CN105280904A - Electrode Composition for Battery - Google Patents

Electrode Composition for Battery Download PDF

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Publication number
CN105280904A
CN105280904A CN201410776582.2A CN201410776582A CN105280904A CN 105280904 A CN105280904 A CN 105280904A CN 201410776582 A CN201410776582 A CN 201410776582A CN 105280904 A CN105280904 A CN 105280904A
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weight
cnt
composition
tube
carbon nano
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CN105280904B (en
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J·马
Y·张
C·邢
O·毛
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New Nai Technology Co Ltd
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Cnano Technology Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

Carbon nanotube-based compositions and methods of making an electrode for a battery are disclosed. It is an objective of the instant invention to disclose a composition for an electrode of a battery incorporating three dimensional networks of carbonaceous materials comprising a bi-modal diameter distribution of carbon nanotubes, CNT(A) and CNT(B), graphene, carbon black and, optionally, other forms of carbon-based pastes.

Description

Electrode for cell composition
Priority
The U.S. Non-provisional Patent application No.14/338 that patent application claims was submitted on July 22nd, 2014, the priority of 325 and rights and interests, the full content of this application is incorporated herein by reference.
The application is the U. S. application No.13/437 submitted on April 2nd, 2012, and the part continued access application of 205 also requires the priority of this application, and the full content of this application is incorporated herein by reference.
The cross reference of related application
The application relates to U.S.7, and 563,427, U.S.2009/0208708,2009/0286675; U.S.12/516,166; In the U. S. application 13/006,266 and 13/006,321 of submission on January 13rd, 2011 and in the U. S. application 13/285,243 of submission on October 31st, 2011, full contents of all these applications are all incorporated herein by reference.
Technical field
The present invention openly relates to the three-dimensional network of carbonaceous material, the composition of carbon intensifier electrode (carbonenhancedelectrode) and prepares the method for electrode for cell, and wherein said carbonaceous material comprises CNT (A), CNT (B), Graphene, carbon black and optional other forms of carbon base paste.
Carbon nano-tube (CNT) has the character of many uniquenesses because of its small size, cylindric graphite-structure and high aspect ratio.Single Walled Carbon Nanotube (SWCNT) forms the mono-layer graphite of cylindrical tubes by convolution or graphene film is formed.Multi-walled carbon nano-tubes (MWCNT) comprises the coaxial monolayer nanotube group arranged along fiber axis with the interlamellar spacing of 0.34 nanometer.Carbon nano-tube has high tensile strength (~ 150Gpa), high-modulus (~ 1Tpa), good chemistry and environmental stability and high-termal conductivity and conductivity.Have been found that carbon nano-tube can be used for many application, comprise preparation and there are the composite material of conductibility, electromagnetic performance and microwave absorbing property and high strength, fiber, transducer, Field Emission Display, ink, the semiconductor device of energy storage and energy conversion device, radiation source and nano-scale, probe and interconnection (interconnect) etc.Usually, carbon nano-tube has different performances according to the diameter of pipe.The material list that diameter is less reveals larger surface area and fibre strength; For major diameter nanotube, its surface to volume ratio is less, and less owing to being wound around, so compared with less nanotube, its surface area more easily utilizes.In addition, major diameter nanotube is usually more straight than minor diameter nanotube; Therefore, major diameter nanotube extends through larger space or volume in the matrix of composite material.
Carbon nano-tube has outstanding material property, but it is difficult to processing and is insoluble in most solvent.Before this, use such as polyvinylpyrrolidone (PVP), poly-sulfonated phenylethylene (PSS), polyphenylacetylene (PAA), poly-between sub-phenylethylene (PmPV), polypyrrole (PPy), polyparaphenylene's benzo two the polymer of azoles (PBO) and natural polymer and so on wraps up or coating carbon nanotube, and makes it in water soluble or organic solvent.In addition, the Amphoteric Materials that work before there was reported Single Walled Carbon Nanotube (SWCNT) and three types is scattered in aqueous solution: (i) aliphat anion surfactant, lauryl sodium sulfate (SDS); (ii) cyclic lipopeptide biosurfactant, surfactant protein; And (iii) water-soluble polymer, polyvinylpyrrolidone (PVP).
Conventional electroconductive paste or ink are primarily of polymeric binder and liquid medium composition, described polymeric binder comprises or is mixed with a small amount of electroconductive stuffing, and wherein said filler is such as the subparticle of metal (as silver, gold, copper, nickel, palladium or platinum) and/or carbonaceous material (as carbon black or graphite).Polymeric binder can make electroconductive stuffing be attached in substrate and/or by electroconductive stuffing and remain conductive pattern, and this conductive pattern plays the effect of conducting channel.Liquid medium comprises solvent (liquid as dissolved solid composition) and non-solvent (liquid as undissolved solid composition).Liquid medium serves and auxiliary polymeric binder and electroconductive stuffing applied or be deposited into the effect of some suprabasil carrier.The electroconductive paste being wherein dispersed with carbon nano-tube is a kind of multi-purpose material, and wherein carbon nano-tube defines low resistance conductive network.
Background technology
Background and supporting technology information can find in below with reference to document, and the full content of all these documents is all incorporated herein by reference: U.S.4, and 427,820, U.S.5,098,711, U.S.6,528,211, U.S.6,703,163, U.S.7,008,563, U.S.7,029,794, U.S.7,362,100, U.S.7,563,427, U.S.7,608,362, U.S.7,682,590, U.S.7,682,750, U.S.7,781,103, U.S.2004/0038251, U.S.2007/0224106, U.S.2008/0038635, U.S.2009/0208708, U.S.2009/0286675, U.S.2010/0021819, U.S.20100273050, U.S.2010/0026324, U.S.2010/0123079, 2010/0143798, 2010/0176337, U.S.2010/0300183, U.S.2011/0006461, U.S.2011/0230672, U.S.2011/0171371, U.S.2011/0171364, U.S.2014/0045065, U.S.2014/0079991, U.S.2014/0154577.
Summary of the invention
The invention discloses carbon nano-tube based composition and use thereof in packaging and prepare the method for battery (being optionally Li ion battery) electrode.This new disclosed technology is a kind of composition of the electrode for the preparation of lithium ion battery, said composition is mixed with carbon nano-tube, and it, by having lower electroconductive stuffing consumption and lower consumption of binder and having more active material, makes battery performance be strengthened.In one embodiment, the electrod composition that performance is strengthened employs less binding agent (such as PVDF), make the absolute magnitude of the electrode material in composition and ratio (by weight) raise thus, which in turn increases total memory capacity.Technology disclosed by the invention proposes for preparing the negative electrode of lithium ion battery or the composition of anode by mixing carbon nano-tube, and said composition is by having the performance of lower electroconductive stuffing consumption, lower consumption of binder and more active material thus enhancing battery.
Technology of the present invention proposes and combinationally uses major diameter carbon nano-tube and minor-diameter carbon nanotube, and optionally combines with other forms of carbon, thus provides negative electrode or the anode material of different size.Usually, the negative electrode that particle diameter is less and/or anode material often have less aperture under compacting, and have oarse-grained negative electrode and/or anode material can have larger pore volume under compacting.Minor-diameter carbon nanotube is applicable to inserting in the little space between negative electrode and/or anode pellets.When major diameter particle is present in electrode, minor diameter nanotube is not easy to fill space.The combination of large carbon nano-tube and little carbon nano-tube and optionally with other forms of carbon be combined as the various negative electrode that processes different-grain diameter and anode material provides solution.The ratio of major diameter nanotube and minor diameter nanotube depends on the selection (such as size, electrical property etc.) of negative electrode and/or anode material, and for all material being depressed into the pressure of current-collector.
As U.S. Provisional Patent Application No.61/294, described in 537, the electroconductive paste based on carbon nano-tube comprises the liquid medium of carbon nano-tube and the preferred amounts as dispersant and/or binding agent.In research process, find surprisingly: by combining with various weight ratio with other forms of carbon (such as CNT, Graphene and carbon black), required consumption of binder can be reduced further.
Accompanying drawing explanation
Figure 1A shows the schematic diagram of the coating be made up of active material, carbon nano-tube and binding agent be positioned on aluminium film, and wherein this aluminium film is as the electrode of lithium battery.Figure 1B and 1C shows large and little negative electrode and/or anode pellets in electrode layer.
Fig. 2 shows the cycle performance of the lithium ion battery comprising carbon nano-tube.
Fig. 3 show by scanning electron microscopy (SEM) observe by being positioned at LiFePO 4on the conductive network of CNT coating formation.
Fig. 4 is the schematic diagram of the Li ion battery showing component parts.
Fig. 5 is the electron micrograph of the carbon nano-tube that infiltration diameter is larger and less.
Fig. 6 A is the electron micrograph of the first example of interlaced graphene film and carbon nano-tube; Fig. 6 B is the cycle performance of the first lithium ion battery, and wherein this first lithium ion battery comprises the first example of the mixture of graphene film and carbon nano-tube.
Fig. 7 A is the electron micrograph of the second example of interlaced graphene film and carbon nano-tube; Fig. 7 B is the cycle performance of the second lithium ion battery, and wherein this second lithium ion battery comprises the second example of the mixture of graphene film and carbon nano-tube.
Embodiment
Definition
Term " three-dimensional network of carbonaceous material " refers to the filamentary structure of carbon nano-tube and other carbon structures in the present invention; Such as in some embodiments, three-dimensional network comprises carbon nano-tube CNT; Optionally, CNT has the first diameter range A and Second bobbin diameter scope B; Optionally, the three-dimensional network of carbonaceous material comprises carbon nano-tube and Graphene (flaky material); Optionally, the three-dimensional network of carbonaceous material comprises carbon nano-tube, Graphene and carbon black (spheroidal material); Optionally, the three-dimensional network of carbonaceous material comprises at least 2 kinds of carbonaceous materials in the group being selected from and being made up of CNT (A), CNT (B), Graphene, carbon black and other forms of carbon.In some embodiments, electrode material can have the three-dimensional network of multiple carbonaceous material.
As used herein, term " carbon nano-tube " refers to that diameter is the hollow carbon structure of about 2nm to about 100nm; With regard to object of the present invention, we refer to the many walls nanotube showing little chirality or do not have chirality.In order to distinguish the carbon nano-tube of different-diameter, term " CNT (A) " refers to that diameter is the nanotube of about 4-15nm more specifically; Term " CNT (B) " refers to that diameter is the nanotube of about 30-100nm more specifically.
Term " multi-walled carbon nano-tubes " (MWNT) refers to such carbon nano-tube, wherein graphene layer define along fiber axis arrange more than the coaxial clyinder of 1.
Term " carbon nanotube-based paste " refers to such conductive composite material, and wherein electroconductive stuffing is the three-dimensional network of carbonaceous material.
Term " composite material " refers to the material comprising at least one polymer and at least one carbonaceous material.
Term " dispersant " refers to and contributes in the composite disperseing and the reagent of the three-dimensional network of Stable Carbon material.
Term " carbon nano tube network " refers to the structure comprising and have the nanotube that " bimodal " distributes, the three-dimensional network of such as carbonaceous material, wherein said " bimodal " is distributed as the mixture of two kinds of different unimodal diameter distributions or only has the mixture of distribution of narrow diameter scope.Major diameter carbon nano-tube CNT (B) plays the effect of the skeleton of various conductive path, and minor diameter nanotube CNT (A) plays the effect connecting individual particle.In some embodiments, the diameter range of little carbon nano-tube CNT (A) is about 4-15nm; The diameter range of major diameter nanotube CNT (B) is about 30-100nm.
Electrod composition refers to that electrode active material adds any matrix of the surrounding being centered around this electrode active material or the composition of composite material.Specifically " electrod composition " material is coated or be bonded in metal conductor plate, as schematically shown in Fig. 4, when battery is in active electric discharge or (again) charged state, described metal conductor plate is collected or is distributed electronics or " electric current ".
The definition of term " carbon black " is identical with Wikipedia ﹛ wikipedia.org/wiki/Carbon_black ﹜ [on July 1st, 2014].Carbon black (its subclass has acetylene black, channel black, furnace black, dim and pyrolytic carbon black) is the material produced by the imperfect combustion of heavy crude product (such as FCC tar, coal tar, ethylene cracking tar), and derives from vegetable oil on a small quantity.Carbon black is para-crystal carbon form, and it has high surface-to-volume ratio (surface-area-to-volumeratio), but its surface-to-volume is than the surface-to-volume ratio lower than activated carbon.Its difference derive from very high surface-to-volume than and extremely low (insignificant and inanimate object usability) PAH (polycyclic aromatic hydrocarbons (PAH)) content.
The definition of term " Graphene " and identical in Wikipedia ﹛ wikipedia.org/wiki/Graphene ﹜ [on July 1st, 2014].Graphene is the crystal allotrope of the carbon with 2 dimension character.In Graphene, carbon atom dense packing becomes atom level wire netting (hexagon) pattern of the sp2 bonding of rule.Graphene can be described as the graphite linings of monoatomic thickness.It is the foundation structure element of other allotropes, comprises graphite, charcoal, carbon nano-tube and fullerene.In addition, Graphene can also be counted as infinitely-great aromatic molecules (limiting case (limitingcase) of plane polycyclic aromatic hydrocarbons (PAH) family).As used herein, term " Graphene " comprises other forms of Graphene, such as graphite tape or graphene nanoribbons, the Graphene formed by cutting openings carbon nano-tube, multi-layer graphene sheet and the Graphene of Powdered or dispersion shape prepared in polymer mechanism or adhesive, elastomer, oil, water-based and non-aqueous solution.
Carbon nano-tube
Report multiple carbon nano tube structure in the art, that is, single-walled nanotube, many walls nanotube, gas-phase growth of carbon fibre, VGCF etc.Notable difference between them is diameter, wherein the diameter >100nm of the diameter of SWCNT to be the diameter of 0.4-1.2nm, MWCNT be 2-100nm, VGCF.Figure 1A shows the schematic diagram of the coating formed by active material 1, carbon nano-tube CNT (A) 2 and binding agent 3 be positioned on aluminium film 4, and wherein aluminium film 4 is as the electrode of lithium battery.As shown in the figure, carbon nano-tube 2 serves the effect of the electroconductive stuffing forming conductive path in whole active material particle, thereby enhances total conductivity.
Figure 1B shows the mixing carbon nano-tube of large and little cathode particles 1, major diameter carbon nano-tube CNT (B) 5 and minor-diameter carbon nanotube CNT (A) 2 in electrode layer and binding agent 3 is formed as carbon nano tube network, thus provides unconventional packed structures and provide the conductive path that another kind can for select.
Fig. 1 C shows the large and little graphite anode carbonaceous particle in electrode layer, its carbon nano-tube with major diameter carbon nano-tube CNT (B) 5 and minor-diameter carbon nanotube CNT (A) 2 and binding agent 3 mix, thus formation carbon nano tube network, thus provide unconventional packed structures and provide the conductive path that another kind can for select.Fig. 5 shows interlaced CNT (A) 505 exemplary in the three-dimensional network of carbonaceous material and the SEM photo of CNT (B) 510 under 5000 times.
The preparation of carbon nano-tube is recorded widely.Usually, under the condition that there is carbonaceous agent, in the reactor of heating, use catalyst.At elevated temperatures, catalyst will decompose carbon precursor, and the carbonizable substance generated can with the form of nanotube deposition on the catalyst particles.As patent documentation U.S.7,563, described in 427, the mist of the hydrogen of fluid bed and low-speed, nitrogen and hydrocarbon can be used to realize the continuous volume production of carbon nano-tube.The carbon nano-tube of manufacture like this is be wound around shape, also referred to as three-dimensional network usually.Patent documentation U.S.7,563,427 (its full content is incorporated herein by reference) describe this winding, it comprises multiple transition metal nanoparticles and solid support, and wherein said multiple metal nanoparticle and described supporter combine multiple catalyst nano and be wound around (nano-entanglements); And multiple multi-walled carbon nano-tubes is deposited on multiple catalyst nano and is wound around.Described winding is of a size of about 0.5 micron to 10,000 micron, wherein the form of carbon nano-tube to be diameter be many walls nanotube of about 4nm to 100nm.The size of the winding so manufactured can be reduced by multiple means.The characteristic features of these windings are their tap densities; According to factors such as catalyst, growth conditions, technological designs, the tap density of the winding so manufactured can change between 0.02g/cm3 to 0.20g/cm3.Rigidity is wound around often has high tap density, and the winding of loose (fluffy) and single-walled nanotube have low tap density.
Dispersant
Dispersant plays the effect of the auxiliary agent of carbon nanotube dispersed in solvent.It can be polar polymeric compounds, surfactant or high viscosity liquid, such as mineral oil or wax.For dispersant of the present invention comprise polyvinylpyrrolidone (PVP), poly-sulfonated phenylethylene (PSS), polyphenylacetylene (PAA), poly-between sub-phenylethylene (PmPV), polypyrrole (PPy), polyparaphenylene's benzo two azoles (PBO), natural polymer, Amphoteric Materials in aqueous solution, aliphat anion surfactant, lauryl sodium sulfate (SDS), cyclic lipopeptide biosurfactant, surfactant protein, water-soluble polymer, polyvinyl alcohol (PVA), lauryl sodium sulfate (SDS), 1-METHYLPYRROLIDONE, polyoxyethylene surfactant, Kynoar (PVdF), carboxymethyl cellulose (CMC), hydroxyethylcellulose (HEC), polyacrylic acid (PAA), polyvinyl chloride (PVC) and their combination.The option of polymeric binder comprises mentioned dispersant, and polyethylene, polypropylene, polyamide, polyurethane, polyvinyl chloride, Kynoar, thermoplastic polyester and their combination.
Polyvinylpyrrolidone (PVP) can bond polar molecule well.When PVP is used as binding agent or dispersant (such as thickener), according to the difference of the molecular weight of PVP, PVP has different character.In some embodiments of the present invention, the molecular weight ranges for dispersant and/or binding agent is about 9,000 to 1,800,000 dalton; In some embodiments, molecular weight is about 50,000 to Isosorbide-5-Nitrae 00, and 000 dalton is preferred; In some embodiments, molecular weight is about 55, and 000 to 80,000 dalton is preferred.
Liquid medium
Water-based or nonaqueous liquid medium can be used as the carrier of carbonaceous material.Whether can dissolve the solid be mixed in wherein according to liquid medium, medium can be solvent or non-solvent.The volatility of liquid medium should be very not high, to such an extent as to it such as, can easily volatilize under relatively low temperature and pressure (such as room moderate pressure, 25 DEG C and 1atm).But volatility should be very not low, to such an extent as in the process of preparation paste, solvent does not volatilize on a small quantity.As used herein, " drying " or remove excessive liquid medium and refer to the volatilization promoting these compositions following, described composition can pass through baking, vacuum bakeout, centrifugal or some other removing liquefaction process and being removed in large quantities at lower than the temperature of 100 DEG C to 200 DEG C.
In one embodiment, liquid medium is used for dissolve polymer dispersant and some carbonaceous material, thus provides and easily put on suprabasil composition.The example of liquid medium includes but not limited to water, alcohol, ether, aromatic hydrocarbon, ester, ketone, 1-METHYLPYRROLIDONE and their mixture.In some cases, water is used as dissolve polymer and forms the solvent of liquid medium.As patent documentation U.S.4, disclosed such in 427,820 (full content of the document is incorporated herein by reference), when these water-based systems and specific combination of polymers, it can substitute solvent-based ink, keeps the thixotropy formulated simultaneously.
The dispersion of nanotube
It is difficult for carbon nano-tube and carbonaceous material being scattered in liquid, this is because nanotube entanglement forms large network.In some embodiments, a kind of means size of large network being decreased to the winding of acceptable size apply shearing force to winding; Shearing force is a kind of technology contributing to disperseing.Apply the means of shearing force to include but not limited to mill (milling), sand milling, ultrasonic, grinding, cavitation erosion or other means well known by persons skilled in the art.In one embodiment, the size first by using airslide disintegrating mill (jet-miller) to reduce carbon nano-tube.In some embodiments, the tap density after (optionally disperseing by milling) is disperseed to be decreased to about 0.06g/cm 3, or in some embodiments, tap density is decreased to 0.04g/cm 3, or in some embodiments, tap density is decreased to 0.02g/cm 3.In some embodiments, according to the needs of application, then use colloid mill, sand milling or other technologies to provide enough shearing forces, thus further broken nanotube entanglement.
The preparation of carbonaceous material network
Known diameter is about 50nm but the carbon nano-tube being less than about 100nm is more straight than less nanotube; Less nanotube is generally the latticed form of winding.In one embodiment, in the carbon nano tube network with the distribution of " bimodal " nanotube, minor diameter nanotube CNT (A) is first scattered in liquid suspension, such as nMP or water; Then directly joined in liquid suspension by major diameter nano-tube material CNT (B), fully stir and mix subsequently, the ratio wherein between major diameter nano-tube material and minor diameter nanotube is required ratio.Then, the paste of gained comprises the mixture of large nanotube and little nanotube, and these large nanotubes and little nanotube mutually intersect and form required network in new paste.Optionally, other carbonaceous material is joined in liquid suspension.
Exemplary lithium-ion active material comprises lithium-based compound and/or comprises lithium and the mixture being selected from one or more elements in following element, and these elements are: oxygen, phosphorus, sulphur, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, aluminium, niobium, zirconium and iron.Typical cathode material comprises lithium metal oxide (such as LiCoO 2, LiMn 2o 4with Li (Ni xmn yco z) O 2), barium oxide, olivine (such as LiFePO 4) and the oxidate for lithium that can again charge.The layered oxide comprising cobalt and nickel is also the material for lithium ion battery.
Exemplary anode material is lithium, carbon, graphite, Zinc-lithium alloy material, intermetallic compound and silicon and silicon base compound (such as silicon dioxide).The carbon anode comprising silicon and lithium is also adopted anode material.In another embodiment of the present invention, disclose (such as) and the combination of battery material and carbon nano tube network is applied to method on male or female liner plate (such as aluminium or copper).
Embodiment 1: carbon nano-tube [CNT (the A)] dispersion in 1-METHYLPYRROLIDONE
By the 30 grams of FloTube manufactured by CNanoTechnology Co., Ltd tM9000 carbon nano-tube are pulverized by jet grinding, and are placed in the beaker of 2 liters.The tap density of this material is 0.03g/mL.In another beaker of 500 milliliters, the PVPk90 of 6 grams (being manufactured by BASF AG) are dissolved in the 1-METHYLPYRROLIDONE of 100 grams.Then, the 1-METHYLPYRROLIDONE of this PVP solution together with 864 grams is transferred in nanotube.After one hour of the stirring, mixture is transferred in colloid mill, and grinds under the speed of 3,000RPM.Within every 30 minutes, take out test sample to be used for evaluating.Brookfield viscosimeter is used at 25 DEG C, to obtain the viscosity of each sample and record; Obtain Hegman scale reading simultaneously.Maximum dispersion is observed after 90 minutes in grinding.In grinding after 60 minutes, the fineness of this paste is less than 10 microns.This sample called after sample A.
Embodiment 2: the preparation of electrode paste
Under constant stirring, 10gPVDF (HSV900) and 100gN-methyl pyrrolidone be placed in 500mL beaker thus prepare PVDF solution.After whole PVDF dissolves, the paste (sample A) of the design flow obtained by embodiment 1 and PVDF solution are mixed 30 minutes under the strong stirring of 500-1000RPM.The mixture called after sample B of gained.
In another container, the active material of required weight of weighing under a nitrogen blanket, such as LiFePO 4or LiCoO 3.The sample B of selected amount is also joined in active material, and under high speed (such as 5000-7000RPM), mixture is stirred 5 hours.For LFP, the viscosity obtained by Brookfield viscosity meter should be controlled in 3000-8000cps, for LiCoO 3, this viscosity should be controlled in 7000-15000cps.At nitrogen environment and temperature implements this mixing and stirring under being no more than the condition of 40 DEG C.Gained sample called after sample C.
Embodiment 3: prepared by electrode
Select clean aluminium foil as cathode current collector also, place it on flat polymethyl methacrylate.Scraper deposit thickness on aluminium foil surface is used to be the shallow layer of the sample C of about 40 microns.Then, coated aluminium foil is placed 2 hours in the baking box of drying at 100 DEG C.Then by blocks for minus plate roll-in.Stamp out discoid coated aluminium foil from this aluminium foil, and be placed in button cell.Lithium metal is used as anode, and seals button cell after assembling cathode/separator/anode and inject electrolyte.Then, obtained battery is tested for various charging and discharging performance.
Embodiment 4: the ratio of components between commercialization electrode and electrode disclosed by the invention comparatively
The method described in embodiment 1-3 of use prepares the various samples comprising different cathode material.Electrode composition is listed in table 1.Battery capacity is measured for different electrodes composition.
Table 1: the comparison of electrode composition
Embodiment 5: the mechanical ratio of electrode comparatively (folding line test)
The adhesiveness of coated aluminium (Al) paper tinsel that further test is obtained by embodiment 3 and anti-folding line.Repeatedly folding aluminium foil, until coating produces slight crack or from stripping down on the surface.Table 2 shows the performance that coated Al paper tinsel stands repeatedly jackknife action.Folding times before numeral lost efficacy.
Table 2
Embodiment 6: the application of carbon nanotube pastes in cathode material for lithium ion battery
Select the CNT (A) comprising the CNT of 2% and the PVPk30 of 0.4% to stick with paste and manufacture lithium-ion button battery.By the LiFePO produced by Phostech/SudChemie 4as cathode material, and lithium paper tinsel is used as anode.Cathode material comprises LiFePO 4, CNT, PVP and PVDF, it is by by appropriate LiFePO 4, CNT to stick with paste with PVDF together with 1-METHYLPYRROLIDONE mixing in the Warren blender (warrenblender) and preparation.Use scraper to be coated on Al paper tinsel by this electrode paste, then carry out drying and compression.In order to be compared, Super-P carbon black (CB) is used to substitute CNT, and to prepare electrode with similar mode noted earlier.Composition and the volume resistivity of these two kinds of battery electrodes are summarized in following table.Significantly, under identical concentration, add the volume resistivity of the electrode of CNT far below the volume resistivity through carbon black modified sample.
The battery composition of table 3:CNT lithium ion battery and carbon black modified lithium ion battery
Inclusion CNT(A) CB
LiFePO 4 86.8％ 88％
Carbonaceous additive 2％ 2％
PVP 0.4％ -
PVDF 5％ 5％
Volume resistivity (ohm-cm) 3.1 31
Embodiment 7: cycle life evaluation
Under different charge rates, test the cycle life performance of the battery assembled by using the method described in embodiment 3.Fig. 2 shows carbon nano-tube [CNT (A)] buried electrode under various charge rate, shows excellent cycle life performance.But, the present inventor finds, when using multi-walled carbon nano-tubes of the present invention as conductive filler and when using multiple polymers (such as polyvinylpyrrolidone (PVP)) as dispersant, can eliminating or significantly reduce the amount of polymeric binder required in electroconductive paste.Thus, the present inventor finds the conductivity that can significantly improve electroconductive paste.
In some embodiments, electrod composition comprises carbon nano tube network, dispersant and liquid medium, wherein according to Hegman scale reading, nanotube network is separated into more than 7, optionally, carbon nano-tube is multi-walled carbon nano-tubes, optionally, carbon nano-tube is spherical network, optionally, electrod composition comprise be selected from by polyvinylpyrrolidone (PVP), poly-sulfonated phenylethylene (PSS), polyphenylacetylene (PAA), poly-between sub-phenylethylene (PmPV), polypyrrole (PPy), polyparaphenylene's benzo two azoles (PBO), natural polymer, Amphoteric Materials in aqueous solution, aliphat anion surfactant, lauryl sodium sulfate (SDS), cyclic lipopeptide biosurfactant, surfactant protein, water-soluble polymer, carboxymethyl cellulose, hydroxyethylcellulose, polyvinyl alcohol (PVA), lauryl sodium sulfate (SDS), polyoxyethylene surfactant, Kynoar (PVdF), carboxymethyl cellulose (CMC), hydroxyethylcellulose (HEC), polyacrylic acid (PAA), dispersant in the group that polyvinyl chloride (PVC) and their combination form, optionally, dispersant is polyvinylpyrrolidone, optionally, electrod composition comprises liquid medium, and it is selected from the group that water, alcohol, ether, aromatic hydrocarbon, ester, ketone, 1-METHYLPYRROLIDONE and composition thereof form, optionally, the solid bodies resistivity of electrod composition is lower than 10 -1Ω-cm, and viscosity is higher than 5,000cps, optionally, electrod composition comprises the carbon nano tube network that maximum dimension is about 0.5 micron to about 1000 microns, optionally, electrod composition has the carbon nano-tube that diameter is about 4nm to about 100nm, optionally, electrod composition comprises carbon nano tube network obtained in a fluidized bed reactor, optionally, electrod composition comprises such carbon nano tube network, the size of this carbon nano tube network is reduced by one or more techniques be selected from following technique group, and described technique group is: airslide disintegrating mill, ultrasonic generator, ultrasonic wave, colloid mill, ball mill, ball mill, sand mill, dry crushing mill and roller mill, optionally, electrod composition has tap density and is greater than about 0.02g/cm 3carbon nano tube network, optionally, in electrod composition, the content of carbon nano tube network is stick with paste about 1 % by weight to 15 % by weight, optionally, in electrod composition, the content of dispersant is stick with paste 0.2 % by weight to about 5 % by weight, optionally, in electrod composition, dispersant weight is less than 1 with the ratio of carbon nano tube network weight.
In some embodiments, the method for the manufacture of electrod composition comprises the following steps: select carbonaceous material network; Carbonaceous material network is joined in liquid medium, thus forms suspension; Carbonaceous material is made to be scattered in suspension; The size of network being decreased to Hegman scale is less than 7; And the partially liq medium in removing suspension, make the carbonaceous materials content in electrod composition be about 1 % by weight to 10 % by weight, volume resistivity is about 10 -1below Ω-cm, and viscosity is higher than 5,000cps; Optionally, the step that dispersant mixes with liquid medium before being included in further and adding carbonaceous material network by described method; Optionally, in the described method, dispersion steps is carried out by the dispensing implement be selected from the group that is made up of airslide disintegrating mill, ultrasonic generator, ultrasonic wave, colloid mill, ball mill, ball mill, sand mill, dry crushing mill and roller mill.
In some embodiments, electrod composition is made up of following composition: diameter is greater than the multi-walled carbon nano-tubes of 4nm, dispersant, its be selected from by polyvinylpyrrolidone (PVP), poly-sulfonated phenylethylene (PSS), polyphenylacetylene (PAA), poly-between sub-phenylethylene (PmPV), polypyrrole (PPy), polyparaphenylene's benzo two azoles (PBO), natural polymer, Amphoteric Materials in aqueous solution, aliphat anion surfactant, lauryl sodium sulfate (SDS), cyclic lipopeptide biosurfactant, surfactant protein, water-soluble polymer, carboxymethyl cellulose, hydroxyethylcellulose, polyvinyl alcohol (PVA), lauryl sodium sulfate (SDS), polyoxyethylene surfactant, Kynoar (PVdF), carboxymethyl cellulose (CMC), hydroxyethylcellulose (HEC), polyacrylic acid (PAA), polyvinyl chloride (PVC) and the group formed thereof, and liquid medium, its group selecting Free water, alcohol, ether, aromatic hydrocarbon, ester, ketone, 1-METHYLPYRROLIDONE and composition thereof to form, in this electrod composition, the content of carbonaceous material network is about 1 % by weight to 10 % by weight thus, and its volume resistivity is about 10 -1below Ω-cm, and its viscosity is higher than 5,000cps, optionally, electrod composition also comprises lithium ion battery electrode material, described lithium ion battery electrode material is selected from: lithium, oxygen, phosphorus, sulphur, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, aluminium, niobium, zirconium and iron, wherein the content of electrod composition is about 30 % by weight to about 50 % by weight, and viscosity is higher than about 5,000cps, optionally, electrod composition also comprises polymeric binder, optionally, electrod composition contacts with metal surface, thus forms lithium ion battery electrode, and liquid medium is removed.
In some embodiments, the method using paste composite disclosed by the invention to prepare battery electrode coating comprises the following steps: mixed with lithium ion oxide compound material by paste composite; Paste is applied on metal film, thus forms lithium ion battery electrode, and remove excessive or at least partially the liquid in coating; Optionally, the step that polymeric binder mixes with liquid medium before being also included in and being mixed with lithium ion battery material by paste composite by described method: optionally, described method employs the polymeric binder be selected from group that polyethylene, polypropylene, polyamide, polyurethane, polyvinyl chloride, Kynoar, thermoplastic polyester and composition thereof form, and this polymeric binder account for paste composite be less than about 5 % by weight; Optionally, described method make use of as invented U.S.7 assignee, 563,427, U.S. application 2009/0208708,2009/0286675 and U.S.12/516, the ball shaped nano pipe manufactured in a fluidized bed reactor described in 166 is wound around (sphericalcarbonnanotube).Optionally, paste composite part disclosed by the invention employs as invented U.S.7 assignee, 563,427, U.S. application 2009/0208708,2009/0286675 and U.S.12/516, the carbonaceous material network manufactured in a fluidized bed reactor described in 166.
In some embodiments, electrode material composite or electrode material for applying lithium battery metal current collector or metallic conductor comprise: the multi-walled carbon nano-tubes in a network in bimodal distribution, electrode active material, it is selected from the group be made up of lithium, oxygen, phosphorus, sulphur, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, graphite, aluminium, niobium, titanium, zirconium and iron, dispersant, its be selected from by polyvinylpyrrolidone (PVP), poly-sulfonated phenylethylene (PSS), polyphenylacetylene (PAA), poly-between sub-phenylethylene (PmPV), polypyrrole (PPy), polyparaphenylene's benzo two azoles (PBO), natural polymer, Amphoteric Materials in aqueous solution, aliphat anion surfactant, lauryl sodium sulfate (SDS), cyclic lipopeptide biosurfactant, surfactant protein, water-soluble polymer, carboxymethyl cellulose, hydroxyethylcellulose, polyvinyl alcohol (PVA), lauryl sodium sulfate (SDS), 1-METHYLPYRROLIDONE, polyoxyethylene surfactant, Kynoar (PVdF), carboxymethyl cellulose (CMC), hydroxyethylcellulose (HEC), polyacrylic acid (PAA), the group that polyvinyl chloride (PVC) and their combination form, and polymeric binder is selected from the group be made up of polyethylene, polypropylene, polyamide, polyurethane, polyvinyl chloride, Kynoar, thermoplastic polyester and their mixture, and what this polymeric binder accounted for electrode material composite is less than about 0.5 % by weight to 5 % by weight, wherein before being coated in metal current collector, the content of electrode active material is 30 % by weight to 50 % by weight, the content of carbonaceous material network is about 1 % by weight to about 10 % by weight, and the content of dispersant is for being less than 0.1 % by weight to 2 % by weight, after coating and drying, the content of electrode active material for being greater than 80 % by weight, and in some embodiments, for being greater than 90 % by weight, optionally, electrode material composite comprises the carbon nano tube network manufactured in a fluidized bed reactor, optionally, electrode material composite comprises the carbon nano tube network that maximum dimension is about 0.5 micron to about 1,000 micron, optionally, electrode material composite comprises the carbon nano-tube that diameter is about 4nm to about 100nm, optionally, electrode material composite comprises such carbon nano-tube, and wherein the tap density of carbon nano-tube winding (carbonnanotubeentanglements) is greater than about 0.02g/cm 3, optionally, electrode material comprises such carbonaceous material network, and wherein the volume resistivity of this material is less than 10ohm-cm, optionally, its volume resistivity is less than 1ohm-cm, optionally, its volume resistivity is less than 0.1ohm-cm, optionally, its volume resistivity is less than 0.05ohm-cm.
In some embodiments, electrode material composite disclosed by the invention is used to comprise the following steps to the method preparing electrode material: to form the paste composite comprising carbonaceous material network, dispersant and polymeric binder; Mixed with lithium ion battery active material composition by paste composite, wherein paste composite accounts for about 30 % by weight to about 50 % by weight of blend compositions; The paste composite of mixing and active material composite are coated on metallic conductor or electrode; And remove excessive volatile ingredient, thus form battery (being optionally lithium ion battery) electrode, like this after the excessive volatile ingredient of removing, what active material composite accounted for the paste of coating and battery material composition is greater than about 80 % by weight; Optionally, in the described method, after the excessive volatile ingredient of removing, what active material composite accounted for the paste of coating and battery material composition is greater than about 90 % by weight; Optionally, the step that before being included in further and paste composite being mixed with lithium ion battery material, polymeric binder mixed with liquid medium of described method; Optionally, in the process, described polymeric binder is selected from by polyethylene, polypropylene, polyamide, polyurethane, polyvinyl chloride, Kynoar, thermoplastic polyester and their mixture, and this polymeric binder account for paste composite be less than about 5 % by weight; Optionally, in the described method, the active material of lithium ion cell electrode is selected from by lithium, oxygen, phosphorus, sulphur, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, graphite, aluminium, niobium, titanium, zirconium and iron; Optionally, in the process, carbonaceous material network, dispersant and polymeric binder are formed dry bead, then it is mixed with lithium ion battery active material composition.In some embodiments, formation comprises the bead of the drying of carbonaceous material network, dispersant and polymeric binder to be conducive to being transported to different areas, can in these areas by itself and liquid medium or other dispersant, and subsequently electrod composition is coated in metallic conductor or base stage, and then dry.
Embodiment 8: in Ni/SiO 2major diameter carbon nano-tube [CNT (B)] prepared by catalyst
Major diameter carbon nano-tube is prepared by the catalytic decomposition of hydrocarbon (such as propylene).Use average grain diameter is that the silica gel of 5 μm carrys out Kaolinite Preparation of Catalyst.Nickel nitrate is flooded these silicon oxide particles with the nickel of about 1 weight portion than the ratio of the silica of 1.5 weight portions.Then, gained particle is calcined 2 hours in atmosphere at 400 DEG C.The crystal reaction tube of two (2) inches is heated to about 600 DEG C, uses nitrogen to purge simultaneously.The mixed flow of the nitrogen of the hydrogen of 1 liter/min and 1 liter/min is fed 5 minutes in heat pipe, thus catalyst is incorporated in reaction tube.After carrying out reducing about 10 minutes, the mixture of propylene/nitrogen (1:1) is made to pass through reactor with 2 liters/min.Make reaction continue 0.5 hour, afterwards under argon gas, make reactor be cooled to room temperature.Nanotube prepared by collection, through showing 15 times that its output is greater than catalyst weight.Reclaim and obtain fluffy black powder end-product.Scanning electron micrograph shows that the diameter of carbon nano-tube is 50-70nm.
Embodiment 9: prepare major diameter nanotube [CNT (B)] on Cu-Ni-Al catalyst
By copper nitrate, nickel nitrate and aluminum nitrate co-precipitation are carried out Kaolinite Preparation of Catalyst.In round-bottomed flask, the ratio being 3:7:1 with the mol ratio of Cu:Ni:Al takes 3 kinds of nitrate, and uses deionized water dissolving.Then, with continuous stirring the solution comprising 20% carbonic hydroammonium is slowly joined in flask.When pH value reaches 9 (under this point, precipitation stops), by the suspension of gained ageing under constant stirring (digest) 1 hour.Then, use deionized water washing sediment, carry out afterwards filtering, dry and calcining.The catalyst of gained comprises the Al of the Ni of 50 % by weight, the Cu of 24 % by weight and 3.5 % by weight.At 680 DEG C, 1 gram of catalyst is used to prepare nanotube according to the step described in embodiment 8.Isolate the nanotube amounting to 30g, its weight production is 29 times of catalyst.Scanning electron micrograph display is 80nm by the average diameter of the carbon nano-tube of this manufacture technics.
Embodiment 10: large nanotube and the mixing of little nanotube and the preparation of electrode
By CNT (B) and electroconductive paste with mass ratio 3:140 in Ross blender blended 5 hours, wherein this electroconductive paste comprises the little nanotube CNT (A) manufactured by embodiment 1 of 5%; " 140 " quality of electroconductive paste of CNT (A) for comprising 5%, result obtains the mixture that 2 kinds of different carbon nano-tube (A) and (B) are formed for 7:3 with mass ratio I:II; The ratio of major diameter nanotube in whole nanotube is 30 % by weight.Then, the large nanotube containing mixing and the paste of little nanotube, average diameter is used to be prepare electrode compound composition together with the graphite granule of 20 microns and other required binding agents (such as PVDF).Then, coating thing is put on Mylar sheet and be used for resistivity measurement, and use Copper Foil as the anode of battery.Further at constant pressure (such as 10kg/cm 2) under to coating sheet material suppress.
Use 4 point probes to measure volume resistivity, and by the results are shown in Table 4.
Table 4
Volume resistivity (Ohm-cm) CNT (A)/graphite CNT (I&II)/graphite
Do not suppress 0.33 0.38
After compacting 0.012 0.0086
Can clearly be seen that from data; compared with using the little carbon nano-tube of single size; mixing large nanotube and between little nanotube and graphite granule matrix, there is better electrical contact; and volume resistivity significantly reduces; the conductibility of the little carbon nano-tube of wherein said single size is better, but is not what optimize for the roomy pore volume existed in large graphite granule.
Embodiment 11: use Graphene and carbon nano-tube to prepare electrode
5 grams of polyvinylpyrrolidone (PVP) powder are joined in 470 grams of 1-METHYLPYRROLIDONE (NMP) solvents, and is stirred to and dissolves completely.(specific area is 150m for the FloTubeTM9000 multi-walled carbon nano-tubes pulverize PVP/NMP solution and 20 grams and a kind of graphene powder of 5 grams 2/ g) together join in colloid mill, and grind with the speed of 3,000RPM.Within every 30 minutes, take out test sample to be used for evaluating.Brookfield viscosimeter is used at 25 DEG C, to obtain the viscosity of each sample and record; Obtain Hegman scale reading simultaneously.Maximum dispersion is observed after 180 minutes in grinding.In grinding after 60 minutes, the fineness of this paste is less than 10 microns.This paste called after sample A1.SEM image is shown in Fig. 6 A.Wherein show the graphene film that some is curling, this is because this graphene film is very thin.Slightly thick graphene film is employed in following embodiment 12.
Use the above-mentioned paste sample A1 comprising the CNT of 4% and the Graphene of 1% to manufacture lithium-ion button battery.By the LiFePO produced by Phostech/SudChemie 4as cathode material, and lithium paper tinsel is used as anode.Cathode material comprises LiFePO 4, CNT, PVP and PVDF, it is by by appropriate LiFePO 4, CNT sticks with paste and PVDF and 1-METHYLPYRROLIDONE one coexist and to mix under the speed of 3,000RPM in high speed blender and to prepare.Use scraper on Al paper tinsel, form the coating of this paste, and carry out drying and compacting subsequently.SEM image is shown in Fig. 6 A.As shown in Figure 6B, under different discharge rates, test the cycle life performance of the battery assembled by using method described in embodiment 3.Result shows, the electrode having imbedded graphene film and carbon nano-tube all has excellent cycle life performance under various charge rate.
Embodiment 12: mixing and the preparation of electrode of Graphene and carbon nano-tube
According to the step identical with embodiment 11, but use the second Graphene (specific area 50m 2/ g) manufacture the second paste (sample A2).SEM image is shown in Fig. 7 A.According to the step identical with embodiment 11, use above-mentioned paste sample A2 to manufacture lithium-ion button battery, and as shown in Figure 7 B, under the condition of different discharge rates, its cycle life performance is tested.Again show that the electrode of the mixture that embedded in graphene film and carbon nano-tube all has excellent cycle life performance under various charge rate.
In some embodiments, advantageously, electrod composition comprises a part of major diameter carbon nano-tube and a part of minor-diameter carbon nanotube.With regard to embodiments more of the present invention, " major diameter " CNT (CNT (B)) is defined as those nanotubes that diameter is about 40nm to about 100nm; " minor diameter " CNT (CNT (A)) is defined as those nanotubes that diameter is about 4nm to 15nm.The major diameter nanotube being defined as 30-100nm is usually very long, at least than minor diameter nanometer pipe range 1-10 micron or longer, thus defines main conductive path.Minor diameter CNT serves as " local path " or network.In some embodiments, ratio (by weight) A of minor diameter nanotube is about 50 % by weight to about 95 % by weight.In above-described embodiment 10, the ratio of " A "/[" A "+" B "] equals about 70%.
In some embodiments, electrode material composite for being applied to the coating on battery conducting electrode (one in negative electrode or anode) comprises: the multi-walled carbon nano-tubes being in winding state, this many walls nanotube comprises the Part I be made up of major diameter carbon nano-tube CNT (B) and the Part II be made up of minor-diameter carbon nanotube CNT (A), makes the weight ratio of the total weight of Part II and Part I and Part II about 0.05 to about between 0.50; Electrode active material; Dispersant; And polymeric binder, what make polymeric binder account for electrode material composite is less than about 0.5 % by weight to about 5 % by weight, wherein before coating is put on electrode, the content of electrode active material is about 30 % by weight to 60 % by weight, the content of whole carbon nano-tube is about 0.2 % by weight to about 5 % by weight, and the content of dispersant is about 0.1 % by weight to 2 % by weight; Optionally, carbon nano-tube is wound around and manufactures in a fluidized bed reactor; Optionally, the maximum dimension that carbon nano-tube is wound around be about 0.5 micron extremely about 1,000 micron; Optionally, the diameter range of major diameter carbon nano-tube is about 40nm to about 100nm, and the diameter range of minor-diameter carbon nanotube is about 5nm to about 20nm; Optionally, the tap density that carbon nano-tube is wound around is greater than about 0.02g/cm 3; Optionally, the volume resistivity of electrode coating is less than 10Ohm-cm (negative electrode) and 1Ohm-cm (anode).
In some embodiments, the method preparing electrode compound comprises the following steps: formed and comprise that carbon nano-tube is wound around, the paste composite of dispersant and polymeric binder; Mixed with battery active material composition by paste composite, wherein paste composite accounts for about 1 % by weight to about 25 % by weight of blend compositions; The paste composite of mixing and active material composite are coated on electric conductor; And remove excessive volatile ingredient, thus formation electrode for cell, make after removing excessive volatile ingredient, what active material composite accounted for the paste of coating and the composition of battery material is greater than about 80 % by weight, and the volume resistivity of coating is less than about 10Ohm-cm (negative electrode) and 1Ohm-cm (anode); Optionally, after the excessive volatile ingredient of removing, what active material composite accounted for the paste of coating and battery material composition is greater than about 90 % by weight; Optionally, before described method is included in further and is mixed with lithium ion battery material by paste composite, by the step that polymeric binder mixes with liquid medium; Optionally, described polymeric binder is selected from the group be made up of polyethylene, polypropylene, polyamide, polyurethane, polyvinyl chloride, Kynoar, thermoplastic polyester and their mixture, and polymeric binder account for paste composite be less than about 5 % by weight; Optionally, battery electrode active material is selected from the group be made up of lithium, oxygen, phosphorus, sulphur, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, graphite, aluminium, niobium, titanium, zirconium and iron; Optionally, multi-walled carbon nano-tubes winding, dispersant and polymeric binder are formed as dry bead, then mix with battery active material composition.
In some embodiments, material compositions for coating electrically conductive collector body or the conductive layer on battery electrode comprises: conductivity additive, and it comprises the three-dimensional network of at least two kinds of carbonaceous materials in the group being selected from the first diameter carbon nano-tube CNT (A), Second bobbin diameter carbon nano-tube CNT (B), Graphene and carbon black formation; Electrode material; Dispersant; And polymeric binder, wherein polymeric binder accounts for about 0.005 weight portion of material compositions to about 0.10 weight portion, and wherein electrode material is about 0.30 weight portion to 0.90 weight portion; Carbonaceous material is that about 0.01 weight portion is to about 0.20 weight portion; Optionally, carbonaceous material is that about 0.01 weight portion is to about 0.10 weight portion; And before being coated on collector body, dispersant is for being less than about 0.001 weight portion to about 0.10 weight portion; Optionally, carbonaceous material is that about 0.05 weight portion is to about 0.20 weight portion; Optionally, the volume resistivity of material compositions is about 0.01ohm-cm to 10ohm-cm; Optionally, dispersant is selected from the group be made up of polyvinylpyrrolidone and HypermerKD-1, and such dispersant is stable under the voltage of about 4.4 volts; Optionally, polymeric binder is PVDF; Optionally, electrode material is selected from the group be made up of lithium and cobalt oxides, LiFePO4, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, Li-S, lithium nickel cobalt aluminum oxide and their combination; Optionally, the three-dimensional network of described carbonaceous material comprises the Part I be made up of minor-diameter carbon nanotube CNT (A) and the Part II be made up of major diameter carbon nano-tube CNT (B), and the weight ratio making the total weight of Part I CNT (A) and Part I and Part II is about 0.50 to about 0.95; Optionally, the three-dimensional network of carbonaceous material comprises Graphene further, makes the weight ratio of Graphene and CNT (A+B) be 0.05 to 0.5 (by weight); Optionally, the three-dimensional network of carbonaceous material comprises Graphene and carbon black further, wherein the carbonaceousfuel component of conductivity additive comprise the CNT (A+B) of about 70 % by weight ± 10 % by weight, the Graphene of about 20 % by weight ± 5 % by weight and about 10 % by weight ± 5 % by weight carbon black.
In some embodiments, comprise the following steps for the preparation of coating electrically conductive collector body or as the method for the material compositions of the conductive layer of battery electrode: the first composition forming three-dimensional network, dispersant and the polymeric binder comprising carbonaceous material, the three-dimensional network of whole first composition is scattered in liquid medium, first composition and liquid medium are mixed with battery material composition, thus prepare such material compositions, wherein the first composition accounts for about 0.01 to about 0.50 weight portion of material compositions, the material compositions of mixing is coated on conductivity collector body, and remove excessive composition thus form electrode for cell, make after the excessive composition of removing, what battery material composition accounted for the composition of mixing is greater than about 80 % by weight, optionally, polymeric binder is selected from the group be made up of polyethylene, polypropylene, polyamide, polyurethane, polyvinyl chloride, Kynoar, thermoplastic polyester and their mixture, and this polymeric binder account for total material compositions be less than about 5 % by weight, optionally, battery material composition is selected from the group be made up of lithium, oxygen, phosphorus, sulphur, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, graphite, aluminium, niobium, titanium, zirconium and iron, optionally, the first composition forms dry bead, then mixes with battery material composition, optionally, the three-dimensional network of carbonaceous material is selected from the carbon nano-tube of at least 2 kinds of different-diameters, makes the part by weight of minor diameter CNT (A) in the total weight of two kinds of diameter CNT be about 0.50 to about 0.95, optionally, the three-dimensional network of carbonaceous material comprises Graphene further, makes the weight ratio of the total weight of Graphene and two kinds of diameter CNT for about 0.05 weight portion to 0.5 weight portion, optionally, the three-dimensional network of carbonaceous material comprises carbon black further, makes in described total weight, and the content of the CNT of 2 kinds of diameters is about 70% ± 10%, the content of Graphene is about 20% ± 5% and the content of carbon black is about 10% ± 5%, optionally, dispersant be selected from by polyvinylpyrrolidone (PVP), poly-sulfonated phenylethylene (PSS), polyphenylacetylene (PAA), poly-between sub-phenylethylene (PmPV), polypyrrole (PPy), polyparaphenylene's benzo two azoles (PBO), natural polymer, Amphoteric Materials in aqueous solution, aliphat anion surfactant, lauryl sodium sulfate (SDS), cyclic lipopeptide biosurfactant, surfactant protein, water-soluble polymer, carboxymethyl cellulose, hydroxyethylcellulose, polyvinyl alcohol (PVA), lauryl sodium sulfate (SDS), 1-METHYLPYRROLIDONE, polyoxyethylene surfactant, Kynoar (PVDF), carboxymethyl cellulose (CMC), hydroxyethylcellulose (HEC), polyacrylic acid (PAA), the group that polyvinyl chloride (PVC) and combination thereof are formed, such dispersant is stable under the voltage of about 4.4 volts.
Although the present invention's mode being described according to specific embodiment by way of example, it should be understood that and the invention is not restricted to disclosed embodiment.On the contrary, the present invention is intended to contain apparent various amendment and similar arrangement for those skilled in the art.Therefore, the scope of appending claims should meet and illustrates the most widely, to contain all such modifications and similar arrangement.With regard to all objects, the full content of all publication, patents and patent applications that the present invention quotes all is incorporated herein by reference.
Preferably, all elements of the present invention, parts and step are all included.Any one that it should be understood that these elements, parts and step all can be substituted by other element, parts and step or all delete, and this is apparent for those skilled in the art.
In the broadest sense, following aspect is disclosed herein.Disclose carbon nano-tube system: compositions and the method preparing electrode for cell.Disclose the composition for battery electrode, said composition introduces the three-dimensional network of carbonaceous material, and said composition comprises the carbon nano-tube CNT (A) and CNT (B), Graphene, carbon black and optional other forms of carbon base paste with the distribution of bimodal diameter.
Viewpoint
Following discloses following viewpoint.
The material compositions of the conductive layer of viewpoint 1. 1 kinds on battery electrode, it comprises:
Conductivity additive, it comprises the three-dimensional network of at least two kinds of carbonaceous materials in the group being selected from and being made up of the carbon nano-tube CNT (B) of the carbon nano-tube CNT of the first diameter (A), Second bobbin diameter, Graphene and carbon black;
Electrode material;
Dispersant; And
Polymer adhesive; Wherein in the composition of described material compositions, described polymer adhesive is that about 0.01 weight portion is to about 0.05 weight portion; Described electrode material is about 0.30 weight portion to 0.90 weight portion; Described carbonaceous material is that about 0.005 weight portion is to about 0.10 weight portion; And described dispersant is that about 0.001 weight portion is to about 0.005 weight portion.
Material compositions described in viewpoint 2. viewpoint 1, the volume resistivity of wherein said material compositions is about 0.01ohm-cm to 10ohm-cm.
Material compositions described in viewpoint 3. viewpoint 1 or 2, wherein said dispersant is selected from the group be made up of polyvinylpyrrolidone and HypermerKD-1, makes described dispersant be stable under the voltage of about 4.4 volts.
The material compositions described in any one in viewpoint 4. foregoing viewpoint, wherein said polymeric binder is PVDF.
The material compositions described in any one in viewpoint 5. foregoing viewpoint, wherein said electrode material is selected from the group be made up of lithium and cobalt oxides, LiFePO4, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, Li-S, lithium nickel cobalt aluminum oxide and their combination.
The material compositions described in any one in viewpoint 6. foregoing viewpoint, the three-dimensional network of wherein said carbonaceous material comprises the Part I be made up of minor-diameter carbon nanotube CNT (A) and the Part II be made up of major diameter carbon nano-tube CNT (B), and the weight ratio making the total weight of Part I CNT (A) and Part I and Part II is about 0.50 to about 0.95.
The material compositions described in any one in viewpoint 7. foregoing viewpoint, the three-dimensional network of wherein said carbonaceous material comprises Graphene further, and the weight ratio making Graphene and described CNT (A+B) is about 0.05 to about 0.5.
Material compositions described in viewpoint 8. viewpoint 7, the three-dimensional network of wherein said carbonaceous material comprises carbon black further, the carbonaceousfuel component of wherein said conductivity additive comprise the CNT (A+B) of about 70 % by weight ± 10 % by weight, the Graphene of about 20 % by weight ± 5 % by weight and about 10 % by weight ± 5 % by weight carbon black.
Viewpoint 9. 1 kinds of methods for the preparation of the material compositions of the conductive layer on battery electrode, it comprises the following steps:
Form the first composition of three-dimensional network, dispersant and the polymeric binder comprising carbonaceous material;
Described three-dimensional network in whole described first compositions is scattered in liquid medium;
Described first composition and described liquid medium are mixed with battery material composition, thus prepare described material compositions, wherein said first composition accounts for about 0.01 weight portion of described material compositions to about 0.50 weight portion;
Described material compositions is coated on described battery electrode; And
Remove excessive composition, thus form electrode for cell, make after the described excessive composition of removing, what described battery material composition accounted for described blend compositions is greater than about 0.80 weight portion.
Method described in viewpoint 10. viewpoint 9, wherein said polymeric binder is selected from the group be made up of polyethylene, polypropylene, polyamide, polyurethane, polyvinyl chloride, Kynoar, thermoplastic polyester and their mixture, and described polymeric binder account for whole described material compositions be less than about 10 % by weight.
Viewpoint 11. viewpoint 9 or the method described in viewpoint 10, wherein said battery material composition is selected from the group be made up of lithium, oxygen, phosphorus, sulphur, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, graphite, aluminium, niobium, titanium, zirconium and iron.
Method described in viewpoint 12. viewpoint 9,10 or 11, the three-dimensional network of wherein said carbonaceous material is selected from the group be made up of the carbon nano-tube of at least 2 kinds of different-diameters, makes minor diameter CNT (A) be about 0.50 to about 0.95 with the weight ratio of the total weight of the CNT of 2 kinds of diameters.
Method described in viewpoint 13. viewpoint 12, the three-dimensional network of wherein said carbonaceous material comprises Graphene further, and the weight ratio making the total weight of the CNT of described Graphene and described 2 kinds of diameters is about 0.05 to 0.5.
Material compositions described in viewpoint 14. viewpoint 13, the three-dimensional network of wherein said carbonaceous material comprises carbon black further, make in described total weight, the content of the CNT of 2 kinds of diameters is about 70% ± 10%, the content of Graphene is about 20% ± 5% and the content of carbon black is about 10% ± 5%.
The method described in any one of viewpoint 15. viewpoint 9-14, wherein said dispersant be selected from by polyvinylpyrrolidone (PVP), poly-sulfonated phenylethylene (PSS), polyphenylacetylene (PAA), poly-between sub-phenylethylene (PmPV), polypyrrole (PPy), polyparaphenylene's benzo two azoles (PBO), natural polymer, Amphoteric Materials in aqueous solution, aliphat anion surfactant, lauryl sodium sulfate (SDS), cyclic lipopeptide biosurfactant, surfactant protein, water-soluble polymer, carboxymethyl cellulose, hydroxyethylcellulose, polyvinyl alcohol (PVA), lauryl sodium sulfate (SDS), 1-METHYLPYRROLIDONE, polyoxyethylene surfactant, Kynoar (PVDF), carboxymethyl cellulose (CMC), hydroxyethylcellulose (HEC), polyacrylic acid (PAA), the group that polyvinyl chloride (PVC) and their combination form, described dispersant is made to be stable under the voltage of about 4.4 volts.

Claims (15)

1. a material compositions for the conductive layer on battery electrode, it comprises:
Conductivity additive, it comprises the three-dimensional network of at least two kinds of carbonaceous materials in the group being selected from and being made up of the carbon nano-tube CNT (B) of the carbon nano-tube CNT of the first diameter (A), Second bobbin diameter, Graphene and carbon black;
Electrode material;
Dispersant; And
Polymer adhesive; Wherein in the composition of described material compositions, described polymer adhesive is that about 0.01 weight portion is to about 0.05 weight portion; Described electrode material is about 0.30 weight portion to 0.90 weight portion; Described carbonaceous material is that about 0.005 weight portion is to about 0.10 weight portion; And described dispersant is that about 0.001 weight portion is to about 0.005 weight portion.
2. material compositions according to claim 1, the volume resistivity of wherein said material compositions is about 0.01ohm-cm to 10ohm-cm.
3. material compositions according to claim 1, wherein said dispersant is selected from the group be made up of polyvinylpyrrolidone and HypermerKD-1, makes described dispersant be stable under the voltage of about 4.4 volts.
4. material compositions according to claim 1, wherein said polymeric binder is PVDF.
5. material compositions according to claim 1, wherein said electrode material is selected from the group be made up of lithium and cobalt oxides, LiFePO4, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, Li-S, lithium nickel cobalt aluminum oxide and their combination.
6. material compositions according to claim 1, the three-dimensional network of wherein said carbonaceous material comprises the Part I be made up of minor-diameter carbon nanotube CNT (A) and the Part II be made up of major diameter carbon nano-tube CNT (B), and the weight ratio making the total weight of Part I CNT (A) and Part I and Part II is about 0.50 to about 0.95.
7. material compositions according to claim 1, the three-dimensional network of wherein said carbonaceous material comprises Graphene further, and the weight ratio making Graphene and described CNT (A+B) is about 0.05 to about 0.5.
8. material compositions according to claim 7, the three-dimensional network of wherein said carbonaceous material comprises carbon black further, the carbonaceousfuel component of wherein said conductivity additive comprise the CNT (A+B) of about 70 % by weight ± 10 % by weight, the Graphene of about 20 % by weight ± 5 % by weight and about 10 % by weight ± 5 % by weight carbon black.
9., for the preparation of a method for the material compositions of the conductive layer on battery electrode, it comprises the following steps:
Form the first composition of three-dimensional network, dispersant and the polymeric binder comprising carbonaceous material;
Described three-dimensional network in whole described first compositions is scattered in liquid medium;
Described first composition and described liquid medium are mixed with battery material composition, thus prepare described material compositions, wherein said first composition accounts for about 0.01 weight portion of described material compositions to about 0.50 weight portion;
Described material compositions is coated on described battery electrode; And
Remove excessive composition, thus form electrode for cell, make after the described excessive composition of removing, what described battery material composition accounted for described blend compositions is greater than about 0.80 weight portion.
10. method according to claim 9, wherein said polymeric binder is selected from the group be made up of polyethylene, polypropylene, polyamide, polyurethane, polyvinyl chloride, Kynoar, thermoplastic polyester and their mixture, and described polymeric binder account for whole described material compositions be less than about 10 % by weight.
11. methods according to claim 9, wherein said battery material composition is selected from the group be made up of lithium, oxygen, phosphorus, sulphur, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, graphite, aluminium, niobium, titanium, zirconium and iron.
12. methods according to claim 9, the three-dimensional network of wherein said carbonaceous material is selected from the group be made up of the carbon nano-tube of at least 2 kinds of different-diameters, makes minor diameter CNT (A) be about 0.50 to about 0.95 with the weight ratio of the total weight of the CNT of 2 kinds of diameters.
13. methods according to claim 12, the three-dimensional network of wherein said carbonaceous material comprises Graphene further, and the weight ratio making the total weight of the CNT of described Graphene and described 2 kinds of diameters is about 0.05 to 0.5.
14. methods according to claim 13, the three-dimensional network of wherein said carbonaceous material comprises carbon black further, make in described total weight, the content of the CNT of 2 kinds of diameters is about 70% ± 10%, the content of Graphene is about 20% ± 5% and the content of carbon black is about 10% ± 5%.
15. methods according to claim 9, wherein said dispersant be selected from by polyvinylpyrrolidone (PVP), poly-sulfonated phenylethylene (PSS), polyphenylacetylene (PAA), poly-between sub-phenylethylene (PmPV), polypyrrole (PPy), polyparaphenylene's benzo two azoles (PBO), natural polymer, Amphoteric Materials in aqueous solution, aliphat anion surfactant, lauryl sodium sulfate (SDS), cyclic lipopeptide biosurfactant, surfactant protein, water-soluble polymer, carboxymethyl cellulose, hydroxyethylcellulose, polyvinyl alcohol (PVA), lauryl sodium sulfate (SDS), 1-METHYLPYRROLIDONE, polyoxyethylene surfactant, Kynoar (PVDF), carboxymethyl cellulose (CMC), hydroxyethylcellulose (HEC), polyacrylic acid (PAA), the group that polyvinyl chloride (PVC) and their combination form, described dispersant is made to be stable under the voltage of about 4.4 volts.
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