invention is a binder, electrolyte or separation film composition comprising a plurality of discrete carbon nanotube fibers having a portion of discrete carbon nanotubes that are open ended and conductive. ions further comprising non-fibrous carbon structures. Non-fibrous carbon structures comprise components selected from the group consisting of carbon black, graphite, graphene, oxidized graphene, fullerenes and their mixtures.
    [025] [025] Yet another embodiment of this invention is a composition comprising a plurality of discrete carbon nanotube fibers, where the binder material has an impedance of less than or equal to about one billion (1 x 109) ohm- m and the electrolyte material has a charge transfer resistance of less than or equal to about 10 million (1 x 107) ohm-m.
    [026] [026] Another embodiment of the present invention comprises an electrolyte or separation film composition comprising a plurality of discrete carbon nanotube fibers, wherein the carbon nanotubes are oriented. Orientation can be achieved by fabrication techniques such as in a sheet, microlayer, microlayer with vertical film orientation, film, molding, extrusion, or fiber spin fabrication method. Orientation can also be done through post-fabrication methods such as stretching, uniaxial orientation, biaxial orientation and thermoforming.
    [027] [027] Another embodiment of the present invention is a composition comprising a plurality of discrete carbon nanotubes, in which the part of open-ended tubes comprises electrolyte. For a polymer comprising electrolyte, the polymer is preferred to comprise a polymer molecular weight of less than 10,000 daltons, such that the polymer can enter the interior of the tube. Electrolyte may contain liquid.
    [028] [028] A further embodiment of the present invention comprises a composition comprising a plurality of discrete carbon nanotube fibers, said fibers having an aspect ratio of from about 10 to about 500, and wherein at least a portion of the fibers of discrete carbon nanotubes is open ended, preferably in which 40% to 90% by number of the carbon nanotubes have an aspect ratio of 30-70, and more preferably an aspect ratio of 40-60, and 1 % to 30% in aspect ratio number 80-140, more preferably an aspect ratio of 90 to 120. In statistics, a bimodal distribution is a continuous probability distribution with two different modes. These appear as distinct peaks (local maxima) in the probability density function. More generally, a multimodal distribution is a continuous probability distribution with two or more modes. Discrete carbon nanotubes can have a unimodal, multimodal or bimodal distribution of diameters and/or lengths. For example, discrete carbon nanotubes can have a bimodal diameter distribution, where one of the peak diameter values is in the range of 2 to 7 nanometers and the other peak value is in the range of 10 to 40 nanometers. Likewise, the lengths of discrete carbon nanotubes can have a bimodal distribution such that one peak has a maximum value in the range of 150-800 nanometers and the second peak has a maximum value in the range of 1000-3000 nanometers. This composition is useful in binders and electrolytes of the invention.
    [029] [029] In yet another embodiment, the invention is an electrode paste, preferably an anode paste, for a lead-acid battery, the paste comprising discrete carbon nanotubes with an average length of from about 400 to about 1400 nm, polyvinyl alcohol, water, lead oxide and sulfuric acid. Preferably, carbon nanotubes, polyvinyl alcohol and water form a dispersion, and the dispersion is then contacted with lead oxide, followed by sulfuric acid to form the electrode paste. BRIEF DESCRIPTION OF THE FIGURES
    [030] [030] The following drawings form part of this specification and are included to further demonstrate certain aspects of the present invention. The invention may be better understood by reference to one or more of these drawings in combination with the detailed description of specific embodiments presented herein.
    [031] [031] Figure 1 shows the discrete carbon nanotubes of the present invention with a bimodal distribution, in which the maximum of a peak is about 700 nanometers and the maximum of the second peak is about 1600 nanometers. Lengths were determined by deposition of discrete carbon nanotubes on a silicon wafer and by using scanning electron microscopy. DETAILED DESCRIPTION
    [032] [032] In the description that follows, certain details are presented, such as specific amounts, sizes, etc., in order to provide a thorough understanding of the present embodiments disclosed herein. However, it will be apparent to those of ordinary skill in the art that the present description can be practiced without these specific details. In many cases, details relating to such considerations and the like have been omitted to the extent that such details are not necessary to obtain a fuller understanding of the present invention and are within the skill of those of ordinary skill in the relevant art.
    [033] [033]While most of the terms used herein are recognized by those skilled in the art, it is to be understood that, when not explicitly defined, the terms are to be interpreted as adopting a meaning presently accepted by those skilled in the art. In cases where the construction of a term would make it meaningless or essentially meaningless, the definition should be taken from Webster's Dictionary, 3rd Edition, 2009. The definitions and/or interpretations should not be incorporated from other patent applications, patents , or publications, related or not, unless expressly stated by this descriptive report.
    [034] [034] In the present invention, discrete oxidized carbon nanotubes, alternatively called exfoliated carbon nanotubes, are obtained from carbon nanotubes grouped by methods such as oxidation, using a combination of concentrated nitric and sulfuric acids and sonication. Packaged carbon nanotubes can be made by any known means such as, for example, chemical vapor deposition, laser ablation and high pressure carbon monoxide synthesis. Packaged carbon nanotubes can be present in a variety of forms, including, for example, soot, dust, fibers and Bucky paper. Furthermore, the grouped carbon nanotubes can be of any length, diameter, or chirality. Carbon nanotubes can be metallic, semi-metallic, semiconductor, or non-metallic based on their chirality and number of walls. They can also include amounts of nitrogen within the carbon wall structure. Discrete oxidized carbon nanotubes can include, for example, single-walled, double-walled carbon nanotubes or multiple-walled carbon nanotubes and combinations thereof. Discrete carbon nanotubes diameters and lengths can be determined by deposition of discrete carbon nanotubes from a diluted solution on a silicon wafer and by means of scanning electron microscopy.
    [035] [035] Those of ordinary skill in the art will recognize that many of the specific aspects of the present invention, illustrated using a particular type of carbon nanotube, can be practiced equivalently within the spirit and scope of the description using other types of carbon nanotubes .
    [036] [036] The functionalized carbon nanotubes of the present invention generally refer to the chemical modification of any of the types of carbon nanotubes described above. Such modifications can involve nanotube ends, sidewalls, or both. Chemical modifications may include, but are not limited to, covalent bonds, ionic bonds, chemisorption, intercalation, surfactant interactions, polymer packaging, shear, solvation, and combinations thereof.
    [037] [037] Any of the aspects disclosed in the present invention with the discrete carbon nanotubes can also be modified within the spirit and scope of the description to replace other tubular nanostructures, including, for example, inorganic or mineral nanotubes. Inorganic or mineral nanotubes include, for example, silicon nanotubes, boron nitride nanotubes and carbon nanotubes with heteroatom substitution in the nanotube structure, such as nitrogen. Nanotubes can include or be associated with elements or organic or inorganic compounds of elements, such as, for example, carbon, silicon, boron and nitrogen. The inorganic elements may comprise the elements of groups two through fourteen of the Periodic Table of Elements, alone or in combination. The association can be inside or outside the inorganic or mineral nanotubes through Van der Waals, ionic or covalent bond to the surfaces of the nanotubes.
    [038] [038] Dispersing agents to help disperse discrete carbon nanotubes or other components of the present invention are, for example, anionic, cationic or non-ionic surfactants such as sodium dodecylsulfonate, cetyltrimethyl bromide or polyethers such as Pluronic made by BASF. They can be physically or chemically bonded to discrete carbon nanotubes. In some cases, the dispersing aid can also act as a binder. For example, with lead-acid batteries, polyvinyl alcohol can be used to disperse the discrete carbon nanotubes of the present invention in water between the pulp particles, then, in addition of sulfuric acid, the polyvinyl alcohol is considered to deposit on the paste particle and act as a binder. The polyvinyl alcohol preferably has an average molecular weight of less than about
    [039] [039] In some embodiments, the present invention comprises a composition for use as a binder material, an electrolyte material or a separating film material of an energy storage or collection device, comprising a plurality of fibers of discrete carbon nanotubes. The nanotube fibers can have an aspect ratio of from about 10 to about 500, and at least a portion of the discrete carbon nanotube fibers can have open ends. The part of discrete carbon nanotubes that is open ended can be conductive.
    [040] [040] In some embodiments of the present invention, the composition may further comprise at least one polymer. The polymer can be selected from the group consisting of vinyl polymers such as poly(styrene-butadiene), copolymers containing partially or fully hydrogenated poly(styrene-butadiene), functionalized poly(styrene butadiene) copolymers such as poly(styrene -butadiene) carboxylated, poly(styrene-isoprene), poly(methacrylic acid), poly(methyl methacrylate), poly(acrylic acid), poly(vinyl alcohols), poly(vinyl acetates), fluorinated polymers, polyvinylpyrrolidone, polymers conductors, polymers derived from natural sources, polyethers, polyesters, polyurethanes and polyamides; block or random homopolymers, grafts, co- or terpolymers, and mixtures thereof.
    [041] [041] According to other embodiments, the composition of the present invention may comprise carbon nanotubes that are further functionalized. The composition of the present invention may comprise additional inorganic structures comprising elements from groups two to fourteen of the Periodic Table of Elements. The composition of the present invention may further comprise at least one dispersing aid.
    [042] [042] The composition of the present invention may further comprise an alcohol such as polyvinyl alcohol.
    [043] [043] In some embodiments, the present invention comprises a binder material that further comprises non-fibrous carbon structures, for example, carbon black, graphite, graphene, oxidized graphene, fullerenes and mixtures thereof. In some embodiments, at least a portion of discrete carbon nanotubes is sandwiched between graphene and/or oxidized graphene plates.
    [044] [044] In other embodiments, the composition of the present invention comprises an electrolyte material or separating film. The composition may have a charge transfer resistance of less than or equal to about 10 million ohm-m.
    [045] [045] In other embodiments, the carbon nanotubes of the present invention are oriented, for example, in a sheet, microlayer, microlayer with vertical orientation of film, film, molding, extrusion or a fiber spinning fabrication method. Orientation can be achieved using post fabrication methods such as stretching, uniaxial orientation, biaxial orientation and thermoforming.
    [046] [046] In some embodiments of the present invention, a part of open ended tubes comprises electrolyte. The electrolyte can comprise a polymer or a liquid.
    [047] [047] In other embodiments of the invention, 40% to 90% by number of the discrete carbon nanotubes have an aspect ratio of 30-70. In other embodiments, 1% to 30% by number of carbon nanotubes have an average aspect ratio of 80-140.
    [048] [048] In some embodiments, the present invention comprises an electrode paste for a lead-acid battery comprising discrete carbon nanotubes with an average length of about 400 to about 1400 nm.
    [049] [049] The present invention also comprises a method for preparing a composition for use as a binding material, an electrolyte material or a separating film material for an energy storage or collection device. The method comprises the steps of a) adding carbon nanotubes to a liquid, solvent or polymer melt; b) vigorous mixing, such as with a sonicator or a high-shear mixer over a period of time; and c) optionally the addition of other materials, such as PVDF, and inorganic fillers, such as carbon black; and mixing continued until a homogeneous dispersion. The mixture can then be further fabricated into shapes by such methods as film extrusion, fiber extrusion, solvent melting and thermoforming. The method may further comprise the addition of a polymer, a dispersion aid, additional inorganic structures or an alcohol such as polyvinyl alcohol. ELECTROLYTES
    [050] [050]The term electrolyte is defined as a solution capable of carrying an electrical current. An ionic salt is dissolved in a medium that allows the transport of ions. Ion transport is defined as the movement of ions through the electrolyte.
    [051] [051] A separation film is often added to batteries with liquid electrolytes to perform the function of electrical isolation between the electrodes, while still allowing the transport of ions. Typically, in lithium batteries, the separating film is a porous polymeric film, the polymer being, for example, a polyethylene, polypropylene or polyvinylidene fluoride. Porosity can be introduced, for example, using a spun fiber mat or by film stretching techniques and/or by solvents. In lead-acid batteries, where the separating film has been used, it is conventionally a fiberglass matte.
    [052] [052] Flexural strength or crack resistance of solid electrolytes can be determined by flexural bending a film or sheet of the solid electrolyte onto a thin film of aluminum or copper in a 3-point bending accessory and an Instron Tensile machine Testing. The test is analogous to the standard test procedures given in ASTM D-790. The resistance to deformation and stress to cracking of the solid electrolyte through the thickness of the solid electrolyte film is recorded. Units are in MPa.
    [053] [053] Ionic salts can be added to a polymeric medium such as polyethylene oxide to produce electrolytes. For example, for ionic salts of lithium ion batteries such as lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfate, lithium bistrifluoromethanesulfonimide, lithium bisoxalate borate can be added to the polymer, by solvent or to the polymer melt. Solvents can be those that are maintained as an electrolyte medium, for example, ethylene carbonate, propylene carbonate, or solvents, which are then removed by drying, such as acetonitrile.
    [054] [054] The electrolyte or separation film containing polymeric material may have a polymer, or a combination of polymers that are dissimilar in molecular weight and/or by type. For example, in a polyethylene oxide containing electrolyte, a portion of the polyethylene oxide may be of a molecular weight above about
    [055] [055]Each dry film sample is obtained using a 22 mm punch.
    [056] [056]The flexural strength or cracking strength of pastes can be determined by flexural bending the paste over a thin aluminum or copper film in a 3-point bending attachment and an Instron Tensile Testing machine. The test is analogous to the standard test procedures given in ASTM D-790. The slurry cracking stress through the slurry thickness is recorded. Units are in MPa.
    [057] [057]The adhesive strength of pastes can be determined using overlap shear strength procedures and the Instron Tensile Testing machine.
    [058] [058] Electrolyte films are placed between two electrodes, resistance and reactance determined at frequencies of 100 Hz, 120 Hz, 1 KHz, 10 KHz and 100 KHz using an LCR meter, (Agilent 4263B) at 25 degrees centigrade and a 2 volt dc bias with a sinusoidal test level of 20mV. The Nyquist graph is constructed from the real and imaginary impedance components, from which the load transfer resistance is obtained.
    [059] [059]General procedure. A dispersion of discrete carbon nanotubes in n-methyl-2-pyrrolidone (NMP) is first made by adding carbon nanotubes of about 2% by weight of oxidized portions and average aspect ratio of about 60 to NMP under vigorous agitation. After addition, sonication is applied for about 15 minutes to exfoliate the carbon nanotubes. An amount of PVDF is slowly added to the system over a period of 30 minutes to obtain the desired weight fraction of carbon nanotube to PVDF. Vigorous stirring and sonication are continued until a homogeneous dispersion has been obtained. A uniform black color film of PVDF is obtained by removing the NMP in vacuum to constant weight.
    [060] [060]Examples 1-3 are dry PVDF films containing discrete carbon nanotubes in the percentage by weight of 2.5, 7.5 and 10%, respectively, and are shown in Table 1.
    [061] [061]Control 1 is done in a similar manner to Example 1, except that discrete carbon nanotubes are not added. The resulting dry film is a pale yellow. Impedance measurements of dry films and films swollen for 20 days in a 50/50 mixture of ethylene carbonate and propylene carbonate and 50% by weight lithium perchlorate are given in Table 1.
    [062] [062] The results presented in Table 1 demonstrate that Examples 1-3 with oxidized discrete carbon nanotubes of the present invention in PVDF provided significantly lower impedance values than the control of a PVDF film alone. Furthermore, the inclusion of carbon nanotubes of the present invention in PVDF demonstrates greater mass absorption of the LiClO4 solvent mixture, which allows better ion transport. These improved properties with the addition of the discrete carbon nanotubes of the present invention should lead to better performance both as a binder and as a separating film.
    [063] [063] A polyether (BASF, Pluronic F-127) as a dispersion aid for the discrete carbon nanotubes is dissolved in clean water by reverse osmosis at a weight ratio of 1.5 to 1 of the polyether to oxidized carbon nanotubes Dry, then oxidized carbon nanotubes are added to a 1.5 weight/volume concentration of carbon nanotubes to water and sonicated for a period of 30 minutes to disperse the oxidized carbon nanotubes. SBR latex (Dow Chemical Company, grade CP 615 ND, 50% solids content) is added directly to carbon nanotubes exfoliated in the desired carbon nanotube to SBR weight ratio and stirred vigorously until homogeneous. A black film is obtained by drying the mixture in air, followed by drying under vacuum until constant film weight is obtained.
    [064] [064]Example 4 is made with five weight percent discrete carbon nanotubes for dry SBR.
    [065] [065]Example 5 is made with seven point five percent by weight discrete carbon nanotubes for dry SBR.
    [066] [066]Control 2 is done as in example 4 and 5, except without adding discrete carbon nanotubes. The film is clear.
    [067] [067] Impedance measurements of dry films and films swollen for 2 days in a mixture of ethylene carbonate, ECO and propylene carbonate, PCO, 50/50 and 50% by weight lithium perchlorate are given in the table
    [068] [068]Oxidized carbon nanotube fibers are made by first sonicating the carbon nanotube fiber bundles (CNane, grade 9000) at 1% w/v in a concentrated sulfuric acid / nitric acid mixture for 2 hours or more at approx of 30°C. After filtration and washing with water, the pH of the final wash is about 4. The oxidized carbon nanotube fibers are vacuum dried for 4 hours at about 80°C. The resulting oxidized tubes generally contain about 1.5-6% by weight of oxygenated species as determined by thermogravimetric analysis in nitrogen between 200 and 600°C and at least a portion of the tubes are open ended as determined by microscopy secondary electronics. The residual ash after burning the oxidized carbon nanotubes in air at 800 °C is about 0.5 to 2% w/w. Monohydroxy poly(ethylene glycol), PEG-MH, molecular weight about 1900 daltons (Sigma Aldridge) is added in excess to the dry oxidized nanotubes together with a small amount of sulfuric acid as a catalyst and the mixture was heated to 100 °C while sonicating for about 1 hour. After cooling and adding water, the functionalized carbon nanotubes are filtered followed by washing to remove excess PEG-MH and sulfuric acid. Functionalized carbon nanotubes are dried under vacuum at 40 °C overnight. 0.5% w/w of the carbon nanotubes reacted with PEG-MH is added to the PEG-MH, heated to 60 °C and sonicated for 30 minutes. A uniform black liquid is obtained, which, upon examination, while in the liquid state by optical microscopy up to a magnification of 150X, did not reveal discernible aggregates of carbon nanotubes, ie the tubes are discrete and dispersed. On cooling, the PEG-MH with discrete carbon nanotubes, the PEG-MH is observed to crystallize and the carbon nanotubes are observed to be between crystal lamellae, ie, in the amorphous regions of the solid polymer. This is considered very advantageous since ions are recognized as preferential travelers in amorphous regions.
    [069] [069] Discrete oxidizing carbon nanotubes of about 2% and an average aspect ratio of 60, with a portion of the carbon nanotubes being open ended, are dried under vacuum at 80 °C for four hours. The compositions are constituted as detailed in Table 3 by first making solutions of the components using acetonitrile (Sigma Aldridge; 99.8% anhydrous) as a solvent; a 1% w/v solution of discrete carbon nanotubes, 2.5% w/v polyethylene oxide, POE, (Alpha Aesar) which consists of a ratio of two PEO, a molecular weight of 300,000 daltons, and a another of molecular weight of 4000 daltons in the weight ratio of 1:0.23, respectively, and 5% w/v of lithium trifluoromethanesulfate solution (Aldrich). The dry discrete carbon nanotubes are first sonicated in acetonitrile for 30 minutes using a bath of sonicator. Solutions are made up to the various compositions (parts per hundred PEO), given in Table 3, then sonicated for 30 minutes at about 30°C in a bath sonicator (Ultrasonics). The mixtures are then transferred to a glass dish and the acetonitrile evaporated for 4 hours to obtain films. The films are vacuum dried at 50 °C for 2 hours, followed by compression, molded at 120 °C for 3 minutes and 20 tons of platinum pressure between polyethylene terephthalate sheets, cooled to room temperature and stored in a desiccator before testing.
    [070] [070]The results in Table 3 show that significant improvements are obtained in the conductivity of solid electrolyte films with addition of discrete carbon nanotubes of the present invention compared to controls. Electrolyte films made with discrete carbon nanotubes are also seen to have greater strength than controls, as judged by their ability to be handled without tearing.
    [071] [071] The compositions for making an anode paste for a lead-acid battery for control 6 and example 16 are shown in Table 4. The expander (Hammond) is a composition of lignin sulphonate, barium sulphate and black carbon. carbon in a weight ratio of 1 : 1 : 0.5, respectively. The expander is added to the dry lead oxide powder, then water is added and mixed, followed by slow addition and acid mixing (sulfuric acid; 1.4 specific gravity), keeping the temperature below 55 °C. In example 16, discrete carbon nanotubes with an average length of 700 nanometers and an oxidation level of about 2% and polyvinyl alcohol, PVA, (Sigma Aldridge, average molecular weight 30,000 to 70,000 daltons, 87 to 90% hydrolyzed) are mixed with water and sonicated to give a dispersion of discrete carbon nanotubes of 2.25% by weight and PVA of 3.375% by weight. The discrete carbon nanotube solution is added together with water to the lead oxide, followed by slow addition of sulfuric acid. The anode material is glued to a lead grid and mounted in a battery with a lead oxide cathode, followed by standard battery formation as noted elsewhere, ie Lead-Acid Batteries: Science and Technology: Science and Technology, Elsevier 2011.
    [072] [072] Compared to control 6, Example 16 showed a higher load efficiency of at least 30% at load voltage 14.2v, a load increase rate of at least 200% and at least 50% less than polarization between 14 and 15 volts. Polarization is the difference between the battery voltage at equilibrium and one with current flowing.
    TABLE 4 Control 6 Example 10 kg kg Lead Oxide 230 230 Fiber Flake 0.15 0.15 Expander 1.4 1.4 Discrete carbon nanotubes 0 0.368 Polyvinyl alcohol 0 0.552 Water 27 27 Sulfuric acid 1.4 sg 23, 1 23.1
    权利要求:
    Claims (19)
    [1]
    1. Composition for use as a binding material, an electrolytic material or a separation film material of an energy storage or collection device, CHARACTERIZED by comprising: a plurality of discrete carbon nanotube fibers, said fibers with a ratio about 10 to about 500 in aspect, and wherein at least a portion of the discrete carbon nanotube fibers is open ended, wherein the portion of the open ended carbon nanotube fibers comprises electrolyte.
    [2]
    2. Composition according to claim 1, CHARACTERIZED by the fact that the electrolyte comprises a polymer or a liquid.
    [3]
    3. Composition according to claim 1 or 2, CHARACTERIZED by the fact that carbon nanotube fibers have a unimodal, bimodal or multimodal distribution of diameters and/or lengths.
    [4]
    4. Composition, according to claim 3, CHARACTERIZED by the fact that 40% to 90% in number of discrete carbon nanotubes have an aspect ratio of 30-70.
    [5]
    5. Composition, according to claim 3 or claim 4, CHARACTERIZED by the fact that 1% to 30% in number of carbon nanotubes have an average aspect ratio of 80-140.
    [6]
    6. Composition, according to claim 1, CHARACTERIZED by the fact that the part of the discrete carbon nanotubes with open ends is conducting ions.
    [7]
    Composition according to claim 6, characterized in that it further comprises additional inorganic structures comprising elements from groups 2 to 14 of the Periodic Table of Elements.
    [8]
    Binder composition according to claim 6, characterized in that it further comprises non-fibrous carbon structures selected from the group consisting of carbon black, graphite, graphene, oxidized graphene, fullerenes and mixtures thereof.
    [9]
    Composition according to claim 8, characterized in that it further comprises at least a part of discrete carbon nanotubes interspersed between graphene and/or oxidized graphene plates.
    [10]
    10. Composition according to claim 1, CHARACTERIZED by the fact that carbon nanotubes are oriented.
    [11]
    11. Composition according to claim 10, CHARACTERIZED by the fact that the orientation is carried out in a sheet, microlayer, microlayer with vertical orientation of film, film, molding, extrusion or a fiber spinning manufacturing method.
    [12]
    12. Composition according to claim 10 or claim 11, CHARACTERIZED by the fact that the orientation includes post-fabrication methods, such as stretching, uniaxial orientation, biaxial orientation and thermoforming.
    [13]
    Composition according to claim 1, characterized in that it further comprises at least one polymer.
    [14]
    14. Composition, according to claim 13, CHARACTERIZED by the fact that the polymer is selected from the group consisting of vinyl polymers, poly(styrene-butadiene), copolymers containing partially or fully hydrogenated poly(styrene-butadiene) , copolymers of poly(styrene-butadiene) functionalized as carboxylated poly(styrene-butadiene), poly(styrene-isoprene), poly(methacrylic acid), poly(methyl methacrylate), poly(acrylic acid), poly(vinyl alcohols) , poly(vinyl acetates), fluorinated polymers, polyvinylpyrrolidone, conductive polymers, polymers derived from natural sources, polyethers, polyesters, polyurethanes and polyamides; homopolymers, grafts, co- or ter-block or random polymers, and mixtures thereof
    [15]
    15. Composition, according to claim 1, CHARACTERIZED by the fact that carbon nanotubes are still functionalized.
    [16]
    16. Composition according to claim 1, CHARACTERIZED by the fact that it further comprises at least one dispersion adjuvant.
    [17]
    The composition of claim 1, characterized in that it is a binding material that has an impedance of less than or equal to about one billion ohm-m.
    [18]
    18. The composition of claim 1, characterized in that it is an electrolytic material or separation film that has a charge transfer resistance of less than or equal to about 10 million ohm-m.
    [19]
    Composition according to claim 1, characterized in that it is an electrode paste for a lead-acid battery comprising: discrete carbon nanotubes with an average length from about 400 to about 1400 nm; and polyvinyl alcohol.
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    同族专利:
    公开号 | 公开日
    AU2013278063A1|2015-01-22|
    CA2876494C|2021-09-21|
    RU2625910C9|2018-01-09|
    JP2015529933A|2015-10-08|
    US20180261884A1|2018-09-13|
    US10608282B2|2020-03-31|
    SG11201408474SA|2015-01-29|
    RU2014150431A|2016-08-20|
    US20130344396A1|2013-12-26|
    IN2015DN00108A|2015-05-29|
    CN104603980A|2015-05-06|
    RU2625910C2|2017-07-19|
    AU2013278063B2|2016-07-07|
    EP2865031B1|2016-08-31|
    KR20150036108A|2015-04-07|
    JP6294873B2|2018-03-14|
    CN104603980B|2017-07-21|
    EP2865031A2|2015-04-29|
    WO2013192513A2|2013-12-27|
    WO2013192513A3|2014-03-06|
    MX2014015896A|2015-08-14|
    CA2876494A1|2013-12-27|
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    法律状态:
    2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: H01M 2/16 (2006.01), H01M 4/14 (2006.01), H01M 4/6 |
    2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-06-23| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-10-05| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2022-03-08| B09B| Patent application refused [chapter 9.2 patent gazette]|
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    US201261662393P| true| 2012-06-21|2012-06-21|
    US61/662.393|2012-06-21|
    US201261663513P| true| 2012-06-22|2012-06-22|
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    PCT/US2013/047029|WO2013192513A2|2012-06-21|2013-06-21|Binders, electrolytes and separator films for energy storage and collection devices using discrete carbon nanotubes|
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