CN1468455A - High performance lithium or lithium ion cell - Google Patents

High performance lithium or lithium ion cell Download PDF

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Publication number
CN1468455A
CN1468455A CNA018168434A CN01816843A CN1468455A CN 1468455 A CN1468455 A CN 1468455A CN A018168434 A CNA018168434 A CN A018168434A CN 01816843 A CN01816843 A CN 01816843A CN 1468455 A CN1468455 A CN 1468455A
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China
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lithium
electrochemical cell
carbonate
graphite
electrolyte
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CNA018168434A
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Chinese (zh)
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H・戴
H·戴
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纳幕尔杜邦公司
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Priority to US09/684,206 priority Critical patent/US6699623B1/en
Priority to US09/684,206 priority
Application filed by 纳幕尔杜邦公司 filed Critical 纳幕尔杜邦公司
Publication of CN1468455A publication Critical patent/CN1468455A/en

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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • H01M4/663Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565Polymeric materials, e.g. gel-type or solid-type
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566Liquid materials
    • H01M10/0568Liquid materials characterised by the solutes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/058Construction or manufacture
    • H01M10/0585Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • H01M4/665Composites
    • H01M4/667Composites in the form of layers, e.g. coatings
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/04Construction or manufacture in general
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0017Non-aqueous electrolytes
    • H01M2300/0025Organic electrolyte
    • H01M2300/0028Organic electrolyte characterised by the solvent
    • H01M2300/0037Mixture of solvents
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00Primary cells; Manufacture thereof
    • H01M6/14Cells with non-aqueous electrolyte
    • H01M6/16Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/166Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

Graphite sheeting having a thickness of less than 250 micrometers and in-plane conductivity of at least 100 S/cm when employed as a cathode current collector in a lithium or lithium ion cell containing a fluorinated lithium imide or methide electrolyte salt imparts high thermal resistance, excellent electrochemical stability, and surprisingly high capacity retention at high rates of discharge.

Description

High-performance lithium or lithium ion battery

Invention field

The present invention relates under the high velocity of discharge, show astoundingly the lithium and the lithium ion battery of high power capacity conservation rate and long circulation life, and relate to the intensification fusion method that is used for its preparation.

Technical background of the present invention

Known in electrochemical cell in this area, particularly in having metal collector corrosion dangerous environment, adopt graphite current collector.This metal collector is except that its potential corrosion, because their high live stream abilities are preferred.Use noble metal in some cases, but their uses in most of commercial application of their expensive obstruction.In most cases generally select aluminium and copper material as current-collector in lithium and the lithium ion battery.

JP-A Sho such as Toyuguchi 58 (1983)-115777 disclose a kind of Delanium plate current-collector that uses in lithium metal/polyacetylene battery, wherein use LiClO 4Solution in propylene carbonate or the LiBF4 solution in gamma-butyrolacton is as electrolyte.The charge efficiency that shows is higher than the comparable battery with metal collector far away.Adopted 2 hours or longer charge-discharge cycles is measured charge efficiency, the electric current that is to say use is no more than 50% of in the 1 hour required electric current of battery discharge.The battery that Toyuguchi uses is not a lithium ion battery.

British patent specification 1,214,4123 (Standard Oil Company) disclose flexible graphite platelet as the current-collector in the carbon electrode that is embedded in molten salt electrolyte battery (it uses the binary salt electrolyte, mainly is the combination of LiCl and KCL) use.The thickness of graphite flake is about 250 microns, it is characterized in that the interior resistance of face of this sheet is 8 * 10 -4Ohm-cm.

The WO99/59218 of Gratzel etc. has related to lithium or lithium ion battery, and one electrode is made up of the solid material that with the mesoscopic structure form is feature.Also disclose secondary (rechargeable) battery, wherein in aprotic solvent, can use two (three fluorosulfonyls) imino group lithium or three (three fluorosulfonyls) lithium methides as electrolyte.Discovery comprises TiO 2As anode and Li yMn 2O 4Keep the 10C velocity of discharge and keep 1.5 volts cell voltage as electrolyte and paper battery as negative electrode, the solution of two (three fluorosulfonyls) imino group lithiums in methoxypropionitrile as dividing plate.Current-collector is the indium tin oxide target that is deposited on the conduction on the substrate of glass.Compare more preferably TiO with carbon anode 2Anode.

The JP Hei 5 (1993)-290887 of Fujimoto etc. discloses secondary lithium battery, it comprise negative electrode, graphite powder and the acrylic resin compound of lithium metal oxide compound cathode collector, powdered graphite anode, Copper Foil anode collector and be dissolved in ethylene carbonate and the mixture of dimethyl carbonate in LiCF 3SO 3Electrolyte.The battery cell of Xing Chenging it is said the employing LiPF with present technology like this 6Electrolyte is compared with the battery that the aluminium cathode collector combines has improvement, the harmfulness of having exploded when its improvement has been to reduce short circuit, and improved the charging and discharging characteristic.Capacity is that the battery of 500mA-h discharges with 200mA in 4.1 to 3 volts voltage range; Used very high volume percent, and when recharging, restored.

The present invention's general introduction

The present invention relates to lithium or lithium ion electrochemical cells, this battery comprises anode, is anode collector that conductivity contacts with this anode, with respect to Li/Li +Reference electrode shows the negative electrode of 3 to 5 volts upper limit charge voltage range, described negative electrode comprises that being not less than 250 microns cathode collector with thickness is the lithium that conductivity contacts and embeds transition metal oxide, phosphate or sulfate, this current-collector comprises graphite, described graphite is characterised in that its bulk density is 0.08-2.25g/cc, conductivity is 500Siemens/cm at least, and the contact of described conductivity is characterised in that resistance is lower than 50ohm-cm 2Ion permeable membrane as the dividing plate between described negative electrode and the anode, and be the electrolyte that diversion son contacts with described anode and negative electrode, this electrolyte comprises that aprotic polar solvent and concentration range are 0.2 to the lithium compound that is up to 3 molar concentrations, and described lithium compound is expressed from the next

R f 1SO 2X -(Li +) YZ aWherein X is C or N, a=0 or 1, and precondition is when X is C, a=1, when X is N, a=0; Wherein when a=1, Y and Z are electron withdraw group independently, are selected from CN, SO 2R f 2, SO 2R, P (O) are (OR) 2, CO 2R, P (O) R 2, C (O) R f 3, C (O) R, the cycloalkenyl group and the H that form with their, precondition be Y and Z the two can not all be H; R wherein in addition f 1, R f 2And R f 3Be C 1-4Perfluoroalkyl, it is randomly replaced by one or more ether oxygen; R is C 1-6Alkyl, it is randomly replaced by one or more ether oxygen, or aryl, it randomly further is substituted; Perhaps wherein when a=0, Y is by formula-SO 2R f 6The electron withdraw group of expression, wherein R f 6Be by formula-(R f 4SO 2N -(Li +) SO 2) mR f 5The group of expression, wherein m=0 or 1, and R f 4Be-C nF 2n-, R f 5Be-C nF 2n+1, n=1-4 is randomly replaced by one or more ether oxygen here.

The present invention also provides the method that forms this electrochemical cell, and this method comprises by making polymer, one or more aprotic, polar mixtures of liquids and lithium compound mix the composition that forms melt-processable in being furnished with the container of mixing arrangement; Mixing described composition is shaped for plasticity to it at least; And by described plastically deformable composition by it being applied heat and/or pressure is made sheet material; Be 0.08-2.25g/cc, thickness less than 250 microns and conductivity with described sheet material and bulk density be that graphite current collector sheet and required other the such element of preparation electrochemical cell of 500Siemens/cm carries out lamination at least; And the described stratiform moulded products of compacting, so that these layers can be conduction and/or the contact of diversion as the formation electrochemical cell is required, described lithium compound is expressed from the next

R f 1SO 2X -(Li +) YZ aWherein X is C or N, a=0 or 1, and precondition is when X is C, a=1, when X is N, a=0; Wherein when a=1, Y and Z are electron withdraw group independently, are selected from CN, SO 2R f 2, SO 2R, P (O) are (OR) 2, CO 2R, P (O) R 2, C (O) R f 3, C (O) R, the cycloalkenyl group and the H that form with their, precondition be Y and Z the two can not all be H; R wherein in addition f 1, R f 2And R f 3Be C 1-4Perfluoroalkyl, it is randomly replaced by one or more ether oxygen; R is C 1-6Alkyl, it is randomly replaced by one or more ether oxygen, or aryl, it randomly further is substituted; Perhaps wherein when a=0, Y is by formula-SO 2Rf 6The electron withdraw group of expression, wherein R f 6Be by formula-(R f 4SO 2N -(Li +) SO 2) mR f 5The group of expression, wherein m=0 or 1, and R f 4Be-C nF 2n-, R f 5Be-C nF 2n+1, n=1-4 is randomly replaced by one or more ether oxygen here.

The accompanying drawing summary

Lithium battery Battery pack in accompanying drawing 1 expression one embodiment of the invention.

Accompanying drawing 2 is represented the assembly that uses in the following embodiments in the substep mode.

Accompanying drawing 3 is schematic diagrames of the laminating machine that adopts in following the specific embodiment of the present invention in preparation.

Accompanying drawing 4 is expression contrast test B, contrast test C and the capability retention of embodiment 2 and the figure of the relation between the discharging current.

                     Describe in detail

The present invention provides several wonderful and important benefits for the lithium ion battery technology. In the present situation of this technology, be dissolved in the LiPF in the aprotic solvent mixture6General with about 3 The aluminum current collector combination of the cathode side of volt or higher lithium ion battery is because it shows ability The good compromise of the known several desirable characteristics of territory professional. Yet, LiPF6Having some lacks Fall into, as middle general introductions such as the Fujimoto that quotes from front. LiPF6Major defect be to lack heat endurance, this has seriously limited the operating temperature of battery, and has hindered to a great extent and need heating LiPF6At about any battery preparation method more than 100 ℃. This point is based on molten The preparation method of melting processing lithium battery parts is such as being described in the United States Patent (USP) such as Dolye Serious restriction in 6,025,092.

The Fujimoto that quote from previously etc. propose to use CF3SO 3 -Li +Replace LiPF6,CF 3SO 3 -Li +Can remedy defects, and good heat endurance further is provided. Because CF3SO 3 -Li +The corrosivity of salt is used by graphite powder and is selected from polyethylene, polypropylene or poly terephthalic acid second two The graphite composite collectors that the polymeric binder of ester is made replaces standard aluminum. Yet, it is as described below, With LiPF6System is compared, CF3SO 3 -Li +Under the high velocity of discharge, cause the heavy losses of capability retention, in any application of needs some but the relatively low velocity of discharge, can not use based on CF thus3SO 3 -Li +Battery. In the present invention, imide salt described herein and methide Salt combine with pure graphite foil cathode collector provide under the high velocity of discharge, have very high Capability retention and high cycle life and the battery of heat endurance. Yet, make us especially Surprised is that in a preferred embodiment of the invention, the capability retention under high-speed is super Cross and comprise LiPF6Capability retention under the present state of the art that combines with aluminum current collector. Change speech It, lithium ion battery Battery pack of the present invention can provide and compare LiPF6The energy that/aluminum cell is higher Amount. When considering that when being in the higher order of magnitude with graphite-phase than the electric conductivity of aluminium, this is one Noticeable result.

In preferred embodiments, adopt any suitable mode known in the art with the present invention Electrod composition be processed into sheet or film-form, and contact to form the lamination knot with current-collector Structure.

An embodiment of lithium battery Battery pack of the present invention, as shown in Figure 1, comprise the cathode collector 1 of graphite foil, the anode 2 that comprises active material of positive electrode, dividing plate 3, the negative electrode 4 that comprises active material of cathode, copper mesh anode collector 5 and comprise aprotic solvent and the electrolyte of lithium compound 6, described electrolyte mutually is diversion with described electrode and contacts, and described lithium compound is expressed from the next:

R f 1SO 2X -(Li +)YZ a

Wherein X is C or N, a=0 or 1, and precondition is when X is C, a=1, when X is N, a=0; Wherein when a=1, Y and Z are electron withdraw group independently, are selected from CN, SO 2R f 2, SO 2R, P (O) are (OR) 2, CO 2R, P (O) R 2, C (O) R f 3, C (O) R, the cycloalkenyl group and the H that form with their, precondition be Y and Z the two can not all be H; R wherein in addition f 1, R f 2And R r 3Be C 1-4Perfluoroalkyl, it is randomly replaced by one or more ether oxygen; R is C 1-6Alkyl, it is randomly replaced by one or more ether oxygen, or aryl, it randomly further is substituted; Perhaps wherein when a=0, Y is by formula-SO 2R f 6The electron withdraw group of expression, wherein R f 6Be by formula-(R f 4SO 2N -(Li +) SO 2) mR f 5The group of expression, wherein m=0 or 1, and R f 4Be-C nF 2n-, R f 5Be-C nF 2n+1, n=1-4 is randomly replaced by one or more ether oxygen here.

The present invention relates to lithium and lithium ion battery these two.For purposes of the present invention, " lithium battery " refers to have the anode that comprises active material of positive electrode such as Li metal and Li metal alloy and comprises that its electric charge deposit and releasing mechanism relate to the lithium battery of negative electrode that lithium ion embedded and took off the active cathode material of embedding.Term " lithium ion battery " is meant to have and comprises that its electric charge deposit and releasing mechanism relate to lithium ion and embed and take off these two lithium battery of the anode of active electrode material of embedding and negative electrode.In preferred embodiments, this is by the embedding in layer structure and takes off embedding and realize.

The preferred anodes of implementing to use when of the present invention comprises the mixture, adhesive preferred polymeric adhesive of the active material of positive electrode that lithium metal or one or more exist with particle form, optional electrical conductivity additive and at least a organic carbonate.The example of useful active material of positive electrode comprises lithium metal, carbon (graphite, coke class, middle carbon (mesocarbon), TPO, carbon fiber etc.), but is not limited to these.Active material of positive electrode comprises that also lithium embeds carbon; Metal lithium nitride is Li for example 2.6Co 0.4N; The lithium metal alloy is LiAl or LiSn for example; Form tin, silicon, antimony or the aluminium compound of lithium alloy, for example at " as the activity/nonactive nano-complex of the anode of lithium ion battery " (the Active/Inactive Nanocomposites asAnodes for Li-Ion Batteries) of O.Mao etc., Electrochemical and Solid StateLetters, 2 (1), the 3rd page, those disclosed in 1999.What other that comprises can be used as active material of positive electrode is metal oxide, for example titanium oxide, iron oxide or tin oxide.When this active material of positive electrode existed with particle form, its particle size should be about 1 to 100 micron.Preferred active material of positive electrode is for example carbon microballon, native graphite, carbon fiber or a graphite plate-shaped material of graphite.Particularly preferably be the graphite microballon, for example those (MCMB 25-28,10-28 or 6-28) that prepare by Japanese Osaka Gas.

The conductive additive that anode composition is fit to comprises carbon for example coke, carbon black, carbon fiber and native graphite; Copper, stainless steel, nickel or other are the sheet metal or the particle of the metal of inertia relatively; Conducting metal oxide is titanium oxide or ruthenium-oxide for example; Perhaps for example polyaniline or polypyrrole of conducting polymer.Preferably relative surface area is lower than the carbon black of about 100 meters squared per gram, for example Super P and the Super S carbon black of buying from Belgian MMM Carbon.

When preparing that wherein active material of positive electrode is the battery of the present invention of particle form, anode can prepare by mixing and forming following composition, said composition comprises 2 to 20% by weight, preferred 3 to 10% polymeric binder, 10 to 50%, preferred 14 to 28% electrolyte described of the present invention, 40 to 80%, preferred 60 to 70% electrode active material and 0 to 5%, preferred 1 to 4% conductive additive.Randomly can also add and be up to 12% aforesaid inert filler, and other additive of substantial effect result's required for the present invention acquisition not that can add that this area professional may need.Preferably do not use inert filler.

Being preferred for implementing battery use of the present invention has with respect to Li/Li +The negative electrode of 3.5 to 4.5 volts upper limit charging voltage of reference electrode.This upper limit charging voltage is this negative electrode accessible maximum voltage that charges under low charging rate and when having obvious reversible idle capacity.Yet, use with respect to Li/Li +The battery of negative electrode that reference electrode has 3 to 5 volts upper limit charging voltage also is fit to.In cathode compositions, be suitable for comprising transition metal oxide, phosphate and the sulfate of transition metal oxide, phosphate and phosphate and lithiumation as the composition that electrode active material uses.Oxide LiCoO for example preferably 2, spinelle LiMn 2O 4, the spinelle manganese oxide lithium LiCr that mixes of chromium yMn 2O 4, stratiform LiMnO 2, LiNiO 2, LiNi xCo 1-xO 2(wherein x is 1<x<1, and preferable range is 0.5<x<0.95) and vanadium oxide be LiV for example 2O 5, LiV 6O 13Perhaps make its composition be above-claimed cpd non-stoichiometric, unordered, unbodied, that cross form lithiumation or that owe lithiumation by modification, for example as known in the art.The cathode activity compound that is fit to can be further by with being less than for example Fe of 5% divalence or trivalent metal cation 2+, Ti 2+, Zn 2+, Ni 2+, Co 2+, Cu 2+, Mg 2+, Cr 3+, Fe 3+, Al 3+, Ni 3+, Co 3+, Mn 3+Come modification Deng doping.Other active material of cathode that is suitable for this cathode compositions comprises the lithiated intercalation compound LiFePO for example with olivine structural 4With the LiFeTi (SO for example of the lithiated intercalation compound with NASICON structure 4) 3, perhaps those are disclosed in " lithium ion battery " (Lithium Ion Batteries) (Wiley-VCH publishing house is by M.Wasihara and O.Yananoto chief editor) by J.B.Goodenough.The particle size of active material of cathode should be about 1 to 100 micron.Preferred transition metal oxide is LiCoO for example 2, LiMn 2O 4, LiNiO 2With above-mentioned their derivative.LiCoO 2Be most preferred.

When preparation electrochemical cell of the present invention, negative electrode can prepare by mixing and forming following composition, said composition comprises 2 to 15% by weight, preferred 4 to 8% polymeric binder, 10 to 50%, preferred 15 to 25% electrolyte described of the present invention, 40 to 85%, preferred 65 to 75% electrode active material and 1 to 12%, preferred 4 to 8% conductive additive.Randomly can add and be up to 12% inert filler, and can add that this area professional may need other do not influence the additive of result's required for the present invention acquisition in fact.Preferably do not use inert filler.

The conductive additive that is suitable in cathode preparation method, using with in above-mentioned anode preparation, adopt identical.As under the anode situation, more preferred electrical conductivity auxiliary agent is a carbon black, and particularly surface area is lower than about 100 meters squared per gram, most preferably is the Super P carbon black that the MMM Carbon from Brussels,Belgium buys.

In preferred embodiments, graphite is active material of positive electrode, and LiCoO 2Be active material of cathode, the negative electrode that the battery of acquisition has is with respect to Li/Li +Reference electrode has about 4.2 volts upper limit charging voltage.

The preferred lithium ion battery of the present invention can be assembled according to any method as known in the art.At United States Patent (USP) 5 by Nagamine etc., 246, in the first method of 796 illustrated this areas, with electrode solvent-be cast on the current-collector, current-collector/electrode band twines to form cylindrical roll with the micropore polyolefin barrier diaphragm spirality, should twine volume and be placed in the metal battery shell, and non-aqueous eletrolyte is immersed in the battery that twines.At United States Patent (USP) 5 by Oliver etc., 688,293 and the United States Patent (USP) 5 of Venuogopal etc., 837, in the second method of 015 illustrated this area, with electrode solvent-be cast on the current-collector and dry, electrolyte and polymeric gel agent are coated on dividing plate and/or the electrode, be pressed onto this carrier ring on current-collector/electrode band or make it and contact with the preparation battery component with current-collector/electrode band, with the cutting of this battery component and pile up, perhaps folding then, perhaps twine, be placed on then in the paper tinsel laminate housing, last heat treatment is so that this electrolyte gelization.At United States Patent (USP) 5 by Gozdz etc., 456,000 and United States Patent (USP) 5,540, in the third method of 741 this areas that provide, electrode and dividing plate are being added solvent cast under the plasticizer, with electrode, netted current-collector, electrode and carrier ring force together with the preparation battery component, use volatile solvent to extract this plasticizer, dry these parts are filled because plasticizer extracts the hole that stays with electrolyte by these parts are contacted with electrolyte, then to obtain the battery of activation, these parts are piled up, folding or twine, and at last with this battery packages in the paper tinsel laminate housing.In the 4th kind of method of this area of describing in the U.S. Patent application 09/383,129 of unexamined,, mix with salt and electrolyte solvent then to obtain active compound at first with electrode and separator material drying; By melt-processed this electrode and dividing plate composition are configured as film, this film laminating to obtain battery component, is piled up this battery component, fold or twines, be then packed in the paper tinsel lamination vessel.Describe in detail in the specific embodiments of the present invention that third and fourth kind of method will be described below.

The cathode collector that is suitable for lithium of the present invention or lithium ion battery comprises graphite.In pure graphite, can obtain maximum conductivity usually, so preferred graphite flake comprises the least possible adhesive, additive and impurity so that realize advantage of the present invention.So adhesive, additive and impurity are because they are not need to the potential adverse effect of battery performance.

Be suitable for graphite current collector of the present invention can with substrate for example the form of the powder coating on metallic substrates, self-supporting sheet or the laminated material exist.This current-collector can be to have other member for example metal forming, adhesive phase and be the composite construction of required other material for given purposes in other words.Yet, according to the present invention, under any circumstance, be graphite linings or the graphite linings that combines with adhesion promotor directly with electrolyte junction of the present invention, and be conductivity with described electrode surface and contact.

Particularly preferred graphite form is the United States Patent (USP) 3 at J.H.Shane etc., 404, the low-density graphite flake of the flexibility of describing in 061, this patent is introduced for your guidance in full at this, and it provides usually the enhancing of chemistry, heat, stretching and electric property relevant with graphite and required pliability, compactibility, conformability, flexible rigidity and elastic mechanical performance.Implement the flexible graphite platelet that the present invention preferably uses and have the bulk density of 0.08 to 2.25 gram/cubic centimetre, the density of native graphite is in this scope, however this density 0.8 to 1.4 gram/cubic centimetre preferably.

The flexible graphite that enforcement the present invention preferably uses is characterised in that its thickness maximum is 250 microns, preferably less than 125 microns, most preferably less than 75 microns.The feature that is preferred for implementing flexible graphite platelet of the present invention is that further along the length of this sheet and the conductivity of width be 100Siemens/cm (S/cm) at least, preferably be 500S/cm at least, most preferably be 1000S/cm at least, measure according to ASTM standard C 611-98.

Being preferred for implementing flexible graphite platelet of the present invention can mix with required other component of application-specific, but the purity of preferred graphite is about 95% or higher.

When thickness is lower than about 10 microns, can reckon with that resistance may be excessively high, be not too preferred so be lower than about 10 microns thickness.

Strictly speaking, operability of the present invention need not add adhesive in this electrod composition.Yet the preferred adhesive, particularly polymeric binder of using in this field also is preferred when enforcement is of the present invention equally.Those skilled in the art it will be understood that many following polymeric materials that are suitable for as adhesive are useful for the iontophoretic injection barrier film that preparation is suitable for using in lithium of the present invention or lithium ion battery.

The adhesive that is fit to comprises polymeric binder, and particularly the polymer dielectric of gelation comprises polyacrylonitrile, poly-(methyl methacrylate), poly-(vinyl chloride) and poly-inclined to one side vinylidene fluoride and their copolymer, but is not limited to these.Equally also comprise solid polymer electrolyte for example based on the electrolyte of polyethers salt, comprise that poly(ethylene oxide) (PEO) and its derivative, poly-(expoxy propane) are (PPO) and its derivative and have ethyleneoxy and poly-(the organic phosphine nitrile) of other side group.Other adhesive that is fit to comprises the ionomer of fluoridizing, and it comprises the polymer backbone of partially or completely fluoridizing and has the side group that comprises fluorinated sulfonic, imino group or methyl lithium salts.Preferred adhesive comprises for example copolymer of perfluoro-methyl, perfluor ethyl or perfluoro propyl vinethene of poly-inclined to one side vinylidene fluoride and itself and hexafluoropropylene, tetrafluoroethene, fluroxene; Comprise the monomeric unit of poly-inclined to one side vinylidene fluoride and the ionomer of the monomeric unit of the side group that comprises fluorinated carboxylic, sulfonic acid, imino group or methyl lithium salts.

The polymer dielectric of gelation is to mix formation by polymeric binder with compatible aprotic polar solvent that is fit to and the electrolytic salt under usable condition.

The polymeric binder of PEO and PPO base can need not solvent and use.Under solvent-free situation, they become favourable solid polymer electrolyte aspect fail safe and cycle life in some cases.

Other adhesive that is fit to comprises the composition of so-called " salt is in polymer ", and its polymer that comprises contains one or more salt greater than 50 weight %.For example referring to Sokid State Ionics such as M.Forsyth, 113, the 161-163 (1998).

Also comprise the glassy solids polymer dielectric as adhesive, it is similarly with the composition of " salt is in polymer ", and just this polymer is to use being lower than under the temperature of its glass transition temperature, and the concentration of this salt is about 30 weight %.

Preferably, the volume parts of preferred adhesive is 4 to 40% in Manufactured electrode.

Preferred electrolyte solvent is aprotic liquids or polymer.It comprises organic carbonate, those that for example become known for the Li-ion battery in this area be suitable for implementing of the present invention.Organic carbonate comprises propylene carbonate, dimethyl carbonate, ethylene carbonate and many associated class.Equally also comprise solid polymer electrolyte, for example polyethers and poly-(organic phosphine nitrile).Further comprise the ion type liquid mixture that contains lithium salts for example as known in the art, comprise ion type liquid, for example the imidazoline cation with based on imide salt, methide salt, PF 6 -Or BF 4The organic derivative of counter ion.For example referring to Nature such as D.R.MarFarlane, 402,792 (1999).

The mixture of the electrolyte solvent that is fit to comprises that the mixture of liquid and polyeletrolyte solvent is fit to equally.Preferred electrolyte solvent is an organic carbonate.The mixture of the mixture of the mixture of ethylene carbonate and dimethyl carbonate, ethylene carbonate and propylene carbonate or ethylene carbonate, propylene carbonate and diethyl carbonate more preferably.

Be suitable for implementing electrolyte solution of the present invention and be by with imino group lithium described herein or methyl lithium salts and the optional LiPF that is selected from 6, LiPF nR Fm(wherein n+m=6) and R f=CF 3Or C 2F 5, LiBF 4, LiAsF 6Or LiClO 4Common salt and described electrolyte solution mix by the dissolving, sliming or the melting mixing that are suitable for this particulate matter together and form.When the concentration of this imide salt or methide salt is 0.2 to being up to 3 molar concentrations, but 0.5 to 2 molar concentration preferably, when most preferably being 0.8 to 1.2 molar concentration, the present invention is exercisable.According to the preparation method of this battery, after winding or lamination formation battery structure, can in this battery, add electrolyte, perhaps before final battery assembling, it is added in electrode or the dividing plate composition.

The dividing plate that is suitable for lithium of the present invention or lithium ion battery is the goods of the moulding of any ion-permeable, preferably film or sheet.Such dividing plate can be for example capillary polypropylene, polyethylene, polytetrafluoroethylene and their layer structure of microporous membrane.But the dividing plate that is fit to also comprises for example poly-inclined to one side vinylidene fluoride of polymer and its copolymer of swelling.Other dividing plate that is fit to comprises that those are known in gelation polymer electrolyte field, for example poly-(methyl methacrylate) and poly-(vinyl chloride).What be fit to equally is polyethers, for example poly-(oxirane) and poly-(expoxy propane).Micropore polyolefin dividing plate preferably, comprise 1,1-difluoroethylene and hexafluoropropylene, perfluoro methyl vinyl ether, the copolymer of perfluoroethylvinyl ether or perfluoro propyl vinyl ether (mixture that comprises them), or the fluorinated ionic cross-linked polymer for example those at US such as Doyle 6,025, describe in 092, contain by 1, the monomeric unit that the 1-difluoroethylene is derived and have the ionomer of skeleton of perfluorinated alkenyl monomer of the ionic side group that following formula represents and the dividing plate of imide salt and methide derivative thereof

-(O-CF 2CFR) aO-CF 2(CFR ') bSO 3-Li +Wherein R and R ' are independently selected from F, Cl or fluoridized C 1-10-alkyl, a=0,1 or 2, b=0 to 6, as Feiring etc. described in the WO 9945048 (A1).

In being suitable for the electrode that the present invention uses, most preferred adhesive is the copolymer (p (VdF-HFP)) of poly-inclined to one side vinylidene fluoride (PVDF) or poly-inclined to one side vinylidene fluoride and hexafluoropropylene, for example commercial with trade (brand) name KYNAR FLEX From Elf Atochem NorthAmerica, Philadelphia, PA obtains.Electrode of the present invention can be mixed together and make easily by all polymers compositionss being dissolved in the conventional solvent and with carbon black pellet and electrode activity particle.For example preferred electrode of lithium cell can be prepared as follows: PVDF is dissolved in the 1-Methyl-2-Pyrrolidone or with p (VdF-HFP) copolymer is dissolved in the acetone solvent, the particle that adds electrode active material and carbon black subsequently, deposit film and dry in substrate then.The preferred electrode that is obtained will comprise electrode active material, conductive carbon black and polymer.Then with this electrode by solution casting at the carrier that is fit to for example on glass plate or the current-collector, and adopt technology well known in the art to form film.

In the present invention, make negative electrode and graphite current collector be conductivity and contact, its contact resistance is as much as possible little.This advantageously can be by deposition skim on this graphite flake the adhesive accelerant layer for example the mixture of acrylic acid ethylene and carbon black realize.The contact that is fit to can be by applying heat and/or pressure so that between current-collector and the electrode closely contact realize.

Be preferred for implementing flexible graphite platelet of the present invention and obtaining to have special advantage aspect the low contact resistance.Because its high ductility, conformability and rigidity, can make and the especially closely and therefore structure of low resistance contact of electrode, this structure can be had a mind to or coarse contact surface by mistake is provided.Under any circumstance, when enforcement was of the present invention, the contact resistance between negative electrode of the present invention and the graphite current collector was no more than 50ohm-cm 2, preferably be no more than 10ohm-cm 2, be most preferably not exceeding 2ohm-cm 2For purposes of the present invention, can measure contact resistance by the known any method easily of those of ordinary skills.Also can use an ohm instrument simply to measure.Have been found that it is easily that the method for describing by following embodiment 3 is measured the real part of complex impedance in enforcement of the present invention.

In the present invention, make anode and anode collector carry out conductivity and contact, this anode collector is metal forming or wire netting preferably, most preferably is copper.Situation with negative electrode is the same, and it is favourable adopting adhesive accelerant between them.Certainly, wish to be reduced to the contact resistance between anode and the anode collector minimum according to the hands-on approach of this area for optimum operation.

In preferred embodiments, the electrode film that will prepare thus then is compound by lamination and current-collector and dividing plate.Be the excellent ionic contact of leading mutually in order to ensure like this lamination or otherwise compound element, these elements are compound with the electrolyte that comprises aprotic solvent (preferred above-mentioned organic carbonate), imino group lithium that following formula is represented or methyl lithium salts,

R f 1SO 2X -(Li +)YZ a

Wherein X is C or N, a=0 or 1, and precondition is when X is C, a=1, when X is N, a=0; Wherein when a=1, Y and Z are electron withdraw group independently, are selected from CN, SO 2R f 2, SO 2R, P (O) are (OR) 2, CO 2R, P (O) R 2, C (O) R f 3, C (O) R, the cycloalkenyl group and the H that form with their, precondition be Y and Z the two can not all be H; R wherein f 1, R f 2And R f 3Be C 1-4Perfluoroalkyl, it is randomly replaced by one or more ether oxygen; R is C 1-6Alkyl, it is randomly replaced by one or more ether oxygen, or aryl, it is randomly further replaced; Perhaps wherein, when a=0, Y is by formula-SO 2R f 6The electron withdraw group of expression, wherein R f 6Be by formula-(R f 4SO 2N -(Li +) SO 2) mR f 5The group of expression, wherein m=0 or 1, and R f 4Be-C nF 2n-, R f 5Be-C nF 2n+1, n=1-4 is randomly replaced by one or more ether oxygen here.Preferably, X is N, m=0, and R f 1And R f 5Be-CF 3

The means that the stratiform thing that will contain entire cell of the present invention is assembled into final working battery are not crucial for purposes of the invention.Those skilled in the art will appreciate that the whole bag of tricks of assembled battery (comprising lithium and lithium ion battery) has been as known in the art and has above summarized.For purposes of the present invention, any such method that requires to adapt with the special chemistry and the machinery of the known execution mode of present environment all is fit to.

Preferable methods be Gozdz etc. at United States Patent (USP) 5,456, the method for describing in 000 and 5,540,741 is about to plastification composite cast and moulding, extracts this plasticizer and add electrolyte in the battery structure of doing.More preferably according to common pending trial U.S. Patent application 09/383 at Barton etc., the processing step of describing in 129 prepares the battery that comprises graphite foil and imide salt or methide salt of the present invention, wherein Huo Hua electrode material is melted processing, most preferably by being extruded as sheet material continuously, and be laminated to single continued operation on another element of battery.

Further describe the present invention in the specific embodiments below, these specific embodiments only are illustrating of some preferred implementations of the present invention.

Embodiment

In the specific embodiment below, measure the relation between the capability retention and the velocity of discharge.Each testing battery of describing in accompanying drawing 1 at first prepares under the discharge attitude.After preparation, use Maccor 9100 test instruments, be 4.15V with current charges to the voltage of 7.5mA, the constant current with 10mA is discharged to 2.7V subsequently.This battery is being circulated 5 times between 2.7 to 4.14V under the constant current of 10mA.After this program, this battery with the discharge of the constant current of 15mA, is measured voltage from 4.15 times that are reduced to 2.7V, as slow velocity of discharge electric capacity reference point.In charging that repeats and discharge cycles, under the electric current of 15mA this battery charge to 4.15 is lied prostrate once more then, discharge in identical voltage range under the constant current that raises gradually, wherein capacity is represented with the percentage of reference discharge capacity.

Embodiment 1

At US5, the method for describing in 456,000 and 5,540,741 prepares battery, yet uses the flexible graphite paper tinsel as cathode collector, and salt is (CF by Gozdz etc. 3SO 2) 2NLi.

With 65 parts of LiCoO 2(FMC Corp.), 6.5 parts of Super P carbon blacks (MMM Carbon), 10 parts of KYNAR FLEX 2801 (Elf Atochem) and 18.5 parts of dibutyl terephthalates mix in acetone solvent and prepare cathodic coating.Use technique casting film and steaming to remove acetone, obtaining coating weight is 19.1mg/cm 2With cast thickness be 79 microns negative electrode approximately.With 65 parts of MCMB 2528 (Osaka Gas), 3.3 parts of Super P carbon blacks, 10 parts of KYNAR FLEX 2801 and 21.7 parts of dibutyl terephthalates mix in acetone solvent and prepare anode film.After cast and acetone evaporated, the coating weight of anode film is 17.5mg/cm 2, thickness is 109 microns approximately.With 26 parts of fumed silicas (Cabot TS530), 32 parts of KYNAR FLEX 2801 and 42 parts of dibutyl terephthalates mix in acetone solvent and prepare dividing plate.The thickness of barrier film is 41 microns.

GTY level Grafoil  paper tinsel is by UCAR Carbon Co.Inc., Cleveland, and OH obtains.Thickness is 75 microns, and resistance is 8 * 10 in the xy plane -6Ohm-m, and density is 1.12g/cm 3Use by Adocotor  50C12 emulsion (Morton InternationInc., Chicago, IL, the copolymer of acrylic acid and ethene), the adhesion promotor formed of the mixture of carbon black (MMM Super P) and ethanol sprays this graphite foil, so that dry adhesive accelerant layer is made up of resin and the 33 weight % carbon blacks of 67 weight %.The coating weight of measuring is 500 μ g/cm 2Downcut a slice graphite current collector with blade from the graphite foil of spraying.This current-collector is " L " type as shown in Figure 1.The area that contacts with negative electrode is 45 millimeters * 55 millimeters a rectangle.Be used for contact pin that external electric connects and be the bar of 2.5 centimetres wide and 6 centimeter length.

Above-mentioned current-collector and film forming are prepared battery for layer structure G/C/C/S/A/Cu, and G represents Grafoil here Layer, C represents two-layer cathodic coating, and 45 * 55 millimeters, S represents carrier ring, and A represents 50 * 60 millimeters anode layer, and Cu represents to adopt Adocote The copper mesh current-collector that adhesive accelerant is handled.(WesternMagnum, El Segundo CA) are laminated to two layers of cathodic coating on the Grafoil under 125 ℃, and nip pressure is 69kPa, and roller speed is 0.25m/min to use Western Magnum XRL120 laminating machine.In forming this laminated material, use than negative electrode and Grafoil The pad of thin 12.5 microns of composite thickness.

Further understand the method for this laminated material of formation that uses in the disclosed specific embodiments here with reference to accompanying drawing 2.The layer for the treatment of lamination at first tries body to form in a top that is placed on another.This examination body 13 is sandwich at two Kapton with relevant U type brass shim spacer 14 (it has by 3 inches 10 inches " arms " that separate and has the thickness of selecting according to the thickness of required final laminated material) Between the polyimide film (obtaining from DuPont company) 15, all being used in brass overcoat 16 are clamped shell together by this laminator.

In an identical manner anode layer is pressed on the copper collector.This dividing plate is placed in the negative electrode and anode construction of lamination then, and makes this whole assembly carry out last lamination step under 95 ℃, wherein nip pressure is 41.4kPa, and roller speed is 0.3m/min.The pad that use is thinner 20 microns than composite thickness.Being laminated in the air of parts carried out.

By remove the dibutyl terephthalate in the battery, each 30 minutes with excessive diethyl ether continuous extraction secondary.Under vacuum, this battery is heated to 80 ℃ of heating carried out drying in 30 minutes, transfer to then in the drying box of filling Ar.

Before use, with salt (CF 3SO 2) 2(3M company is MN) vacuum and 120 ℃ dry 48 hours down for NLi.Electrolyte is by this salt is dissolved in 2 weight portion ethylene carbonates and 1 weight portion dimethyl carbonate (from the carbonic ester that EM Science obtains, Selectipur with the concentration of 1.0M LITHIUM BATTERY) in the solvent mixture and the preparation.

In the test of carrying out according to procedures known in the art, it is 87.8% that the first circulation electrochemistry is renderd a service.The capacitance loss of 5 circulative accumulations be for the first time discharge capacity 1.9%.The capacity under the 2C velocity of discharge be same battery under the C/5 velocity of discharge measured value 85.3%.The relation of current capacity conservation rate and battery discharge is illustrated in the accompanying drawing 3 with the form of chart.

Contrast test A

Adopt the battery preparation method of embodiment 1 and comprise 1M (CF 3SO 2) 2The NLi electrolysed saline solution obtained is at interior material, but cathode collector is 304 type stainless steels.Use with embodiment 1 in identical evaluation method, it is that the discharge capacity loss of 88.4%, 5 circulative accumulation is 68.1% that the first circulation electrochemistry is renderd a service.The capability retention of undetermined under the 2C velocity of discharge is because the capacity in the battery is lost fast.

Embodiment 2

In this embodiment, with described herein the same, adopt the Grafoil  of embodiment 1.All solid constituents are all dry under 120 ℃ in a vacuum, and comprise the H that is lower than 30ppm 2O.Except as otherwise noted, all carry out in the drying box at applying argon gas in all last technologies of drying steps.Adhesive in the electrode and the polymer in the dividing plate be according to Doyle etc. at US6, the sulfonic acid lithium form of the vinylidene fluoride (VF) of the method preparation of describing in 025,092 and the hydrolyzed copolymer of perfluor sulfonyl base fluorine ethoxycarbonyl propyl vinyl ethers (PSEPVE).This polymer comprises the PSEPVE of 9 to 10 moles of %, and estimates that its molecular weight is about 200000Da.Solvent be a kind of weight ratio be 2: 1 carbonic acid ethylidene ester (EC, LITHIUM BATTERY, from EMIndustries, Hawthorn, NY) and carbonic acid butylidene ester (JEFFSOL  BC, HuntsmanCorporation, Salt Lake City, mixture UT).

By 8.7 gram binding agents, 7 grams are restrained the LiCoO that obtains from FMC Corporation from the Super P carbon black, 58 of MMM Carbon 2Mix with 26.3 gram EC/BC mixtures and to prepare cathode compositions.

By with identical polymer in 8 grams and the negative electrode, 4.5 gram carbon blacks, 64 grams from OSAKA GAS obtain carbon microballon (MCMB level 2528) and 23.5 restrain the EC/BC mixtures and mix and prepare anode composition.

The composition that dividing plate is made up of the EC/BC of the same polymer of 25 weight % and 75% is made.

Prepared described anode and cathode compositions in about 1 minute by respectively the component of drying being mixed in the Waring mixer.Described EC/BC solvent mixture is added in this mixer, and this mixture is continued to mix 1 minute.Simultaneously still in drying box, the mixture that forms is like this added Haake Rhomix  600 mixers of being furnished with the roll-type rotor, and (Haake (USA), Paramus is in mixing chamber NJ), and in about 5rmp and 125 ℃ mixing 20 minutes down.The mixture that obtains is taken out from this mixer fast, and in 1 minute, be placed in the glass jar.The composition of preparation is thus taken out from drying box, put into the Kapton of sealing In the polyimides bag, and (Ferd CarverInc., Menomonee Falls WI) went up under the pressure that applies 30psi on the sample pre-densification 3 minutes at Carver Model M hydraulic press under 125 ℃ in this bag.The film of acquisition is got back in the drying box.

The calender that is used for preparing this battery is shown in accompanying drawing 3.Stratiform battery component 7 is transported in the horizontal access heater unit of being made up of bottom heating feedboard 8 (it is 205 millimeters with length that width is 218 millimeters) and top heat plate 9 (it is 205 millimeters with length that width is 154 millimeters), wherein said top heat plate 9 is placed on the top of top heat plate feedboard 8, and keep enough distances to enter, and can not touch this top heat plate to allow the stratiform battery component.The shape of this whole inlet heater unit is the rectangular electric heating hollow tube in cross section.This stratiform battery component enters nip rolls 10 two polishings, electrically heated chromium surface from inlet heater unit, and (diameter is 100 millimeters, wide is 150 millimeters) gap 11 in, wherein drive a roller 10, described gap can be regulated between 0.025 to 0.250mm.After passing through nip rolls, the battery band 12 of lamination transfers out through reclaiming plate 17 (its width is 210 millimeters, and length is 165 millimeters).

Anode for preparing in hydraulic press as mentioned above and cathode thin film are rolling under the roller temperature at 130 ℃ after inlet heater unit preheating 2 minutes under 135 ℃, pass through this nip rolls amounting under the roller speed of 260 kilograms folder power and 0.1 meter/minute then.With the electrode film of cutter from 45 millimeters * 55 millimeters of this calendered film cutting-outs.

Dividing plate prepares by at first using scraper that polymer is mixed with EC/BC.Use the copper backing of 5 mils this mixture manually to be spread over two Kapton that describe above with reference to accompanying drawing 2 Between the polyimide film.The assembly that forms like this 115 ℃ of following preheatings 2 minutes, is prolonged in the linear velocity of 0.1m/min, the temperatures that amounts to 170 kilograms of folder power and 125 ℃ then, obtain the dividing plate of 4 mil thick.The setting of this laminator is: 0.1 meter/minute of roller speed, 86 kilograms of roller power are 125 ℃ in 115 ℃ of following preheatings 2 minutes and roll temperature.Downcut 50 millimeters * 60 millimeters barrier film from the film of such preparation.

Top alinement (this top is the place that negative electrode contact pin is stretched out as shown in Figure 1) with cathodic coating and flexible graphite current-collector is laminated on this current-collector then.It is 125 ℃ that the roller of this laminator is set to temperature, and folder power is 170 kilograms, and speed is 0.25m/min, uses the pad thinner approximately 12.5 microns than the composite thickness of negative electrode and current-collector.

Top (this top is the place that contact pin the is stretched out as shown in Figure 1) alinement of the Cu net that anode and Adocote are handled adopts the condition lower floor identical with negative electrode to be pressed onto on this copper mesh current-collector then.

Dividing plate is placed between the anode and negative electrode of lamination according to the above-mentioned method of describing with reference to accompanying drawing 2, and make this whole assembly under 95 ℃, carry out final lamination step, wherein folder power is 6.0psi, linear velocity is 0.3m/min, uses the pad thinner approximately 12.5 microns than the composite thickness of this battery component.

Then the battery that obtains was flooded 60 minutes in the LiTFSI of embodiment 1 electrolyte.This is immersed in the petri diss and carries out.The electrolytical weight that this battery absorbs is 0.318 gram.Then with this cell sealing in sack.The material of the sack that uses is from ShieldPack (West Monroe, LA) the ES class material of Huo Deing.The sealer that adopts be the Audion Futura Poly Twin type handed (Packaging Aids Corp., San Rafael, CA).

The sealing bag is transferred to the outside of drying box, and (Vertrod, Brooklyn seal NY), and it is water-cooled impulse type sealer to use the Model20A V-60966 that fixes on the ground once more.The battery that obtains is described in the accompanying drawing 1.

It is 78.2% that the first circulation electrochemistry of measuring is renderd a service.The capacitance loss of 5 circulative accumulations be for the first time discharge capacity 3.1%.This battery does not carry out the test of the 2C velocity of discharge, because internal short-circuit appears in this battery after initial cycle.Therefore no longer further test.Loss after 5 initial cycle is 3.1%, than the battery height among the embodiment 1, but much better than Comparative Examples A still.

Contrast test B

Prepare battery according to the method among the embodiment 1, but be to use LiCF 3SO 31M solution in EC/DMC (weight ratio 2: 1) replaces LiTFSI solution.LiCF 3SO 3Obtain from Aldrich, and dry 48 hours down at 120 ℃ under vacuum.Final moisture content is 10ppm.Selectipur  EC and DMC obtain from EM Industries Inc.Estimate the performance of this battery in the mode identical with embodiment 1.It is 89.6% that the first circulation electrochemistry is renderd a service.The cumulative capacity loss of 5 circulations be for the first time discharge capacity 1.4%.Capacity under the 2C velocity of discharge be under the C/5 capacity 35.7%.

The battery capacity conservation rate of contrast test B and the relation of discharging current are illustrated in the accompanying drawing 3 with the form of chart.

Contrast test C

Method according to embodiment 1 prepares battery, but cathode collector is the aluminium net, and uses LiPF 61M solution in EC/DMC (weight ratio 2: 1) replaces LiTFSI solution.

Identical with the situation during graphite foil among the embodiment 1, (DelkerCorporation, Branford CT) handle with adhesive accelerant with this aluminium net 2A15-077.As generally accepted, use LITHIUM BATTERY LiPF6 (Hashimoto Chemical).Selectipur EC and DMC obtain from EMIndustries Inc.Estimate the performance of this battery in the mode identical with embodiment 1.It is 90.4% that the first circulation electrochemistry is renderd a service.Capacity under the 2C velocity of discharge be under the C/5 capacity 79.8%, it is lower than the battery among the embodiment 1 that uses graphite foil and LiTFSI combination.The result is described in the accompanying drawing 3.

Embodiment 3

The contact impedance at following mensuration negative electrode-graphite current collector interface.Adopt cathode thin film, untreated Grafoil among the embodiment 1, and under 135 ℃ with these film laminatings together, preparation structure C/G/C/C/G/C, C is that negative electrode and G are Grafoil here.The contact pin of Grafoil is stretched out outside the negative electrode, and the size of negative electrode is 2.2cm * 5.0cm.Use the impedance between two Grafoil sheets of four-point probe AC voltmeter measurement.Find that the impedance under 1Hz to the 10kHz frequency almost completely is real number value (resistance) (having low-down imaginary number (electric capacity) component), and be the 0.5ohm order of magnitude.The resistance that observed resistance ratio calculates according to the volume conduction rate of negative electrode is much bigger, so this impedance is the measuring of resistance on the interface between negative electrode and the current-collector.Because this structure has 2 continuous C/G interfaces, the contact impedance at a C/G interface of calculating is 0.5ohm * 2.2cm * 5.0cm * (1/2)=2.8ohm cm 2

Embodiment 4

Anode composition is by 39 gram MCMB, 4.8 are restrained KYNAR Flex 2801,14.4 gram 1M Li (CF 3SO 2) 2Electrolyte and the 1.8 gram carbon blacks of N in 1: 1 weight ratio EC/PC (propylene carbonate) mixture mix and form.Cathode compositions is by restraining LiCoO with 52 2, 5.6 gram KYNAR Flex 2801, the 17 above-mentioned electrolyte of gram and 5.6 gram carbon blacks mix and form.The dividing plate composition is by with 1 part of KYNAR Flex 2801 and 2.4 parts of electrolyte and 0.4 part of fumed silica (Cab-O-Sil , Ts530, Cabot Corporation) mix and form.

According to the step of embodiment 2 and use the equipment of embodiment 2, the component of drying was mixed in the Waring mixer about 1 minute.Jar and its content with this mixer is heated to 130 ℃ of heating 30 minutes on the hot plate that covers then.Continue then to mix, add electrolyte simultaneously with speed slowly.The mixture that is obtained was mixed 1 minute again, and this mixer jar is added a cover in the mixed process.The mixture that mixes is transported in HaakeRhomix  600 mixers (sequence number 557-1030) of being furnished with the roll-type rotor, and under 125 ℃, mixed 20 minutes, wherein rotating speed is 1rpm under the situation of anode composition, and rotating speed is 20rpm under the situation of cathode compositions.Then, the mixture that the obtains pressure on 125 ℃ and sample for hot pressing under about 300psi, is prolonged pressure according to the method for embodiment 2 subsequently.

According to the method for embodiment 2, equally the dividing plate composition is made barrier film.

With cathode thin film and top alinement, be laminated to then on this current-collector with the described flexible graphite current-collector of handling with adhesive accelerant of embodiment 1.It is 125 ℃ that the roller of this laminator is set to temperature, and folder power is 170 kilograms, and speed is 0.25m/min, uses the pad thinner approximately 12.5 microns than the composite thickness of negative electrode and current-collector.

Top (part is stretched out in the contact pin) alinement of the Cu net that anode and Adocote are handled adopts with the used identical condition of negative electrode to be laminated on this copper mesh current-collector then.

Dividing plate is placed between the anode and negative electrode of lamination, and makes this whole assembly carry out final lamination step under 95 ℃, wherein folder power is 100kg, and speed is 0.3m/min, uses the pad thinner approximately 12.5 microns than the composite thickness of this battery component.

Then with this cell sealing in sack.The material of the sack that uses is from ShieldPack (West Monroe, LA) the ES class material of Huo Deing.The sealer that adopts be the Audion Futura Poly Twin type handed (Packaging Aids Corp., San Rafael, CA).

The battery of sealing is migrated out drying box, and (Vertrod, Brooklyn seal NY), and it is water-cooled impulse type sealer with the Model 20AV-60966 that fixes on the ground once more.

Estimate the performance of this battery in the mode identical with embodiment 1.It is 86.9% that the first circulation electrochemistry is renderd a service.The capacitance loss of 5 circulative accumulations be for the first time discharge capacity 3.7%.Capacity under the 2C velocity of discharge be under the C/5 capacity 52.4%.

Claims (37)

1, lithium or lithium ion electrochemical cells, this battery comprise fellatio utmost point active material anode, be anode collector that conductivity contacts with this anode, with respect to Li/Li +Reference electrode shows the negative electrode of 3 to 5 volts upper limit charging voltage, described negative electrode comprises and is lower than 250 microns cathode collector with thickness and is the lithium that conductivity contacts and embeds transition metal oxide, phosphate or sulfate, this cathode collector comprises graphite, described graphite is characterised in that its bulk density is 0.08-2.25g/cc, conductance is 500Siemens/cm at least, and the contact of described conductivity is characterised in that resistance is lower than 50ohm-cm 2As the ion-permeable film between described negative electrode and the anode as dividing plate; And be with described anode and negative electrode and lead the ionic electrolyte that contacts, it is 0.2 to the lithium compound that is up to 3 molar concentrations that this electrolyte comprises aprotic polar solvent or polymer and concentration, described lithium compound is expressed from the next
R f 1SO 2X -(Li +) YZ aWherein X is C or N, a=0 or 1, and precondition is when X is C, a=1, when X is N, a=0; Wherein when a=1, Y and Z are electron withdraw group independently, are selected from CN, SO 2R f 2, SO 2R, P (O) are (OR) 2, CO 2R, P (O) R 2, C (O) R f 3, C (O) R, the cycloalkenyl group and the H that form with their, precondition be Y and Z the two can not all be H; R wherein in addition f1, R f2 and R f 3Be C 1-4Perfluoroalkyl, it is randomly replaced by one or more ether oxygen; R is C 1-6Alkyl, it is randomly replaced by one or more ether oxygen, or aryl, it randomly further is substituted; Perhaps wherein when a=0, Y is by formula-SO 2R f 6The electron withdraw group of expression, wherein R f 6Be by formula-(R f 4SO 2N -(Li +) SO 2) mR f 5The group of expression, wherein m=0 or 1, and R f 4Be-C nF 2n-, R f 5Be-C nF 2n+1, n=1-4 is randomly replaced by one or more ether oxygen here.
2, the electrochemical cell of claim 1, wherein said active material of positive electrode are the carbon that is selected from graphite microballon, native graphite, carbon fiber or graphite flake.
3, the electrochemical cell of claim 1, wherein active material of positive electrode or lithium embed transition metal oxide, phosphate or sulfate or these two is a particle form, and described particle size is that average equivalent sphere diameter is 1 to 100 micron.
4, the electrochemical cell of claim 1, wherein negative electrode is with respect to Li/Li +Reference electrode shows 3.5 to 4.5 volts upper limit charging voltage.
5, the electrochemical cell of claim 1, wherein lithium embeds transition metal oxide, phosphate or sulfate and is selected from LiCoO 2, spinelle LiMn 2O 4, the chromium spinel lithium-manganese oxide, the stratiform LiMnO that mix 2, LiNiO 2, LiNi xCo 1- xO 2, wherein x is 0<x<1, barium oxide, LiFePO 4And LiFeTi (SO 4) 3
6, the electrochemical cell of claim 5, wherein lithium embedding transition metal oxide, phosphate or sulfate are to be selected from LiCoO 2, LiMn 2O 4, LiNiO 2, LiNi xCo 1- xO 2, wherein x is 0<x<1, and the lithium of derivative embeds transition metal oxide.
7, the electrochemical cell of claim 1, wherein the cathode collector of graphitiferous is a purity greater than 95% graphite flake.
8, the electrochemical cell of claim 7, wherein said graphite flake are characterised in that its bulk density is 0.8 to 1.4 gram/cubic centimetre.
9, the electrochemical cell of claim 1, the thickness of wherein said graphite flake is less than 75 microns.
10, the electrochemical cell of claim 1, wherein said graphite flake are characterised in that conductance is 1000Siemens/cm at least in its face.
11, the electrochemical cell of claim 1, wherein the cathode collector of graphitiferous also comprises adhesive accelerant.
12, the electrochemical cell of claim 1, wherein said electrolyte comprises organic carbonate.
13, the electrochemical cell of claim 12, wherein said organic carbonate are selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and its mixture.
14, the electrochemical cell of claim 1, wherein the concentration of lithium compound is 0.5 to 2 molar concentration in described electrolyte.
15, the electrochemical cell of claim 1, wherein the concentration of lithium compound is 0.8 to 1.2 molar concentration in described electrolyte.
16, the electrochemical cell of claim 1, wherein lithium compound is expressed from the next
CF 3SO 2N -(Li +)SO 2CF 3
17, constitute the method for electrochemical cell, this method comprises by making first polymer, one or more aprotic, polar mixtures of liquids and lithium compound mix the composition that forms melt-processable in being furnished with the container of mixing arrangement; Mixing described composition is that plasticity is shaped to it at least; And by described plasticity forming composition by it being applied heat and/or pressure forms sheet material; Described sheet material and graphite current collector sheet, ion permeable separator, the anode strip that contains the anode active material and second polymer and anode collector are carried out lamination, the bulk density of described graphite current collector sheet be 0.08-2.25g/cc, thickness less than 250 microns, and conductance is 500Siemens/cm at least; And the described stratiform sheet material of compacting, so that these layers can be conduction and/or lead ionic contact as the formation electrochemical cell be required, described lithium compound is expressed from the next
R f 1SO 2X -(Li +) YZ aWherein X is C or N, a=0 or 1, and precondition is when X is C, a=1, when X is N, a=0; Wherein when a=1, Y and Z are electron withdraw group independently, are selected from CN, SO 2R f 2, SO 2R, P (O) are (OR) 2, CO 2R, P (O) R 2, C (O) R f 3, C (O) R, the cycloalkenyl group and the H that form with their, precondition be Y and Z the two can not all be H; R wherein in addition f 1, R f 2And R f 3Be C 1-4Perfluoroalkyl, it is randomly replaced by one or more ether oxygen; R is C 1-6Alkyl, it is randomly replaced by one or more ether oxygen, or aryl, it randomly further is substituted; Perhaps wherein when a=0, Y is by formula-SO 2R f 6The electron withdraw group of expression, wherein R f 6Be by formula-(R f 4SO 2N -(Li +) SO 2) mR f 5The group of expression, wherein m=0 or 1, and R f 4Be-C nF 2n-, R f 5Be-C nF 2n+1, n=1-4 is randomly replaced by one or more ether oxygen here.
18, the method for claim 17 wherein comprises the compacting of described stratiform sheet material applying heat and/or pressure with the step that constitutes electrochemical cell.
19, the method for claim 17, wherein active material of positive electrode or lithium embed transition metal oxide, phosphate or sulfate or these two is a particle form, and described particle size is that average equivalent sphere diameter is 1 to 100 micron.
20, the method for claim 17, wherein lithium embedding transition metal oxide, phosphate or sulfate are to be selected from LiCoO 2, LiMnO 4, LiNiO 2, LiNi xCo 1- xO 2, wherein x is 0<x<1, and the lithium of derivative embeds transition metal oxide.
21, the method for claim 17, wherein the cathode collector of graphitiferous is a purity greater than 95% graphite flake.
22, the method for claim 21, wherein said graphite flake are characterised in that its bulk density is 0.8 to 1.4 gram/cubic centimetre.
23, the method for claim 17, the thickness of wherein said graphite flake is less than 75 microns.
24, the method for claim 17, wherein said graphite flake are characterised in that conductance is 1000Siemens/cm at least in its face.
25, the method for claim 17, wherein the cathode collector of graphitiferous also comprises adhesive accelerant.
26, the method for claim 17, wherein said electrolyte comprises organic carbonate.
27, the method for claim 26, wherein said organic carbonate are selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and its mixture.
28, the method for claim 17, wherein the concentration of lithium compound is 0.5 to 2 molar concentration in described electrolyte.
29, the method for claim 17, wherein this lithium compound is expressed from the next
CF 3SO 2N -(Li +)SO 2CF 3
30, the ionomer that the method for claim 17, wherein said first and second polymer are selected from poly-inclined to one side vinylidene fluoride and its copolymer and have fluorinated sulfonic acid, imino group or methyl lithium salts side group.
31, the method for claim 30, wherein said first and second polymer are poly-inclined to one side vinylidene fluoride or its copolymer.
32, the method for claim 17, wherein said ion permeable separator comprise be selected from micro pore sheet, solvent swellable polymers, the polymeric component of the fluidized polymer electrolyte that condenses, polyethers, fluorinated ionic cross-linked polymer and its combination.
33, the method for claim 17, wherein said ion permeable separator comprises poly-inclined to one side 1,1-difluoroethylene and vinylidene fluoride and be selected from the copolymer of the monomer of hexafluoropropylene, perfluoro methyl vinyl ether, perfluoroethylvinyl ether and perfluoro propyl vinyl ether.
34, the method for claim 17, wherein said ion permeable separator comprises the micropore polyolefin sheet.
35, the method for claim 17, wherein said ion permeable separator comprises and containing by 1, ionomer and the imide salt and the methide derivative of the 1-difluoroethylene repeat units derived and the skeleton of perfluorinated alkenyl monomer with the ion side group that is expressed from the next
-(O-CF 2CFR) aO-CF 2(CFR ') bSO 3-xLi +Wherein R and R ' are independently selected from F, Cl or fluoridized C 1-10-alkyl, a=0,1 or 2, b=0 to 6.
36, the electrochemical cell of claim 1, wherein cathode collector is a purity greater than 95%, bulk density is 0.8-1.4g/cm 3, thickness is the graphite flake of 1000Siemens/cm less than conductance in 75 microns and its face at least; And electrolyte is the solution of 0.5 to 2 molar concentration of lithium compound in the organic carbonate that is selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and its mixture; This lithium compound is expressed from the next
CF 3SO 2N -(Li +)SO 2CF 3
37, the method for claim 17, wherein cathode collector is a purity greater than 95%, bulk density is 0.8-1.4g/cm 3, thickness is the graphite flake of 1000Siemens/cm less than conductance in 250 microns and its face at least; Aprotic liquids is the organic carbonate that is selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and its mixture; And by following formula
CF 3SO 2N -(Li +) SO 2CF 3The amount of the lithium compound of expression makes when it mixes with described organic carbonate, will obtain the solution of 0.5 to 2 molar concentration of lithium compound in this organic carbonate.
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