Patent Application
20130323571
There is currently great interest in developing a new generation of high temperature stable, high voltage, non-flammable and durable rechargeable batteries in various applications including consumer electronics and automobile industries.
Conventional electrolytes with organic solvent are high on the list of hazardous chemicals because they are typically volatile liquids that are used in large quantity and produce harmful spills that are difficult to contain. It is known for organic-solvent based electrolytes that a wider stability window is found when inert electrodes are used, like glassy-carbon or platinum, than when electrodes containing active materials are used, like intercalation compounds. In the case of electrodes containing active materials, smaller electrolyte stability windows are found due to interaction of the electrolyte with the active materials. Furthermore, increasing the temperature enhances these interactions, resulting in an even smaller stability window.
Ionic liquids are salts that are liquid at ambient or near ambient temperatures. Unlike conventional organic solvents, ionic liquids are non-volatile, non-flammable, and chemically stable over a wide temperature ranges, up to 500° C. These properties are advantageous to help reduce losses to evaporation, eliminate volatile organic emissions, and improve safety. Other properties of ionic liquids have also proved advantageous. For example, many ionic liquids have a broad temperature range at which they remain liquid and are stable over a broad pH range. This is beneficial for high temperature processes with a demanding pH. Ionic liquids also show the widest electrochemical stability windows of up to 5.5 V, measured between glassy carbon electrodes at 25° C. (see, MacFarlane, et al. Journal of Physical Chemistry B. 1999, 103, 4164).
Therefore, there is a need to develop ionic liquid electrolytes based lithium-ion electrochemical cells and batteries that have high thermal stability, wide electrochemical stability windows, low corrosivity, excellent durability and high ion conductivity. The present invention satisfies these and other needs.
The present invention provides thermally stable lithium-ion electrochemical cells. The cells include an electrolyte solution, which comprises a lithium compound, an ionic liquid or a mixture of an organic solvent and an ionic liquid. Compared to conventional organic solvents, ionic liquids allow the obtaining of very high electrolyte concentration at ease. Advantageously, the electrochemical cell has high thermal stability, wide electrochemical stability windows, low corrosivity, excellent durability, high working voltage and high ion conductivity. Higher anodic stability of carbon current collector than other common metallic current collectors such as Al and Ni; in conjunction with higher anodic stability of ionic liquids allows for higher voltage cathode active materials to be used which will increase the energy density of the cell.
In one aspect, the present invention provides a lithium-ion electrochemical cell. The cell includes a positive electrode comprising a positive electrode active material and a carbon sheet current collector in electronically conductive contact with the positive electrode material, a negative electrode comprising an negative electrode active material and a current collector in electronically conductive contact with the negative electrode material, an ion permeable separator, and an electrolyte solution in ionically conductive contact with the negative electrode and positive electrode. The electrolyte solution comprises a lithium compound and a solvent selected from an ionic liquid of formula (I) or a mixture of an organic solvent and an ionic liquid of formula (I):
Q+E− (I)
Q+ is a cation selected from the group consisting of dialkylammonium, trialkylammonium, tetraalkylammonium, dialkylphosphonium, trialkylphosphonium, tetraalkylphosphonium, trialkylsulfonium, (Rf)4N+ and an N-alkyl or N-hydrogen cation of a 5- or 6-membered heterocycloalkyl or heteroaryl ring having from 1-3 heteroatoms as ring members selected from N, O or S, wherein the heterocycloalkyl or heteroaryl ring is optionally substituted with from 1-5 optionally substituted alkyls and Rf is alkyl or alkoxyalkyl. E− is an anion selected from the group consisting of R1—X−R2(R3)m, NC—S−, BF4−, PF6−, RaSO3−, RaP−F3, RaCO2−, ClO4−, (FSO2)2N—, AsF6−, SO4−, B−(ORa1)2(ORa2)2 and bis[oxalate(2-)-O,O′]borate. The subscript m is 0 or 1. X is N when m is 0. X is C when m is 1. R1, R2 and R3 are each independently an electron-withdrawing group selected from the group consisting of halogen, —CN, —SO2Rb, —SO2Rb, —SO2-La-SO2N−Li+SO2Rb, —P(O)(ORb)2, —P(O)(Rb)2, —CO2Rb, —C(O)Rb and —H, with the proviso that R1 and R2 are other than hydrogen when m=0, and no more than one of R1, R2 and R3 is hydrogen when m=1. Each Ra is independently C1-8 perfluoroalkyl. La is C1-4 perfluoroalkylene. Each Rb is independently selected from the group consisting of C1-8alkyl, C1-8haloalkyl, C1-8 perfluoroalkyl, perfluorophenyl, aryl, optionally substituted barbituric acid and optionally substituted thiobarbituric acid. At least one carbon-carbon bond of the alkyl or perfluoroalkyl are optionally substituted with a member selected from —O— or —S— to form an ether or a thioether linkage and the aryl is optionally substituted with from 1-5 members selected from the group consisting of halogen, C1-4haloalkyl, C1-4perfluoroalkyl, —CN, —SO2Rc, —P(O)(ORc)2, —P(O)(Rc)2, —CO2Rc and —C(O)Rc, wherein Rc is independently C1-8 alkyl, C1-8 perfluoroalkyl or perfluorophenyl and La is C1-4 perfluoroalkylene. Ra1 and Ra2 are each independently an alkyl. In one embodiment, two Ra1 groups together with the oxygen atoms to which the two Ra1 groups are attached and the boron atom to which the oxygen atoms are attached form a five- or six-member ring, which is optionally fused with a six-membered aromatic ring having 0-1 nitrogen heteroatom, and optionally two Ra2 groups together with the oxygen atoms to which the two Ra groups are attached and the boron atom to which the oxygen atoms are attached form a five- or six-member ring, which is optionally fused with a six-membered aromatic ring having 0-1 nitrogen heteroatom. In some embodiments, at least one positive electrode tab having a first attachment end and a second attachment end, wherein the first attachment end is connected to the positive electrode current collector; optionally, at least one negative electrode tab having a first attachment end and a second attachment end, wherein the first attachment end is connected to the negative electrode current collector.
In another aspect, the present invention provides a battery pack. The battery pack includes a plurality of cells, wherein each cell comprises an ionic liquid of formula (I):
Q+E− (I)
wherein Q+ is a cation selected from the group consisting of dialkylammonium, trialkylammonium, tetraalkylammonium, dialkylphosphonium, trialkylphosphonium, tetraalkylphosphonium, trialkylsulfonium, (Rf)4N+ and an N-alkyl or N-hydrogen cation of a 5- or 6-membered heterocycloalkyl or heteroaryl ring having from 1-3 heteroatoms as ring members selected from N, O or S, wherein the heterocycloalkyl or heteroaryl ring is optionally substituted with from 1-5 optionally substituted alkyls and each Rf is independently alkyl or alkoxyalkyl. E− is an anion selected from the group consisting of R1—X−R2(R3)m, NC—S−, BF4−, PF6−, RaSO3−, RaP−F3, RaCO2−, I−, ClO4−, (FSO2)2N—, ASF6−, SO4− and bis[oxalate(2-)-O,O′]borate, wherein m is 0 or 1. X is N when m is 0. X is C when m is 1. R1, R2 and R3 are each independently an electron-withdrawing group selected from the group consisting of halogen, —CN, —SO2Rb, —SO2-La-SO2N−Li+SO2Rb, —P(O)(ORb)2, —P(O)(Rb)2, —CO2Rb, —C(O)Rb and —H; with the proviso that R1 and R2 are other than hydrogen when m=0, and no more than one of R1, R2 and R3 is hydrogen when m=1. Each Ra is independently C1-8 perfluoroalkyl. Each Rb is independently selected from the group consisting of C1-8alkyl, C1-8haloalkyl, C1-8 perfluoroalkyl, perfluorophenyl, aryl, optionally substituted barbituric acid and optionally substituted thiobarbituric acid. At least one carbon-carbon bond of the alkyl or perfluoroalkyl are optionally substituted with a member selected from —O— or —S— to form an ether or a thioether linkage and the aryl is optionally substituted with from 1-5 members selected from the group consisting of halogen, C1-4haloalkyl, C1-4perfluoroalkyl, —CN, —SO2Rc, —P(O)(ORc)2, —P(O)(Rc)2, —CO2Rc and —C(O)Rc, wherein Rc is independently C1-8 alkyl, C1-8 perfluoroalkyl or perfluorophenyl and La is C1-4perfluoroalkylene. These and other aspects and advantages of the present invention will become apparent to one of skill in the art from the following detailed description and figures.
The term “alkyl”, by itself or as part of another substituent, means, unless otherwise stated, a straight or branched chain hydrocarbon radical, having the number of carbon atoms designated (i.e. C1-8 means one to eight carbons). Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and the like. For each of the definitions herein (e.g., alkyl, alkylene and haloalkyl), when a prefix is not included to indicate the number of main chain carbon atoms in an alkyl portion, the radical or portion thereof will have 20 or fewer main chain carbon atoms.
The term “alkylene” by itself or as part of another substituent means a linear or branched saturated divalent hydrocarbon radical derived from an alkane having the number of carbon atoms indicated in the prefix. For example, (C1-C6)alkylene is meant to include methylene, ethylene, propylene, 2-methylpropylene, pentylene, and the like. Perfluoroalkylene means an alkylene where all the hydrogen atoms are substituted by fluorine atoms. Fluoroalkylene means an alkylene where hydrogen atoms are partially substituted by fluorine atoms.
The terms “halo” or “halogen,” by themselves or as part of another substituent, mean, unless otherwise stated, a fluorine, chlorine, bromine, or iodine atom.
The term “haloalkyl,” are meant to include monohaloalkyl and polyhaloalkyl. For example, the term “C1-4 haloalkyl” is mean to include trifluoromethyl, 2,2,2-trifluoroethyl, 4-chlorobutyl, 3-bromopropyl, 3-chloro-4-fluorobutyl and the like.
The term “perfluoroalkyl” means an alkyl where all the hydrogen atoms in the alkyl are substituted by fluorine atoms. Examples of perfluoroalkyl include —CF3, —CF2CF3, —CF2—CF2CF3, —CF(CF3)2, —CF2CF2CF2CF3, —CF2CF2CF2CF2CF3 and the like. The term “perfluoroalkylene” means a divalent perfluoroalkyl.
The term “aryl” means a monovalent monocyclic, bicyclic or polycyclic aromatic hydrocarbon radical of 5 to 10 ring atoms which is unsubstituted or substituted independently with one to four substituents, preferably one, two, or three substituents selected from alkyl, cycloalkyl, cycloalkyl-alkyl, halo, cyano, hydroxy, alkoxy, amino, acylamino, mono-alkylamino, di-alkylamino, haloalkyl, haloalkoxy, heteroalkyl, COR (where R is hydrogen, alkyl, cycloalkyl, cycloalkyl-alkyl, phenyl or phenylalkyl, aryl or arylalkyl), —(CR′R″)n—COOR (where n is an integer from 0 to 5, R′ and R″ are independently hydrogen or alkyl, and R is hydrogen, alkyl, cycloalkyl, cycloalkylalkyl, phenyl or phenylalkyl aryl or arylalkyl) or —(CR′R″)n—CONR′″R″″(where n is an integer from 0 to 5, R′ and R″ are independently hydrogen or alkyl, and R′″ and R″″ are each independently hydrogen, alkyl, cycloalkyl, cycloalkylalkyl, phenyl or phenylalkyl, aryl or arylalkyl). More specifically the term aryl includes, but is not limited to, phenyl, biphenyl, 1-naphthyl, and 2-naphthyl, and the substituted forms thereof.
The term “heteroaryl” refers to aryl groups (or rings) that contains from one to five heteroatoms selected from N, O, or S, wherein the nitrogen and sulfur atoms are optionally oxidized, and the nitrogen atom(s) are optionally quaternized. Non-limiting examples of heteroaryl groups include pyridyl, pyridazinyl, pyrazinyl, pyrimindinyl, triazinyl, quinolinyl, quinoxalinyl, quinazolinyl, cinnolinyl, phthalaziniyl, benzotriazinyl, purinyl, benzimidazolyl, benzopyrazolyl, benzotriazolyl, benzisoxazolyl, isobenzofuryl, isoindolyl, indolizinyl, benzotriazinyl, thienopyridinyl, thienopyrimidinyl, pyrazolopyrimidinyl, imidazopyridines, benzothiaxolyl, benzofuranyl, benzothienyl, indolyl, quinolyl, isoquinolyl, isothiazolyl, pyrazolyl, indazolyl, pteridinyl, imidazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiadiazolyl, pyrrolyl, thiazolyl, furyl, thienyl and the like.
The term “cycloalkyl” refers to hydrocarbon rings having the indicated number of ring atoms (e.g., C3-6cycloalkyl) and being fully saturated or having no more than one double bond between ring vertices. One or two C atoms may optionally be replaced by a carbonyl. “Cycloalkyl” is also meant to refer to bicyclic and polycyclic hydrocarbon rings such as, for example, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, etc.
The term “heterocycloalkyl” refers to a cycloalkyl group that contain from one to five heteroatoms selected from N, O, and S, wherein the nitrogen and sulfur atoms are optionally oxidized, and the nitrogen atom(s) are optionally quaternized, the remaining ring atoms being C. The heterocycloalkyl may be a monocyclic, a bicyclic or a polycylic ring system of 3 to 12, preferably 5 to 8, ring atoms in which one to five ring atoms are heteroatoms. The heterocycloalkyl can also be a heterocyclic alkyl ring fused with an aryl or a heteroaryl ring. Non limiting examples of heterocycloalkyl groups include pyrrolidine, piperidiny, imidazolidine, pyrazolidine, butyrolactam, valerolactam, imidazolidinone, hydantoin, dioxolane, phthalimide, piperidine, 1,4-dioxane, morpholine, thiomorpholine, thiomorpholine-5-oxide, thiomorpholine-S,S-oxide, piperazine, pyran, pyridone, 3-pyrroline, thiopyran, pyrone, tetrahydrofuran, tetrahydrothiophene, quinuclidine, and the like. A heterocycloalkyl group can be attached to the remainder of the molecule through a ring carbon or a heteroatom.
The above terms (e.g., “alkyl” and “aryl”), in some embodiments, will include both substituted and unsubstituted forms of the indicated radical. Preferred substituents for each type of radical are provided below. For brevity, the terms aryl and heteroaryl will refer to substituted or unsubstituted versions as provided below, while the term “alkyl” and related aliphatic radicals is meant to refer to unsubstituted version, unless indicated to be substituted.
Substituents for the alkyl radicals (including those groups often referred to as alkylene and heterocycloalkyl) can be a variety of groups selected from: -halogen, —OR′, —NR′R″, —SR′, —SiR′R″R′″, —OC(O)R′, —C(O)R′, —CO2R′, —CONR′R″, —OC(O)NR′R″, —NR″C(O)R′, —NR′—C(O)NR″R′″, —NR″C(O)2R′, —NH—C(NH2)═NH, —NR′C(NH2)═NH, —NH—C(NH2)═NR′, —S(O)R′, —S(O)2R′, —S(O)2NR′R″, —NR′S(O)2R″, R′, —CN and —NO2 in a number ranging from zero to (2 m′+1), where m′ is the total number of carbon atoms in such radical. R′, R″ and R′″ each independently refer to hydrogen, unsubstituted C1-8 alkyl, unsubstituted heteroalkyl, unsubstituted aryl, perfluorophenyl, aryl substituted with 1-3 halogens, C1-8 perfluoroalkyl, partially fluorinated alkyls such as C1-8alkyl substituted with from 1-17 fluorine atoms, C1-8 alkoxy or C1-8 thioalkoxy groups, or unsubstituted aryl-C1-4 alkyl groups. When R′ and R″ are attached to the same nitrogen atom, they can be combined with the nitrogen atom to form a 3-, 4-, 5-, 6-, or 7-membered ring. For example, —NR′R″ is meant to include 1-pyrrolidinyl and 4-morpholinyl. The term “acyl” as used by itself or as part of another group refers to an alkyl radical wherein two substitutents on the carbon that is closest to the point of attachment for the radical is replaced with the substitutent ═O (e.g., —C(O)CH3, —C(O)CH2CH2OR′ and the like).
Substituents for the aryl groups are varied and are generally selected from: -halogen, —OR′, —OC(O)R′, —NR′R″, —SR′, —R′, —CN, —NO2, —CO2R′, —CONR′R″, —C(O)R′, —OC(O)NR′R″, —NR″C(O)R′, —NR″C(O)2R′, —NR′—C(O)NR″R′″, —NH—C(NH2)═NH, —NR′C(NH2)═NH, —NH—, C(NH2)═NR′, —S(O)R′, —S(O)2R′, —S(O)2NR′R″, —NR′S(O)2R″, —N3, perfluoro(C1-C4)alkoxy, and perfluoro(C1-C4)alkyl, perfluorophenyl, and C1-4alkyl substituted with from 1-9 fluorine atoms, in a number ranging from zero to the total number of open valences on the aromatic ring system; and where R′, R″ and R′″ are independently selected from hydrogen, C1-8 alkyl, unsubstituted aryl and heteroaryl, (unsubstituted aryl)-C1-4 alkyl, and unsubstituted aryloxy-C1-4 alkyl.
The term “positive electrode” refers to one of a pair of rechargeable lithium-ion cell electrodes that under normal circumstances and when the cell is fully charged will have the highest potential. This terminology is retained to refer to the same physical electrode under all cell operating conditions even if such electrode temporarily (e.g., due to cell overdischarge) is driven to or exhibits a potential below that of the other (the negative) electrode.
The term “negative electrode” refers to one of a pair of rechargeable lithium-ion cell electrodes that under normal circumstances and when the cell is fully charged will have the lowest potential. This terminology is retained to refer to the same physical electrode under all cell operating conditions even if such electrode is temporarily (e.g., due to cell overdischarge) driven to or exhibits a potential above that of the other (the positive) electrode.
The term “ionic liquid” means a salt comprising a cation and an anion. The salt is a liquid at ambient or near ambient temperatures. Preferably, the cations are organic cations.
In one aspect, the present invention provides a lithium-ion electrochemical cell. The cell includes a positive electrode comprising a positive electrode active material and a carbon sheet current collector in electronically conductive contact with the positive electrode material; a negative electrode comprising an negative electrode active material and a current collector in electronically conductive contact with the negative electrode material; an ion permeable separator; and an electrolyte solution in ionically conductive contact with the negative electrode and positive electrode, wherein the electrolyte solution comprises a lithium compound and a solvent selected from an ionic liquid of formula (I) or a mixture of an organic solvent and an ionic liquid of formula (I):
Q+E− (I)
Q+ is a cation selected from the group consisting of dialkylammonium, trialkylammonium, tetraalkylammonium, dialkylphosphonium, trialkylphosphonium, tetraalkylphosphonium, trialkylsulfonium, (Rf)4N+ and an N-alkyl or N-hydrogen cation of a 5- or 6-membered heterocycloalkyl or heteroaryl ring having from 1-3 heteroatoms as ring members selected from N, O or S, wherein the heterocycloalkyl or heteroaryl ring is optionally substituted with from 1-5 optionally substituted alkyls and each Rf is independently an alkyl or an alkoxyalky. E− is an anion selected from the group consisting of R1—X−R2(R3)m, NC—S−, BF4−, PF6−, RaSO3−, RaP−F3, RaCO2−, I−, ClO4−, (FSO2)2N—, AsF6−, SO4−, B−(ORa1)2(ORa2)2 and bis[oxalate(2-)-O,O′]borate, wherein m is 0 or 1. In one embodiment, the substituent for alkyl can be alkoxy or any substituents as defined above. X is N when m is 0. X is C when m is 1. R1, R2 and R3 are each independently an electron-withdrawing group selected from the group consisting of halogen, —CN, —SO2Rb, —SO2-La-SO2N−Li+SO2Rb, —P(O)(ORb)2, —P(O)(Rb)2, —CO2Rb, —C(O)Rb and —H, with the proviso that R1 and R2 are other than hydrogen when m=0, and no more than one of R1, R2 and R3 is hydrogen when m=1. In one embodiment, halogen is F−. Each Ra is independently C1-8 perfluoroalkyl. La is C1-4 perfluoroalkylene. Each Rb is independently selected from the group consisting of C1-8alkyl, C1-8haloalkyl, C1-8 perfluoroalkyl, perfluorophenyl, aryl, optionally substituted barbituric acid and optionally substituted thiobarbituric acid. At least one carbon-carbon bond of the alkyl or perfluoroalkyl are optionally substituted with a member selected from —O— or —S— to form an ether or a thioether linkage and the aryl is optionally substituted with from 1-5 members selected from the group consisting of halogen, C1-4haloalkyl, C1-4perfluoroalkyl, —CN, —SO2Rc, —P(O)(ORc)2, —P(O)(Rc)2, —CO2Rc and —C(O)Rc, wherein Rc is independently C1-8 alkyl, C1-8 perfluoroalkyl or perfluorophenyl and La is C1-4 perfluoroalkylene. Ra1 and Ra2 are each independently an alkyl. In certain instances, Ra, Rb and Rc are each independently selected from perfluorophenyl and phenyl optionally substituted with from 1-3 members selected from —F or C1-4 perfluoroalkyl. In one instance, two Ra1 groups taken together with the oxygen atoms to which the two Ra1 groups are attached and the boron atom to which the two oxygen atoms are attached form a five- or six-member ring, which is optionally fused with a six-membered aromatic ring having 0-1 nitrogen heteroatom, and optionally two Ra2 groups taken together with the oxygen atoms to which the two Ra1 groups are attached and the boron atom to which the two oxygen atoms are attached form a five- or six-member ring, which is optionally fused with a six-membered aromatic ring having 0-1 nitrogen heteroatom.
In one group of embodiments of compounds of formula (I), cation Q+ has a formula (Ia):
wherein R4 is H, a C1-20 alkyl or alkoxyalkyl, optionally substituted with from 1-3 members selected from the group consisting of halogen and C1-4 perfluoroalkyl; Y1 and Y3 are each independently selected from the group consisting of ═N— and ═CRd—; Y2 and Y4 are each independently selected from the group consisting of ═N—, —O—, —S—, —NRd— and CRd—, with the proviso that Y2 and Y4 are neither simultaneously a member selected from the group consisting of —NRd— and ═CRd—, nor simultaneously a member selected from the group consisting of —O—, —NRd— and —S—; wherein each Rd is independently —H, an alkyl or an alkoxyalky. In certain instances, Y1, Y2, Y3 and Y4 are ═N—. In certain other instances, Y1, Y2, Y3 and Y4 are ═CRd—. In yet other instances, Y1 is ═CRd—, Y2 is ═N—, Y3 is ═N— or ═CRd— and Y4 is ═N—, —O—, —S— or ═CRd—. In still other instances, Y′ is ═CRd—, Y2 is —O— or —S—, Y3 is ═N— or ═CRd— and Y4 is ═N— or ═CRd—. In other instances, Y1 is CRd—, Y2 is ═CRd—, Y3 is ═N— or ═CRd— and Y4 is ═N—, —O—, —S— or ═CRd—. In yet other instances, Y1 is ═N—, Y2 is ═N—, Y3 is ═N— or ═CRd— and Y4 is ═N—, —O—, —S— or ═CRd—. In still other instances, Y1 is ═N—, Y2 is —O— or —S—, Y3 is ═N— or ═CRd— and Y4 is ═N— or ═CRd—. In other instances, Y1 is ═N—, Y2 is ═CRd—, Y3 is ═N— or ═CRd— and Y4 is ═N—, —O—, —S— or ═CRd—.
In another group of embodiments of compounds of formula (I), cation Q+ has a subformula (Ia-1):
wherein the substituents Y1, Y3, Y4, R4 and Rd are as defined above. In certain instances, Y1 is ═N— or ═CRd. In one occurrence, Y1 is ═CRd. In certain other instances, Y4 is —O—. In yet other instances, R4 is H. In yet other instances, Y1, Y3 and Y4 are CH—, R4 is methyl and Rd is C1-8alkyl or C1-8alkoxyalkyl.
In yet another group of embodiments of compounds of formula (I), cation Q+ has a formula (Ib):
wherein R5 is —H, C1-20alkyl or alkoxyalkyl, optionally substituted with from 1-3 members selected from the group consisting of halogen and C1-4 perfluoroalkyl; and Z1, Z2, Z3, Z4 and Z5 are each independently selected from the group consisting of ═N— and CRe—, wherein each Re is independently selected from the group consisting of —H and alkyl, or optionally the Re substituents on the adjacent carbons are combined with the atoms to which they are attached form a 5- or 6-membered ring having from 0-2 addition heteroatoms as ring members selected from O, N or S. In certain instances, Z1 is ═N. In one occurrence, Z2, Z3, Z4 and Z5 are ═CRe—. In certain other instances, Z2 is ═N—. In one occurrence, Z1, Z3, Z4 and Z5 are ═CRe—. In yet other instances, Z3 is ═N—. In one occurrence, Z1, Z2, Z4 and Z5 are CRe—. In still other instances, Re is —H.
In still another group of embodiments of compounds of formula (I), cation Q+ has a formula (Ic):
wherein the subscript p is 1 or 2; and R6 and R7 are each independently H or an optionally substituted C1-8alkyl. In certain instances, p is 1 and R6 and R7 are each independently an optionally substituted C1-8alkyl. In one occurrence, R6 and R7 are each independently a C1-8alkyl. In certain other instances, p is 1, R6 is methyl and R7 is C1-8alkyl. In one occurrence, R7 is butyl. In yet other instances, p is 2.
In another group of embodiments of compounds of formula (I), cation Q+ is selected from the group consisting of:
The organic cations used in the present invention include at least one cation selected from the group consisting of, for example, imidazolium ions such as dialkyl imidazolium cation and trialkyl imidazolium cation, tetraalkyl ammonium ion, alkyl pyridinium ion, dialkyl pyrrolidinium ion, and dialkyl piperidinium ion. Organic cations such as imidazolium ion, dialkyl piperidinium ion and tetraalkyl ammonium ion are excellent in electrical conductivity. These organic cations are ranked in the order of imidazolium ion>>dialkyl piperidinium ion>tetraalkyl ammonium ion, if arranged in the order of the electrical conductivity.
In one group of embodiments of compounds of formula (I), anion E− is selected from the group consisting of R1—X−R2(R3)m, NC—S−, BF4−, PF6−, RaSO3−, RaP−F3, RaCO2−, I−, ClO4−, (FSO2)2N—, AsF6−, SO4−, B−(ORa1)2(ORa2)2 and bis[oxalate(2-)-O,O′]borate. The substituents R1, R2, R3, Ra1, Ra2 and subscript m are as defined above. In certain instances, E− is CF3SO2X−R2(R3)m. In other instances, E− is selected from the group consisting of (CF3SO2)3C−, (CF3SO2)2CH−, CF3(CH2)3SO3−, (CF3SO2)2N−, (CN)2N−, SO4−, CF3SO3−, NC—S−, BF4−, PF6−, (CF3CF2)3P−F3, CF3CO2−, I−, SO4− and bis[oxalate(2-)-O,O′]borate. In other instances, E− is PF6−, BF4− or ClO4−. In yet other instances, E− is a borate compound having the formulas:
wherein Ra1 and Ra2 groups are as defined above and each Ra3 is independently —H or alkyl. One of the ordinary skill in the art will understand that these anions can also be used to form lithium compounds.
In one embodiment, the lithium-ion electrochemical cell contains a lithium compound having formula: Li+E−, wherein E− is as defined above. In certain instances, E−is R1—X−R2(R3)m, BF4−, PF6−, ClO4− or SO4−. In other instances, E− is BF4−, PF6−, ClO4−, (FSO2)2N—, AsF6−, or SO4−. In another embodiment, the lithium-ion electrochemical cell contains a lithium compound having formula (II): R1—X−(Li+)R2(R3)n, wherein: n is 0 or 1; X is N when n is 0; X is C when n is 1; R1, R2 and R3 are each independently an electron-withdrawing group selected from the group consisting of halogen, —CN, —SO2Rb, —SO2(—Rb—SO2Li+)SO2—Rb, —P(O)(ORb)2, —P(O)(Rb)2, —CO2Rb, —C(O)Rb and —H; with the proviso that R1 and R2 are other than hydrogen when n=0, and no more than one of R1, R2 and R3 is hydrogen when n=1; and wherein each Rb is independently selected from the group consisting of C1-8 alkyl, C1-8haloalkyl, C1-8 perfluoroalkyl, perfluorophenyl, aryl, optionally substituted barbituric acid and optionally substituted thiobarbituric acid, wherein at least one carbon-carbon bond of the alkyl or perfluoroalkyl are optionally substituted with a member selected from —O— or —S— to form an ether or a thioether linkage and the aryl is optionally substituted with from 1-5 members selected from the group consisting of halogen, C1-4haloalkyl, C1-4perfluoroalkyl, —CN, —SO2Rc, —P(O)(ORc)2, —P(O)(Rc)2, —CO2Rc and —C(O)Rc, wherein Rc is C1-8 alkyl, perfluorophenyl or C1-8 perfluoroalkyl. Preferably, the compound has an oxidation potential above the recharged potential of the positive electrode. In one instance, the lithium compound has the formula: CF3SO2N−(Li+)SO2CF3.
The electrolyte solvents can be pure ionic liquid or a mixture of ionic liquids with organic solvents. Suitable organic solvents include carbonates and lactones. Organic carbonates and lactones include compounds having the formula: RxOC(═O)ORy, wherein Rx and Ry are each independently selected from the group consisting of C1-4alkyl and C3-6cycloalkyl, or together with the atoms to which they are attached to form a 4- to 8-membered ring, wherein the ring carbons are optionally substituted with 1-2 members selected from the group consisting of halogen, C1-4alkyl and C1-4haloalkyl. In one embodiment, the organic carbonates include propylene carbonate, dimethyl carbonate, ethylene carbonate, diethyl carbonate, ethylmethyl carbonate and a mixture thereof as well as many related species. The lactones can be β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, hexano-6-lactone or a mixture thereof, each of which is optionally substituted with from 1-4 members selected from the group consisting of halogen, C1-4alkyl and C1-4haloalkyl.
In certain embodiments, the electrolyte solvent is a mixture of an ionic liquid and an organic solvent. The organic solvent and the ionic liquid can have a volume ratio from about 1:100 to about 100:1. In other embodiments, the volume ratio is from about 1:10 to about 10:1. Exemplary ratios organic solvent and ionic liquid include 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 and 10:1.
The electrolyte solution suitable for the practice of the invention is formed by combining the lithium compounds of formula (II) with an electrolyte solvent comprising ionic liquids of formula (I). For example, lithium imide such as lithium bis(trifluorosulfonyl)imide (LiTFSI) or methide salts of compounds of formula (II) are optionally combined with a co-salt selected from LiPF6, LiBF4, LiAsF6, LiB(C2O4)2, (Lithium bis(oxalato)borate), LiF or LiClO4, along with the electrolyte solvent/ionic liquid by dissolving, slurrying or melt mixing as appropriate to the particular materials. The present invention is operable when the concentration of the imide or methide salt is in the range of 0.2 to up to 3 molar, but 0.5 to 2 molar is preferred, with 0.8 to 1.2 molar most preferred. Depending on the fabrication method of the cell, the electrolyte solution may be added to the cell after winding or lamination to form the cell structure, or it may be introduced into the electrode or separator compositions before the final cell assembly.
In some embodiments, the current collector for the electrode is a non-metal conductive substrate. Exemplary non-metal current collectors include, but are not limited to, a carbon sheet such as a graphite sheet, a carbon fiber sheet, a carbon foam, a carbon nanotube film, and a mixture of the foregoing or other conducting polymeric materials. Those of skill in the art will know of these conducting polymeric materials.
In some embodiments, the electrochemical cell has one or more tabs attached to each electrode. In one instance, each electrode has at least one tab. In another instance, each electrode has multiple tabs. In yet another instance, the positive electrode has multiple metal tabs attached to the positive electrode on the carbon current collector. For example, each electrode can have from 2 to 20 tabs. The positive and the negative electrode can have different numbers of tabs. The tabs can be made of a single metal, a metal alloy or a composite material. Preferably, the tabs are metallic. Suitable metals include, but are not limited to, iron, stainless steel, copper, nickel, chromium, zinc, aluminum, tin, gold, tantalum, niobium, hafnium, zirconium, vanadium, indium, cobalt, tungsten, beryllium and molybdenum and alloys thereof or an alloy thereof. Preferably, the metal is anticorrosive. The tabs can have anticorrosive coatings made of any of the above metals, anodizing and oxide coatings, conductive carbon, epoxy and glues, paints and other protective coatings. The coatings can be nickel, silver, gold, palladium, platinum, rhodium or combinations thereof for improving conductivity of the tabs. In one instance, the tabs are made of copper, aluminum, tin or alloys thereof. The tabs can have various shapes and sizes. In general, the tabs are smaller than the current collector to which the tabs are attached to. In one embodiment, the tabs can have a regular or an irregular shape and form. In one instance, the tabs have L-shape, I-shape, U-shape, V-shape, inverted T-shape, rectangular-shape or combinations of shapes. Preferably, the tabs are metal strips fabricated into a particular shape or form. The alloys can be a combinations of metals described herein or formed by combining the metals described above with other suitable metals known to persons of skill in the art.
Typically, each of the tabs has a first attachment end and a second attachment end. The first attachment end is an internal end for attaching to a current collector and the second attachment end is an external or an open end for connecting to an external circuit. The first attachment end can have various shapes and dimensions. In one embodiment, the first attachment end of the tabs has a shape selected from the group consisting of a circle, an oval, a triangle, a square, a diamond, a rectangle, a trapezoidal, a U-shape, a V-shape, an L-shape, a rectangular-shape and an irregular shape. In one instance, the tabs are strips with the first attachment end having a dimension of at least 500 micrometers in width and 3 mm in length. In one embodiment, the attachment end has a dimension of at least 0.25 mm2. In certain instances, the dimension is from about 1 mm2 to about 500 mm2. The second attachment end can connect either directly to an external circuit or through a conductive member. The conductive member can be a metal tab, rod or wire. The suitable metal can be copper, aluminum, iron, stainless steel, nickel, zinc, chromium, tin, gold, tantalum, niobium, hafnium, zirconium, vanadium, indium, cobalt, tungsten, beryllium and molybdenum and alloys thereof or an alloy thereof.
In one embodiment, the tabs are in direct contact with the current collector. In another embodiment, the tabs are in contact with the current collector through a conductive layer. The conductive layer can be attached to the surface of the tab, for example, by depositing a layer of carbon black on the tab. The conductive layer can include a conductive filler and a binder. In one instance, the conductive filler is selected from the group consisting of carbon black, conducting polymers, carbon nanotubes and carbon composite materials. Suitable binders include, but are not limited to, a polymer, a copolymer or a combination thereof. Exemplary binders include, but are not limited to, polymeric binders, particularly gelled polymer electrolytes comprising polyacrylonitrile, poly(methylmethacrylate), poly(vinyl chloride), and polyvinylidene fluoride and copolymers thereof. Also, included are solid polymer electrolytes such as polyether-salt based electrolytes including poly(ethylene oxide)(PEO) and its derivatives, poly(propylene oxide) (PPO) and its derivatives, and poly(organophosphazenes) with ethyleneoxy or other side groups. Other suitable binders include fluorinated ionomers comprising partially or fully fluorinated polymer backbones, and having pendant groups comprising fluorinated sulfonate, imide, or methide lithium salts. Preferred binders include polyvinylidene fluoride and copolymers thereof with hexafluoropropylene, tetrafluoroethylene, fluorovinyl ethers, such as perfluoromethyl, perfluoroethyl, or perfluoropropyl vinyl ethers; and ionomers comprising monomer units of polyvinylidene fluoride and monomer units comprising pendant groups comprising fluorinated carboxylate, sulfonate, imide, or methide lithium salts.
The tabs can be attached to the positive electrode or the negative electrode using a process selected from the group consisting of riveting, conductive adhesive lamination, hot press, ultrasonic press, mechanical press, staking, crimping, pinching, and a combination thereof. The process offers the advantages of providing strong binding to the current collector and yet maintaining high electrical conductivity and low impedance across the junction of tab and the current collector. The process is particularly suitable for attaching metal tabs to carbon sheet.
In one embodiment, the first attachment end includes an array of preformed micro indentations. The tabs can have an indentation density from about 1 to about 100 per square millimeter. The indentations can be produced by either a micro indentation hand tool or an automatic indentation device. In one instance, each indentation is about 1-100 μm in depth, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100 micrometers and about 1-500 μm in dimension, such as 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 160, 180, 200, 250, 300, 400, 450, 500 micrometers. The micro indentations can be either evenly or randomly spaced.
The tabs having an array of micro indentations are attached to the current collector via mechanical pressing or riveting to provide a close contact between the tabs and the current collector. Alternatively, the tabs are joint to the current collector through a conductive adhesive layer or staking.
In another embodiment, the first attachment end of the tabs includes an array of preformed micro openings having a plurality of protrusions, such as protruding edges. In one instance, the protrusions are sharp edges. The protrusions can be either generated during the process of making micro openings or prepared by a separate fabrication process. The protrusions extend from about 0.01 mm to about 10 mm above the surface of the tabs and can have various shapes. For example, the protrusions can be triangular, rectangular or circular. The micro openings can have a dimension from micrometers to millimeters. In certain instances, the protrusions extend between about 0.01 mm to 0.04 mm, such as about 0.01, 0.02, 0.03, or 0.04 mm above the surface of the tabs. Preferably, the openings have a dimension of about 1-1000 μm. In one embodiment, the micro openings are evenly spaced. In another embodiment, the openings are randomly distributed. The micro openings can have various shapes. In one embodiment, the micro openings have a shape selected from the group consisting of a circle, an oval, a triangle, a square, a diamond, a rectangle, a trapezoidal, a rhombus, a polygon and an irregular shape.
The tabs having an array of micro openings with protrusions are welded to the current collector through a conductive adhesive layer or by staking, mechanical pressing, staking, riveting or a combination of processes and techniques. The electrically conductive adhesives are generally known to persons of skill in the art. For example, certain conductive adhesives are commercially available from 3M corporation, Aptek laboratories, Inc. and Dow Corning. Exemplary electrically conductive adhesive include, but are not limited to, urethane adhesive, silicone adhesive and epoxy adhesive.
The tabs applicable for the positive electrode as described above can also be used for the negative electrode. In one embodiment, the negative electrode has a carbon current collector.
In one embodiment, the pores in the carbon current collector can be sealed with resins, for example, by treating, contacting of the carbon current collector with resins. The resins can be conductive resins or non-conductive resins known to a person of skill in the art. Exemplary conductive resins are described in U.S. Pat. Nos. 7,396,492, 7,338,623, 7,220,795, 6,919,394, 6,894,100, 6,855,407, 5,371,134, 5,093,037, 4,830,779, 4,772,422, 6,565,772 and 6,284,817. Exemplary non-conductive resins, for example, in adhering, sealing and coating include, but are not limited to, epoxy resin, polyimide resin and other polymer resins known to persons skill in the art.
In one embodiment, the present invention provides a positive electrode, which includes electrode active materials and a current collector. The positive electrode has an upper charging voltage of 3.5-4.5 volts versus a Li/Li+ reference electrode. The upper charging voltage is the maximum voltage to which the positive electrode may be charged at a low rate of charge and with significant reversible storage capacity. In some embodiments, cells utilizing positive electrode with upper charging voltages from 3-5.8 volts versus a Li/Li+ reference electrode are also suitable. In certain instances, the upper charging voltages are from about 3-4.2 volts, 4.0-5.8 volts, preferably, 4.5-5.8 volts. In certain instances, the positive electrode has an upper charging voltage of about 5 volts. For example, the cell can have a charging voltage of 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7 or 5.8 volts. A variety of positive electrode active materials can be used. Non-limiting exemplary electrode active materials include transition metal oxides, phosphates and sulfates, and lithiated transition metal oxides, phosphates and sulfates.
In some embodiments, the electrode active materials are oxides with empirical formula LixMO2, where M is a transition metal ion selected from the group consisting of Mn, Fe, Co, Ni, Al, Mg, Ti, V, and a combination thereof, with a layered crystal structure, the value x may be between about 0.01 and about 1, suitably between about 0.5 and about 1, more suitably between about 0.9 to 1. In other embodiments, the electrode active materials are oxides with the formula LixMa1Mb2Mc3O2, where M1, M2, and M3 are each independently a transition metal ion selected from Mn, Fe, Co, Ni, Al, Mg, Ti, or V. The subscripts a, b and c are each independently a real number between about 0 and 1 (0≦a≦1; 0≦b≦1; 0≦c≦1; 0.01≦x≦1), with the proviso that a+b+c is 1. In certain instances, the electrode active materials are oxides with empirical formula LixNiaCobMncO2, wherein the subscript x is between 0.01 and 1, for example, x is 1; the subscripts a, b and c are each independently 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.9 or 1, with the proviso that a+b+c is 1. In other instances, the subscripts a, b and c are each independently from about 0-0.5, 0.1-0.6, 0.4-0.7, 0.5-0.8, 0.5-1 or 0.7-1 with the proviso that a+b+c is 1. In yet other embodiments, the active materials are oxides with empirical formula Li1+xAyM2-7O4, where A and M are each independently a transition metal ions selected from the group consisting of Fe, Mn, Co, Ni, Al, Mg, Ti, V, and a combination thereof, with a spinel crystal structure, the value x may be between about −0.11 and 0.33, suitably between about 0 and about 0.1, the value of y may be between about 0 and 0.33, suitably between 0 and 0.1. In one embodiment, A is Ni, x is 0 and y is 0.5. In yet some other embodiments the active materials are vanadium oxides such as LiV2O5, LiV6O13, or the foregoing compounds modified in that the compositions thereof are nonstoichiometric, disordered, amorphous, overlithiated, or underlithiated forms such as are known in the art. The suitable positive electrode-active compounds may be further modified by doping with less than 5% of divalent or trivalent metallic cations such as Fe2+, Ti2+, Zn2+, Ni2+, Co2+, Cu2+, Mg2+, Cr3+, Fe3+, Al3+, Ni3+, Co3+, or Mn3+, and the like. In other embodiments, positive electrode active materials suitable for the positive electrode composition include lithium insertion compounds with olivine structure such as LixMXO4 where M is a transition metal ions selected from the group consisting of Fe, Mn, Co, Ni, and a combination thereof, and X is a selected from a group consisting of P, V, S, Si and combinations thereof, the value of the value x may be between about 0 and 2. In certain instances, the compound is LiMXO4. In some embodiments, the lithium insertion compounds include LiMnPO4, LiVPO4, LiCoPO4 and the like. In other embodiments, the active materials with NASICON structures such as YxM2(XO4)3, where Y is Li or Na, or a combination thereof, M is a transition metal ion selected from the group consisting of Fe, V, Nb, Ti, Co, Ni, Al, or the combinations thereof, and X is selected from a group of P, S, Si, and combinations thereof and value of x between 0 and 3. The examples of these materials are disclosed by J. B. Goodenough in “Lithium Ion Batteries” (Wiley-VCH press, Edited by M. Wasihara and O. Yamamoto). Particle size of the electrode materials are preferably between 1 nm and 100 μm, more preferably between 10 nm and 100 um, and even more preferably between 1 μm and 100 μm.
In other embodiments, the electrode active materials are oxides such as LiCoO2, spinel LiMn2O4, chromium-doped spinel lithium manganese oxides LixCryMn2O4, layered LiMnO2, LiNiO2, LiNixCo1-xO2 where x is 0<x<1, with a preferred range of 0.5<x<0.95, and vanadium oxides such as LiV2O5, LiV6O13, or the foregoing compounds modified in that the compositions thereof are nonstoichiometric, disordered, amorphous, overlithiated, or underlithiated forms such as are known in the art. The suitable positive electrode-active compounds may be further modified by doping with less than 5% of divalent or trivalent metallic cations such as Fe2+, Ti2+, Zn2+, Ni2+, Co2+, Cu2+, Mg2+, Cr3+, Fe3+, Al3+, Ni3+, Co3+, or Mn3+, and the like. In yet other embodiments, positive electrode active materials suitable for the positive electrode composition include lithium insertion compounds with olivine structure such as LiFePO4 and with NASICON structures such as LiFeTi(SO4)3, or those disclosed by J. B. Goodenough in “Lithium Ion Batteries” (Wiley-VCH press, Edited by M. Wasihara and O. Yamamoto). In still other embodiments, electrode active materials include LiFePO4, LiMnPO4, LiVPO4, LiFeTi(SO4)3, LiNixMn1-xO2, LiNixCoyMn1-x-yO2 and derivatives thereof, wherein x is 0<x<1 and y is 0<y<1. In certain instances, x is between about 0.25 and 0.9. In one instance, x is ⅓ and y is ⅓. Particle size of the positive electrode active material should range from about 1 to 100 microns. In some preferred embodiments, transition metal oxides such as LiCoO2, LiMn2O4, LiNiO2, LiNixMn1-xO2, LiNixCoyMn1-x-yO2 and their derivatives, where x is 0<x<1 and y is 0<y<1. LiNixMn1-xO2 can be prepared by heating a stoichiometric mixture of electrolytic MnO2, LiOH and nickel oxide to about 300 to 400° C. In certain embodiments, the electrode active materials are xLi2MnO3(1-x)LiMO2 or LiM′PO4, where M is selected from Ni, Co, Mn, LiNiO2 or LiNixCo1-xO2; M′ is selected from the group consisting of Fe, Ni, Mn and V; and x and y are each independently a real number between 0 and 1. LiNixCoyMn1-x-yO2 can be prepared by heating a stoichiometric mixture of electrolytic MnO2, LiOH, nickel oxide and cobalt oxide to about 300 to 500° C. The positive electrode may contain conductive additives from 0% to about 90%. In one embodiment, the subscripts x and y are each independently selected from 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9 or 0.95. x and y can be any numbers between 0 and 1 to satisfy the charge balance of the compounds LiNixMn1-xO2 and LiNixCoyMn1-x-yO2.
Representative positive electrodes and their approximate recharged potentials include FeS2 (3.0 V vs. Li/Li+), LiCoPO4 (4.8 V vs. Li/Li+), LiFePO4 (3.45 V vs. Li/Li+), Li2FeS2 (3.0 V vs. Li/Li+), Li2FeSiO4(2.9 V vs. Li/Li+), LiMn2O4 (4.1 V vs. Li/Li+), LiMnPO4 (4.1 V vs. Li/Li+), LiNiPO4 (5.1 V vs. Li/Li+), LiV3O8 (3.7 V vs. Li/Li+), LiV6O13 (3.0 V vs. Li/Li+), LiVOPO4 (4.15 V vs. Li/Li+), LiVOPO4F (4.3 V vs. Li/Li+), Li3V2(PO4)3 (4.1 V (2 Li) or 4.6 V (3 Li) vs. Li/Li+), MnO2 (3.4 V vs. Li/Li+), MoS3 (2.5 V vs. Li/Li+), sulfur (2.4 V vs. Li/Li+), TiS2(2.5 V vs. Li/Li+), TiS3 (2.5 V vs. Li/Li+), V2O5 (3.6 V vs. Li/Li+), and V6O13 (3.0 V vs. Li/Li+) and combinations thereof.
A positive electrode can be formed by mixing and forming a composition comprising, by weight, 0.01-15%, preferably 4-8%, of a polymer binder, 10-50%, preferably 15-25%, of the electrolyte solution of the invention herein described, 40-85%, preferably 65-75%, of an electrode-active material, and 1-12%, preferably 4-8%, of a conductive additive. Optionally, up to 12% of inert filler may also be added, as may such other adjuvants as may be desired by one of skill in the art, which do not substantively affect the achievement of the desirable results of the present invention. In one embodiment, no inert filler is used.
In one embodiment, the present invention provides a negative electrode, which includes electrode active materials and a current collector. The negative electrode comprises either a metal selected from the group consisting of Li, Si, Sn, Sb, Al and a combination thereof, or a mixture of one or more negative electrode active materials in particulate form, a binder, preferably a polymeric binder, optionally an electron conductive additive, and at least one organic carbonate. Examples of useful negative electrode active materials include, but are not limited to, lithium metal, carbon (graphites, coke-type, mesocarbons, polyacenes, carbon nanotubes, carbon fibers, and the like). Negative electrode-active materials also include lithium-intercalated carbon, lithium metal nitrides such as Li26Co0.4N, metallic lithium alloys such as LiAl or Li4Sn, lithium-alloy-forming compounds of tin, silicon, antimony, or aluminum such as those disclosed in “Active/Inactive Nanocomposites as Anodes for Li-Ion Batteries,” by Mao et al. in Electrochemical and Solid State Letters, 2 (1), p. 3, 1999. Further included as negative electrode-active materials are metal oxides such as titanium oxides, iron oxides, or tin oxides. When present in particulate form, the particle size of the negative electrode active material should range from about 0.01 to 100 microns, preferably from 1 to 100 microns. Some preferred negative electrode active materials include graphites such as carbon microbeads, natural graphites, carbon nanotubes, carbon fibers, or graphitic flake-type materials. Some other preferred negative electrode active materials are graphite microbeads and hard carbon, which are commercially available.
A negative electrode can be formed by mixing and forming a composition comprising, by weight, 2-20%, preferably 3-10%, of a polymer binder, 10-50%, preferably 14-28%, of the electrolyte solution of the invention herein described, 40-80%, preferably 60-70%, of electrode-active material, and 0-5%, preferably 1-4%, of a conductive additive. Optionally up to 12% of an inert filler as hereinabove described may also be added, as may such other adjuvants as may be desired by one of skill in the art, which do not substantively affect the achievement of the desirable results of the present invention. It is preferred that no inert filler be used.
Suitable conductive additives for the positive and negative electrode composition include carbons such as coke, carbon black, carbon nanotubes, carbon fibers, and natural graphite, metallic flake or particles of copper, stainless steel, nickel or other relatively inert metals, conductive metal oxides such as titanium oxides or ruthenium oxides, or electronically-conductive polymers such as polyacetylene, polyphenylene and polyphenylenevinylene, polyaniline or polypyrrole. Preferred additives include carbon fibers, carbon nanotubes and carbon blacks with relatively surface area below ca. 100 m2/g such as Super P and Super S carbon blacks available from MMM Carbon in Belgium.
The current collector suitable for the positive and negative electrodes includes a metal foil and a carbon sheet selected from a graphite sheet, carbon fiber sheet, carbon foam and carbon nanotubes sheet or film. High conductivity is generally achieved in pure graphite and carbon nanotubes film so it is preferred that the graphite and nanotube sheeting contain as few binders, additives and impurities as possible in order to realize the benefits of the present invention. Carbon nanotubes can be present from 0.01% to about 99%. Carbon fiber can be in microns or submicrons. Carbon black or carbon nanotubes may be added to enhance the conductivities of the certain carbon fibers. In one embodiment, the negative electrode current collector is a metal foil, such as copper foil. The metal foil can have a thickness from about 5 to about 300 micrometers.
The carbon sheet current collector suitable for the present invention may be in the form of a powder coating on a substrate such as a metal substrate, a free-standing sheet, or a laminate. That is the current collector may be a composite structure having other members such as metal foils, adhesive layers and such other materials as may be considered desirable for a given application. However, in any event, according to the present invention, it is the carbon sheet layer, or carbon sheet layer in combination with an adhesion promoter, which is directly interfaced with the electrolyte of the present invention and is in electronically conductive contact with the electrode surface.
The flexible carbon sheeting preferred for the practice of the present invention is characterized by a thickness of at most 2000 micrometers, with less than 1000 micrometers preferred, less than 300 micrometers more preferred, less than 75 micrometers even more preferred, and less than 25 micrometers most preferred. The flexible carbon sheeting preferred for the practice of the invention is further characterized by an electrical conductivity along the length and width of the sheeting of at least 1000 Siemens/cm (S/cm), preferably at least 2000 S/cm, most preferably at least 3000 S/cm measured according to ASTM standard C611-98.
The flexible carbon sheeting preferred for the practice of the present invention may be compounded with other ingredients as may be required for a particular application, but carbon sheet having a purity of ca. 95% or greater is highly preferred. At a thickness below about 10 um, it may be expected that electrical resistance could be unduly high, so that thickness of less than about 10 μm is less preferred.
In some embodiments, the carbon current collector is a flexible free-standing graphite sheet. The flexible free-standing graphite sheet cathode current collector is made from expanded graphite particles without the use of any binding material. The flexible graphite sheet can be made from natural graphite, Kish flake graphite, or synthetic graphite that has been voluminously expanded so as to have d002 dimension at least 80 times and preferably 200 times the original d002 dimension. Expanded graphite particles have excellent mechanical interlocking or cohesion properties that can be compressed to form an integrated flexible sheet without any binder. Natural graphites are generally found or obtained in the form of small soft flakes or powder. Kish graphite is the excess carbon which crystallizes out in the course of smelting iron.
In one embodiment, the current collector is a flexible free-standing expanded graphite. In another embodiment, the current collector is a flexible free-standing expanded natural graphite.
A binder is optional, however, it is preferred in the art to employ a binder, particularly a polymeric binder, and it is preferred in the practice of the present invention as well. One of skill in the art will appreciate that many of the polymeric materials recited below as suitable for use as binders will also be useful for forming ion-permeable separator membranes suitable for use in the lithium or lithium-ion battery of the invention.
Suitable binders include, but are not limited to, polymeric binders, particularly gelled polymer electrolytes comprising polyacrylonitrile, poly(methylmethacrylate), poly(vinyl chloride), and polyvinylidene fluoride and copolymers thereof. Also, included are solid polymer electrolytes such as polyether-salt based electrolytes including poly(ethylene oxide)(PEO) and its derivatives, poly(propylene oxide) (PPO) and its derivatives, and poly(organophosphazenes) with ethyleneoxy or other side groups. Other suitable binders include fluorinated ionomers comprising partially or fully fluorinated polymer backbones, and having pendant groups comprising fluorinated sulfonate, imide, or methide lithium salts. Preferred binders include polyvinylidene fluoride and copolymers thereof with hexafluoropropylene, tetrafluoroethylene, fluorovinyl ethers, such as perfluoromethyl, perfluoroethyl, or perfluoropropyl vinyl ethers; and ionomers comprising monomer units of polyvinylidene fluoride and monomer units comprising pendant groups comprising fluorinated carboxylate, sulfonate, imide, or methide lithium salts.
Gelled polymer electrolytes are formed by combining the polymeric binder with a compatible suitable aprotic polar solvent and, where applicable, the electrolyte salt. PEO and PPO-based polymeric binders can be used without solvents. Without solvents, they become solid polymer electrolytes, which may offer advantages in safety and cycle life under some circumstances. Other suitable binders include so-called “salt-in-polymer” compositions comprising polymers having greater than 50% by weight of one or more salts. See, for example, M. Forsyth et al, Solid State Ionics, 113, pp 161-163 (1998).
Also included as binders are glassy solid polymer electrolytes, which are similar to the “salt-in-polymer” compositions except that the polymer is present in use at a temperature below its glass transition temperature and the salt concentrations are ca. 30% by weight. In one embodiment, the volume fraction of the preferred binder in the finished electrode is between 4 and 40%.
The electrochemical cell optionally contains an ion conductive layer or a separator. The ion conductive layer suitable for the lithium or lithium-ion battery of the present invention is any ion-permeable shaped article, preferably in the form of a thin film, membrane or sheet. Such ion conductive layer may be an ion conductive membrane or a microporous film such as a microporous polypropylene, polyethylene, polytetrafluoroethylene and layered structures thereof. Suitable ion conductive layer also include swellable polymers such as polyvinylidene fluoride and copolymers thereof. Other suitable ion conductive layer include those known in the art of gelled polymer electrolytes such as poly(methyl methacrylate) and poly(vinyl chloride). Also suitable are polyethers such as poly(ethylene oxide) and poly(propylene oxide). Preferable are microporous polyolefin separators, separators comprising copolymers of vinylidene fluoride with hexafluoropropylene, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, or perfluoropropyl vinyl ether, including combinations thereof, or fluorinated ionomers, such as those described in Doyle et al., U.S. Pat. No. 6,025,092.
In another aspect, the present invention provides a battery pack. The battery pack includes a plurality of lithium-ion electrochemical cells. Each cell comprises an ionic liquid of formula (I):
Q+E− (I)
wherein Q+ is a cation selected from the group consisting of dialkylammonium, trialkylammonium, tetraalkylammonium, dialkylphosphonium, trialkylphosphonium, tetraalkylphosphonium, trialkylsulfonium, (Rf)4N+ and an N-alkyl or N-hydrogen cation of a 5- or 6-membered heterocycloalkyl or heteroaryl ring having from 1-3 heteroatoms as ring members selected from N, O or S, wherein the heterocycloalkyl or heteroaryl ring is optionally substituted with from 1-5 optionally substituted alkyls and Rf is alkyl or alkoxyalkyl; E− is an anion selected from the group consisting of R1—X−R2(R3)m, NC—S−, BF4−, PF6−, RaSO3−, RaP−F3, RaCO2−, I−, ClO4−, (FSO2)2N—, AsF6−, SO4− and bis[oxalate(2-)-O,O′]borate, wherein m is 0 or 1. X is N when m is 0. X is C when m is 1. R1, R2 and R3 are each independently an electron-withdrawing group selected from the group consisting of halogen, —CN, —SO2Rb, —SO2-La-SO2N−Li+SO2Rb, —P(O)(ORb)2, —P(O)(Rb)2, —CO2Rb, —C(O)Rb and —H, with the proviso that R1 and R2 are other than hydrogen when m=0, and no more than one of R1, R2 and R3 is hydrogen when m 1. Each Ra is independently C1-8perfluoroalkyl. Each Rb is independently selected from the group consisting of C1-8alkyl, C1-8haloalkyl, C1-8perfluoroalkyl, perfluorophenyl, aryl, optionally substituted barbituric acid and optionally substituted thiobarbituric acid, and wherein at least one carbon-carbon bond of the alkyl or perfluoroalkyl are optionally substituted with a member selected from —O— or —S— to form an ether or a thioether linkage and the aryl is optionally substituted with from 1-5 members selected from the group consisting of halogen, C1-4haloalkyl, C1-4perfluoroalkyl, —CN, —SO2Rc, —P(O)(ORc)2, —P(O)(Rc)2, —CO2Rc and —C(O)Rc, wherein Rc is independently C1-8 alkyl, C1-8 perfluoroalkyl or perfluorophenyl and La is C1-4perfluoroalkyl.
In some embodiments, the present invention provides a method of connecting a tab to an electrode in an electrochemical cell. The method includes (a) providing an electrode comprising an electrode active material and a carbon current collector in electronically conductive contact with the electrode; (b) providing a tab having a first attachment end for attaching to the electrode; and (c) connecting the first attachment end of the tab to the carbon current collector through a process selected from the group consisting of riveting, conductive adhesive lamination, staking, hot press, ultrasonic press, mechanical press, crimping, pinching, and a combination thereof. In one embodiment, the electrochemical cell is a lithium-ion electrochemical cell.
In one embodiment, the method includes aligning the carbon current collector with the tab and applying riveting, staking, conductive adhesive lamination, hot press, ultrasonic press, mechanical press, crimping, pinching, and a combination thereof to the carbon current collector. The tab can have various shapes, such as a U-shape, a V-shape, a L-shape, a rectangular-shape or a inverted T-shape. In one instance, the carbon current collector and the tab can be aligned to any desirable position for attachment. The carbon current collector can be aligned to any suitable part of the tab. For example, the carbon current collector is aligned to the middle, the side or a predetermined position of the tab. The tab and the current collector are joined together through riveting or staking.
In another embodiment, the tab is connected to the carbon current collector through a conductive adhesive layer. In certain instances, the conductive layer is deposited on the tab. In one instance, the conductive layer is an adhesive layer comprising a conductive filler and a binder. The conductive filler is selected from the group consisting of carbon black, conducting polymers, carbon nanotubes and carbon composite materials. The conductive layer can have a thickness from about 1 nm to about 1000 micrometers. For example, the conductive layer has a thickness of about 1, 10, 20, 30, 40, 50, 60, 70, 80, 90 100, 200, 300, 400, 500, 600, 700, 800, 900 or 1000 nm. The conductive layer can also have a thickness of about 1, 10, 20, 30, 40, 50, 60, 70, 80, 90 100, 200, 300, 400, 500, 600, 700, 800, 900 or 1000 um.
In another aspect, the present invention provides a battery. The battery includes a housing, a positive connector, a negative connector, a electrochemical cell disposed in the housing, where the positive and the negative connector are mounted on the housing. In one embodiment, the housing is a sealed container. In yet another embodiment, the tab is connected to the carbon current collector through a conductive adhesive layer then riveted, hot pressed, ultrasonic pressed, mechanical pressed, staked, crimped, or pinched.
In one embodiment, both the positive connector and the negative connectors have an inner end disposed within the housing and an outer end protrudes outside the housing. The positive electrode tab is welded to the inner end of the positive connector and the negative electrode tab is welded to the inner end of the negative connector to provide a battery having a positive outer end and a negative outer end for connecting to external devices. For example, the battery can have multiple tabs welded to the positive connector or the negative connector. The battery can be prepared by first attaching the tabs to the electrodes of the lithium-ion electrochemical cell. The electrodes and separator layers are then jelly-wound or stacked and placed in a battery container. The tabs for the positive electrode are welded to the inner end of the positive connector of the housing, and the tabs for the negative electrode are welded to the inner end of the negative connector of the housing. The housing is sealed and no tabs are exposed. In one embodiment, the housing is a container.
In another embodiment, the second attachment ends of the tabs of the battery are protruded outside the housing for connecting to an external device. For example, the battery can be prepared by first attaching the tabs to the electrodes of a lithium-ion electrochemical cell. The electrodes and separator are then jelly-wound or stacked and placed in a housing then sealed with only the tabs are protruded outside the housing. In one embodiment, the housing is a container.
In another embodiment, the carbon current collector for the positive electrode and/or the carbon current collector for the negative electrode protrude outside the housing. In one instance, the housing is a foil-polymer laminate package. The pores in the carbon current collector are closed or sealed by a resin or other material to provide as close to a hermetic seal as possible when the carbon current collector(s) are heat-sealed between two layers of the foil-laminate. The resins can be conductive or non-conductive resins.
The benefit of this design is that the metal tabs can be attached to the carbon current collectors outside of the cell and are not in contact with the corrosive electrolyte solution. This allows the use of a plurality of metals, metal alloys or composites.
The Li-ion electrochemical cell can be assembled according to any method known in the art (see, U.S. Pat. Nos. 5,246,796; 5,837,015; 5,688,293; 5,456,000; 5,540,741; and 6,287,722 as incorporated herein by reference). In a first method, electrodes are solvent-cast onto current collectors, the collector/electrode tapes are spirally wound along with microporous polyolefin separator films to make a cylindrical roll, the winding placed into a metallic cell case, and the nonaqueous electrolyte solution impregnated into the wound cell. In a second method electrodes are solvent-cast onto current collectors and dried, the electrolyte and a polymeric gelling agent are coated onto the separators and/or the electrodes, the separators are laminated to, or brought in contact with, the collector/electrode tapes to make a cell subassembly, the cell subassemblies are then cut and stacked, or folded, or wound, then placed into a foil-laminate package, and finally heat treated to gel the electrolyte. In a third method, electrodes and separators are solvent cast with also the addition of a plasticizer; the electrodes, mesh current collectors, electrodes and separators are laminated together to make a cell subassembly, the plasticizer is extracted using a volatile solvent, the subassembly is dried, then by contacting the subassembly with electrolyte the void space left by extraction of the plasticizer is filled with electrolyte to yield an activated cell, the subassembly(s) are optionally stacked, folded, or wound, and finally the cell is packaged in a foil laminate package. In a fourth method, the electrode and separator materials are dried first, then combined with the salt and electrolyte solvent to make active compositions; by melt processing the electrodes and separator compositions are formed into films, the films are laminated to produce a cell subassembly, the subassembly(s) are stacked, folded, or wound and then packaged in a foil-laminate container.
In one embodiment, the electrodes can conveniently be made by dissolution of all polymeric components into a common solvent and mixing together with the carbon black particles and electrode active particles. For example, a lithium battery electrode can be fabricated by dissolving polyvinylidene (PVDF) in 1-methyl-2-pyrrolidinone or poly(PVDF-co-hexafluoropropylene (HFP)) copolymer in acetone solvent, followed by addition of particles of electrode active material and carbon black or carbon nanotubes, followed by deposition of a film on a substrate and drying. The resultant electrode will comprise electrode active material, conductive carbon black or carbon nanotubes, and polymer. This electrode can then be cast from solution onto a suitable support such as a glass plate or a current collector, and formed into a film using techniques well known in the art.
The positive electrode is brought into electronically conductive contact with the graphite current collector with as little contact resistance as possible. This may be advantageously accomplished by depositing upon the graphite sheet a thin layer of an adhesion promoter such as a mixture of an acrylic acid-ethylene copolymer and carbon black. Suitable contact may be achieved by the application of heat and/or pressure to provide intimate contact between the current collector and the electrode.
The flexible carbon sheeting, such as carbon nanotubes or graphite sheet for the practice of the present invention provides particular advantages in achieving low contact resistance. By virtue of its high ductility, conformability, and toughness it can be made to form particularly intimate and therefore low resistance contacts with electrode structures that may intentionally or unintentionally proffer an uneven contact surface. In any event, in the practice of the present invention, the contact resistance between the positive electrode and the graphite current collector of the present invention preferably does not exceed 50 ohm-cm2, in one instance, does not exceed 10 ohms-cm2, and in another instance, does not exceed 2 ohms-cm2. Contact resistance can be determined by any convenient method as known to one of ordinary skill in the art. Simple measurement with an ohm-meter is possible.
The negative electrode is brought into electronically conductive contact with an negative electrode current collector. The negative electrode current collector can be a metal foil, a mesh or a carbon sheet. In one embodiment, the current collector is a copper foil or mesh. In a preferred embodiment, the negative electrode current collector is a carbon sheet selected from a graphite sheet, carbon fiber sheet or a carbon nanotube sheet. As in the case of the positive electrode, an adhesion promoter can optionally be used to attach the negative electrode to the current collector.
In one embodiment, the electrode films thus produced are then combined by lamination with the current collectors and separator. In order to ensure that the components so laminated or otherwise combined are in excellent ionically conductive contact with one another, the components are combined with an electrolyte solution comprising an ionic liquid of formula (I) and a lithium imide or methide salt represented by the formula (II). In one embodiment, the electrolyte solution comprises a pure ionic liquid of formula (I). In another embodiment, the electrolyte solution comprises an ionic liquid of formula (I) and an organic carbonate or lactone as hereinabove described.
Ninety-two parts by weight of carbon mesosphere as the anode electrode active material, 1 part Super P Li as the conductive material, 107 parts by weight of a solution of 7 parts Kynar 301F, 0.4 parts oxalic acid and 99.6 parts N-methyl-2-pyrrolidinone were stirred and mixed together giving an anode electrode composition. This anode electrode composition was applied onto copper foil using a vacuum table and a doctor blade, then initially dried on a hotplate and followed by drying in an oven at 110° C. under vacuum for 2 hours and roll-pressed to an electrode with a thickness of about 1 micron to about 100 microns, thereby forming a negative electrode. Preferably, the thickness is about 49 microns.
Ninety-two parts by weight of lithium nickel manganese cobalt oxide as the cathode electrode active material, 4 part Super P Li as the conductive material, 104 parts by weight of a solution of 7 parts Kynar 301F and 100 parts N-methyl-2-pyrrolidinone were stirred and mixed together giving a cathode electrode composition. This cathode electrode composition was applied onto 50 micron graphite sheet using a vacuum table and a doctor blade, then initially dried on a hotplate and followed by drying in an oven at 110° C. under vacuum for 2 hours and roll-pressed to an electrode with thickness of about 1 micron to about 100 microns microns, thereby forming a positive electrode. Preferably, the thickness is about 41 microns
An electrolyte solution was prepared by dissolving 28.69 g of lithium bis(trifluoromethane)imide in a solution of 50 parts by weight of ethylene carbonate and 50 parts 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethane)imide that is sufficient to prepare a total of 100 ml of electrolyte solution.
The positive and negative electrodes obtained as described above were cut in circular shape with a diameter of 1.2 cm. Hoshen 2032 coin cells were used to test the electrodes as a cell. The coin cell bottom, a spacer disk, the positive electrode saturated with electrolyte solution, a porous Celgard separator saturated with electrolyte solution, the negative electrode saturated with electrolyte solution, a spacer disk, a wave spring and the coin cell top with gasket were assembled in the order listed and crimped with a manual crimper to give a lithium-ion electrochemical cell.
The lithium-ion electrochemical cell produced as described in Example 4 was subjected to charge/discharge test with charging including constant current of C/5 to 4.2 V and then constant voltage at 4.2 V for 3 hrs or until current drops below C/100 and discharging including constant current of C/5 to 3.0 V. The first cycle discharge capacity was 4.3 mAh and the first cycle charge-discharge efficiency was 71%. The capacity versus cycle number is plotted in
The cell was fabricated as in Example 4 except a lithium metal disk was used in place of the positive electrode.
The electrochemical cell of Example 6 was subjected to charge/discharge test with charging including constant current of C/5 to 0.02 V and then constant voltage at 0.02 V for 3 hrs or until current drops below C/100 and discharging including constant current of C/5 to 1.5 V. The first cycle discharge capacity was 275 mAh/g and the first cycle charge-discharge efficiency was 89%. The capacity versus cycle number is plotted in
The cell was fabricated as in Example 4 except a lithium metal disk was used in place of the negative electrode.
The electrochemical cell produced in Example 8 was subjected to charge/discharge test with charging including constant current of C/5 to 4.3 V and then constant voltage at 4.3 V for 3 hrs or until current drops below C/100 and discharging including constant current of C/5 to 3.0 V. The first cycle discharge capacity was 149 mAh/g and the first cycle charge-discharge efficiency was 79%. The capacity versus cycle number is plotted in
Ninety-two parts by weight of carbon mesosphere as the anode electrode active material, 1 part Super P Li as the conductive material, 107 parts by weight of a solution of 7 parts Kynar 301F, 0.4 parts oxalic acid and 99.6 parts N-methyl-2-pyrrolidinone were stirred and mixed together giving an anode electrode composition. This anode electrode composition was applied onto copper foil using a vacuum table and a doctor blade, then initially dried on a hotplate and followed by drying in an oven at 110° C. under vacuum for 2 hours and roll-pressed to an electrode with a thickness of about 1 micron to about 100 microns, thereby forming a negative electrode. Preferably, the thickness is about 49 microns.
Ninety-two parts by weight of lithium nickel manganese oxide (LiNi0.5Mn1.5O4) as the cathode electrode active material, 4 part Super P Li as the conductive material, 104 parts by weight of a solution of 7 parts Kynar 301F and 100 parts N-methyl-2-pyrrolidinone is stirred and mixed together giving a cathode electrode composition. This cathode electrode composition is applied onto 50 micron graphite sheet using a vacuum table and a doctor blade, then initially dried on a hotplate and followed by drying in an oven at 110° C. under vacuum for 2 hours and roll-pressed to an electrode with thickness of about 1 micron to about 100 microns microns, thereby forming a positive electrode. Preferably, the thickness is about 41 micron.
An electrolyte solution is prepared by dissolving 28.69 g of lithium bis(trifluoromethane)imide in a solution of 50 parts by weight of ethylene carbonate and 50 parts 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethane)imide that is sufficient to prepare a total of 100 ml of electrolyte solution.
The positive and negative electrodes obtained as described above are cut in circular shape with a diameter of 1.2 cm. Hoshen 2032 coin cells are used to test the electrodes as a cell. The coin cell bottom, a spacer disk, the positive electrode saturated with electrolyte solution, a porous Celgard separator saturated with electrolyte solution, the negative electrode saturated with electrolyte solution, a spacer disk, a wave spring and the coin cell top with gasket is assembled in the order listed and crimped with a manual crimper to give a lithium-ion electrochemical cell.
The lithium-ion electrochemical cell produced as described in Example 4 are subjected to charge/discharge test with charging including constant current of C/5 to 5.0 V and then constant voltage at 5.0 V for 3 hrs or until current drops below C/100 and discharging including constant current of C/5 to 3.7 V. The voltage versus test time for the first cycle is plotted in
While the invention has been described by way of example and in terms of the specific embodiments, it is to be understood that examples and embodiments described herein are for illustrative purposes only and the invention is not limited to the disclosed embodiments. It is intended to cover various modifications and similar arrangements as would be apparent to those skilled in the art. Therefore, the scope of the appended claims should be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements. All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety for all purposes.
This application claims priority to and is a continuation of U.S. Nonprovisional patent application Ser. No. 12/953,335, filed Nov. 23, 2010, which is a continuation of International Patent Application No. PCT/US2009/045723, filed May 29, 2009, which claims the benefit of priority of U.S. Provisional Patent Application No. 61/057,179 filed May 29, 2008. This application expressly incorporates by reference the above International and U.S. Provisional Application in their entirety for all purposes.
| Number | Date | Country | |
|---|---|---|---|
| 61057179 | May 2008 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12953335 | Nov 2010 | US |
| Child | 13893203 | US | |
| Parent | PCT/US2009/045723 | May 2009 | US |
| Child | 12953335 | US |
