Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/56—Ring systems containing three or more rings
  • C07D209/80—[b, c]- or [b, d]-condensed
  • C07D209/82—Carbazoles; Hydrogenated carbazoles
  • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/56—Ring systems containing three or more rings
  • C07D209/80—[b, c]- or [b, d]-condensed
  • C07D209/82—Carbazoles; Hydrogenated carbazoles
  • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
  • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
  • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
  • C07D241/46—Phenazines
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
  • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
  • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
  • C07D279/18—[b, e]-condensed with two six-membered rings
  • C07D279/20—[b, e]-condensed with two six-membered rings with hydrogen atoms directly attached to the ring nitrogen atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
  • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
  • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
  • C07D279/18—[b, e]-condensed with two six-membered rings
  • C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
  • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
  • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
  • C07D279/18—[b, e]-condensed with two six-membered rings
  • C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
  • C07D279/24—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom with hydrocarbon radicals, substituted by amino radicals, attached to the ring nitrogen atom
  • C07D279/26—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom with hydrocarbon radicals, substituted by amino radicals, attached to the ring nitrogen atom without other substituents attached to the ring system
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators 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
  • H01M10/0566—Liquid materials
  • H01M10/0567—Liquid materials characterised by the additives
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators 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
  • H01M10/0566—Liquid materials
  • H01M10/0569—Liquid materials characterised by the solvents
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the disclosure generally relates to a rechargeable lithium-ion cell. More specifically, this disclosure relates to a lithium-ion cell that includes a particular redox shuttle.
• Rechargeable lithium-ion cells can exhibit excellent charge-discharge cycle life, little or no memory effect, and high specific and volumetric energy. However, lithium-ion cells typically exhibit an inability to tolerate recharging to potentials above the manufacturer's recommended end of charge potential without degradation in cycle life. Recharging to potentials above the manufacturer's recommended end of charge potential is typically described as overcharge. Overcharge generally occurs when a current is forced through the cells and the charge delivered exceeds the charge-storing capability of the cell. Overcharge of lithium-ion cells can lead to the chemical and electrochemical degradation of cell components, rapid temperature elevation, and can also trigger self-accelerating reactions in the cells.
• Redox shuttles are chemical compounds that are incorporated into lithium-ion cells for overcharge protection.
• the redox shuttle can be reversibly electrochemically oxidized at a potential slightly higher than the working potential of a positive electrode of the lithium-ion cell.
• Use of the redox shuttles allows lithium-ion cells to normally operate in a voltage range less than the redox potential of the redox shuttle.
• the voltage will increase to the redox potential of the redox shuttle first and activate a redox mechanism, which will proceed as the only active component to transfer the excessive charge through the lithium-ion cells while minimizing damage. Use of such a mechanism inhibits overcharging.
• the rechargeable lithium-ion cell having a cell capacity and including a positive electrode having a recharged potential and a negative electrode.
• the rechargeable lithium-ion cell also includes a charge-carrying electrolyte.
• the charge-carrying electrolyte includes a charge-carrying medium and a lithium salt.
• the rechargeable lithium-ion cell also includes a redox shuttle having the following structure:
• X is a covalent bond (such that the center ring is a five membered ring), a sulfur atom (S), or a nitrogen atom bonded to R 6 (N—R 6 ).
• each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is independently an alkyl group, a haloalkyl group (e.g.
• a perhaloalkyl group an acyl group, an acyloxy group, an acetyl group, a haloacetyl group, an alkaryl group, an alkoxy group, an acetamido group, an amido group, an aryl group, an aralkyl group, an alkyl carboxyl group, an aryl carboxyl group, an alkylsulfonyl group, a benzoyl group, a carbamoyl group, a carboxy group, a cyano group, a formyl group, a halo group, a haloacetamido group, a haloacyl group, a haloalkylsulfonyl group, a haloaryl group, a methylsulfonyloxyl group, a nitro group, an oxo group, an alkyl ether group, a trialkylam
• the cell can be alternatively described as a battery, i.e., a rechargeable lithium-ion cell battery.
• the cell has a cell capacity, which is known in the art as an amount of electric charge the cell can deliver at a rated voltage.
• Cell capacity is typically measured in units such as amp-hour (A ⁇ h).
• a ⁇ h amp-hour
• the capacity of the cell is often expressed as a product of 20 hours multiplied by the current that a new battery can consistently supply for 20 hours at 68° F. (20° C.), while remaining above a specified terminal voltage per cell.
• the capacity of the instant cell is not particularly limited and may be chosen by one of skill in the art.
• the cell may be sealed in a suitable case, e.g. in mating cylindrical metal shells such as in a coin-type cell, in an elongated cylindrical AAA, AA, C or D cell casing or in a replaceable battery pack.
• the cell may be sealed in a Li-ion format such as in an 18650 format, in a pouch cell, etc.
• the cell may be used in a variety of devices, including portable computers, tablet displays, personal digital assistants, mobile telephones, motorized devices (e.g. personal or household appliances and vehicles), instruments, illumination devices (e.g. flashlights) and heating devices.
• the cell may have particular utility in low-cost mass market electrical and electronic devices such as flashlights, radios, CD players and the like, which heretofore have usually been powered by non-rechargeable batteries such as alkaline cells.
• the cell includes a positive electrode having a recharged potential.
• the cell may have a single positive electrode or more than one positive electrode.
• the terminology “positive electrode” may describe one of a pair of electrodes that, under typical circumstances, and when the cell is fully charged, will have the highest potential that it can achieve under normal operation. This terminology also typically describes the same physical electrode under all cell operating conditions even if the electrode temporarily (e.g. due to cell overdischarge) is driven to or exhibits a potential less than that of another (e.g. negative) electrode.
• the positive electrode is not particularly limited and may be any known in the art.
• the positive electrode may be or include the following (with approximate recharged potentials) FeS 2 (3.0 V vs. Li/Li + ), LiCoPO 4 (4.8 V vs. Li/Li + ), LiFePO 4 (3.6 V vs. Li/Li + ), Li 2 FeS 2 (3.0 V vs. Li/Li + ), Li 2 FeSiO 4 (2.9 V vs. Li/Li + ), LiMn 2 O 4 (4.1 V vs. Li/Li + ), LiMnPO 4 (4.1 V vs. Li/Li+), LiNiPO 4 (5.1 V vs.
• Li/Li + TiS 3 (2.5 V vs. Li/Li + ), V 2 O 5 (3.6 V vs. Li/Li + ), V 6 O 13 (3.0 V vs. Li/Li + ), LiCoO 2 (4.2 V vs. Li/Li + ), LiNiMnCoO 2 (4.2 V vs. Li/Li + ), LiNiCoAlO 2 (4.3 V vs. Li/Li + ), and combinations thereof.
• the positive electrode includes LiFePO 4 , Li 2 FeSiO 4 , MnO 2 , Li x MnO 2 , LiNiMnCoO 2 , and/or LiNiCoAlO 2 , wherein x is 0.3 to 0.4.
• Some positive electrode materials may, depending upon their structure or composition, be charged at a number of voltages, and thus may be used as a positive electrode if an appropriate form and appropriate cell operating conditions are chosen.
• Electrodes that are or include LiFePO 4 , Li 2 FeSiO 4 , Li x MnO 2 (wherein x is about 0.3 to about 0.4, and made for example by heating a stoichiometric mixture of electrolytic manganese dioxide and LiOH to about 300 to about 400° C.) or MnO 2 (made for example by heat treatment of electrolytic manganese dioxide to about 350° C.) can provide cells having especially desirable performance characteristics when used with the redox shuttle having oxidation potentials of about 3.5, 4, 4.5, or 5, V.
• the positive electrode may include additives, e.g. carbon black, flake graphite and the like.
• the positive electrode may be in any convenient form including foils, plates, rods, pastes or as a composite made by forming a coating of the positive electrode material on a conductive current collector or other suitable support.
• the positive electrode is or includes LiFePO 4 , Li 2 FeSiO 4 , MnO 2 , or Li x MnO 2 wherein x is 0.3 to 0.4.
• the positive electrode is or includes Li[B(C 2 O 4 ) 2 ], Li[BF 2 (C 2 O 4 )], Li[PF 2 (C 2 O 4 ) 2 ], LiClO 4 , LiBF 4 , LiAsF 6 , LiPF 6 , Li[CF 3 SO 3 ], Li[N(CF 3 SO 2 ) 2 ], Li[C(CF 3 SO 2 ) 3 ], Li[N(SO 2 C 2 F 5 ) 2 ], lithium alkyl fluorophosphates, or combinations thereof.
• the positive electrode is chosen from LiFePO 4 , LiCoO 2 , LiMN 2 O 4 , LiNiMnCoO 2 and LiNiCoAlO 2 , and combinations thereof.
• charged potential typically describes a value E cp measured relative to Li/Li + by constructing a cell including the positive electrode, a negative electrode, a charge-carrying electrolyte, and no substituted phenothiazine, substituted carbazole, substituted phenazine, or other redox shuttle, carrying out a charge/discharge cycling test and observing the potential at which the positive electrode becomes delithiated during the first charge cycle to a lithium level corresponding to at least 90% of the available recharged cell capacity.
• this lithium level may correspond to approximately complete delithiation (e.g. to Li 0 FePO 4 ).
• this lithium level may correspond to partial delithiation.
• the cell includes a negative electrode.
• the cell may have a single negative electrode or more than one negative electrode.
• the terminology “negative electrode” may describe one of a pair of electrodes that, under normal circumstances and when the cell is fully charged, have the lowest potential. This terminology also typically describes 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 (e.g. positive) electrode.
• the negative electrode is not particularly limited and may be any known in the art.
• Non-limiting examples of negative electrodes include graphitic carbons e.g. those having a spacing between (002) crystallographic planes, d 002 of 3.45 Angstroms>d 002 >3.354 Angstroms and existing in forms such as powders, flakes, fibers or spheres (e.g. mesocarbon microbeads); lithium metal; Li 4/3 Ti 5/3 O 4 ; Sn—Co-based amorphous negative electrodes, and combinations thereof.
• a negative electrode including extractible lithium e.g. a lithium metal electrode, extractible lithium alloy electrode, or electrode including powdered lithium
• the negative electrode may include additives, e.g. carbon black.
• the negative electrode may be in any convenient form including foils, plates, rods, pastes or as a composite made by forming a coating of the negative electrode material on a conductive current collector or other suitable support.
• the negative electrode includes graphitic carbon, lithium metal or a lithium alloy or a combination thereof.
• the rechargeable lithium-ion cell also includes a charge-carrying electrolyte.
• the charge-carrying electrolyte includes a charge-carrying medium and a lithium salt.
• the charge-carrying electrolyte is not particularly limited and may be any known in the art. Typically, the charge-carrying electrolyte provides a charge-carrying pathway between the positive and negative electrodes, and initially includes at least the charge-carrying medium and the lithium salt.
• the charge-carrying electrolyte may include other additives typically utilized in the art.
• the charge-carrying electrolyte may be in any convenient form including liquids and gels.
• the charge-carrying electrolyte may include the redox shuttle (as described in detail below) that may or may not be dissolved therein.
• the charge-carrying electrolyte may be formulated without the redox shuttle and incorporated into a cell whose positive or negative electrode includes a dissolvable redox shuttle that can dissolve into the charge-carrying electrolyte after cell assembly or during the first charge-discharge cycle, so that the charge-carrying electrolyte will include a redox shuttle once the cell has been put into use.
• the charge-carrying medium is also not particularly limited and may be any known in the art.
• suitable charge-carrying medium include liquids and gels capable of solubilizing sufficient quantities of lithium salt and the redox shuttle so that a suitable quantity of charge can be transported from the positive electrode to negative electrode.
• the charge-carrying medium can typically be used over a wide temperature range, e.g. from about ⁇ 30° C. to about 70° C. without freezing or boiling, and is typically stable in the electrochemical window within which the electrodes operate.
• Non-limiting examples of charge carrying mediums include, but are not limited to, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, butylene carbonate, vinylene carbonate, fluoroethylene carbonate, fluoropropylene carbonate, ⁇ -butyrolactone, methyl difluoroacetate, ethyl difluoroacetate, dimethoxyethane, diglyme (bis(2-methoxyethyl)ether), and combinations thereof.
• the charge-carrying medium includes ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, or combinations thereof.
• the charge-carrying medium is typically present in an amount of from 60% to 99% by weight, from 65% to 95% by weight, or from 70% to 90% by weight, each based on a total weight of the charge-carrying electrolyte.
• all values and ranges of values within those values described above are hereby expressly contemplated in various non-limiting embodiments.
• the lithium salt is also not particularly limited and may include any known in the art.
• suitable lithium salts are stable and soluble in the chosen charge-carrying medium and perform well in the chosen lithium-ion cell, and can include or be LiPF 6 , LiBF 4 , LiClO 4 , lithium bis(oxalato)borate (“LiBOB”), LiN (CF 3 SO 2 ) 2 , LiN(C 2 F 5 SO 2 ) 2 , LiAsF 6 , LiC(CF 3 SO 2 ) 3 and combinations thereof.
• the lithium salt is typically present in an amount of from 1 to 40, from 5 to 35, or from 10 to 30, parts by weight per 100 parts by weight of the charge-carrying electrolyte.
• All values and ranges of values within those values described above are hereby expressly contemplated in various non-limiting embodiments.
• the cell includes a redox shuttle.
• the terminology “redox shuttle” describes an electrochemically reversible moiety or compound that can become oxidized at the positive electrode, migrate to the negative electrode, become reduced at the negative electrode to reform the unoxidized (or less-oxidized) shuttle species, and migrate back to the positive electrode.
• the redox shuttle may be described as an electroactive compound, which may be heterocyclic, wherein the terminology “electroactive” is as understood by those of skill in the art.
• any one of more of the compounds described below, e.g. substituted phenothiazines, substituted phenazines, and/or substituted carbazoles may be described as a redox shuttle and/or a compound that protects against overcharging.
• a redox shuttle may have an oxidation potential above the recharged potential of the positive electrode and may serve as a cyclable redox chemical shuttle providing cell overcharge protection.
• the terminology “oxidation potential” typically refers to a value E 1/2 which may be measured by dissolving the redox shuttle in the chosen charge-carrying electrolyte, measuring current vs.
• E pa i.e., the potential at which the peak anodic current is observed
• E pc i.e., the potential at which the peak cathodic current is observed
• E 1/2 is typically taken as the average of E pa and E pc .
• Shuttle oxidation potentials may be estimated (to provide a value “E obs ”) by constructing a cell including the shuttle, carrying out a charge/discharge cycling test, and observing during a charging sequence the potential at which a voltage plateau indicative of shuttle oxidation and reduction occurs.
• the observed result may be corrected by the amount of the negative electrode potential vs. Li/Li + to provide an E obs value relative to Li/Li + .
• Shuttle oxidation potentials may be approximated (to provide a value “E calc ”) using modeling software such as GAUSSIAN 03 from Gaussian Inc. to predict oxidation potentials (e.g. for compounds whose E 1/2 is not known) by correlating model ionization potentials to the oxidation potentials and lithium-ion cell behavior of measured compounds.
• the redox shuttle may, for example, have an oxidation potential from 3.5 to 5, from 3.6 to 5, from 3.7 to 5, from 3.8 to 5, from 3.9 to 4.9, from 4 to 4.8, from 4.1 to 4.7, from 4.2 to 4.6, from 4.3 to 4.5, or from 4.4 to 4.5, V, above the recharged potential of the positive electrode.
• LiFePO 4 positive electrodes have a recharged potential of about 3.6 V vs. Li/Li +
• one embodiment of a redox shuttle has an oxidation potential of about (3.5-3.7) to about 4.2 V vs. Li/Li + .
• Li 2 FeSiO 4 positive electrodes have a recharged potential of around 2.8 V vs.
• Li/Li+ and another embodiment of a redox shuttle has an oxidation potential of about 3.5 V to about 4.0 V vs. Li/Li + .
• another embodiment of a redox shuttle has an oxidation potential of about 3.7 to about 4.4 V vs. Li/Li + .
• the redox shuttle has an oxidation potential from 3.5 to 5 V as compared to Li/Li + .
• the redox shuttle has an oxidation potential from 4 to 5 V as compared to Li/Li + .
• the redox shuttle has an oxidation potential from 3.5 to 4 V as compared to Li/Li + . In a further embodiment, the redox shuttle has an oxidation potential from 3.7 to 3.9 V as compared to Li/Li+, e.g. for LiFePO 4 cells. Alternatively, all values and ranges of values within those values described above are hereby expressly contemplated in various non-limiting embodiments.
• the redox shuttle may be disposed in a charge-carrying electrolyte and/or in another location in the cell.
• the oxidized redox shuttle carries a charge quantity corresponding to the applied charging current to the negative electrode, thus preventing or at least minimizing cell overcharge.
• the redox shuttle is cyclable to provide at least 10, at least 30, at least 100, or at least 500 cycles of overcharge protection at a charging voltage sufficient to oxidize the redox shuttle and at an overcharge charge flow equivalent to 100% of the cell capacity during each cycle.
• the aforementioned number of cycles is 500-1000, greater than 1,000, from 1,000 to 10,000, or even greater than 10,000.
• the redox shuttle is different from the positive electrode and typically has an oxidation potential different from and higher (e.g. more positive) than the recharged potential of the positive electrode.
• the potential of the redox shuttle may be slightly greater than the recharged potential of the positive electrode, less than the potential at which irreversible cell damage might occur, and less than the potential at which excessive cell heating or outgassing may occur.
• the substituted phenothiazine is utilized alone as a redox shuttle or in combination with other redox shuttles.
• other redox shuttles may be used to the complete exclusion of the substituted phenothiazine.
• various embodiments of the cell of this disclosure are entirely free of the substituted phenothiazine and include alternative redox shuttles instead.
• the redox shuttle typically has the following structure:
• X is a covalent bond (such that the center ring is a five membered ring), a sulfur atom (S), or a nitrogen atom bonded to R 6 (N—R 6 ). If X is a covalent bond, then the center ring is a five membered ring (such as in a carbazole) wherein the carbon atoms of the two benzyl rings (i.e., the carbon atoms are meta to R 1 and R 2 ) are singly bonded to each other.
• each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is independently an alkyl group, a haloalkyl group (e.g.
• a perhaloalkyl group an acyl group, an acyloxy group, an acetyl group, a haloacetyl group, an alkaryl group, an alkoxy group, an acetamido group, an amido group, an aryl group, an aralkyl group, an alkyl carboxyl group, an aryl carboxyl group, an alkylsulfonyl group, a benzoyl group, a carbamoyl group, a carboxy group, a cyano group, a formyl group, a halo group, a haloacetamido group, a haloacyl group, a haloalkylsulfonyl group, a haloaryl group, a methylsulfonyloxyl group, a nitro group, an oxo group, an alkyl ether group, a trialkylam
• any one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 for any structure herein may be as described in greater detail below.
• various non-limiting embodiments are hereby expressly contemplated wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are independently chosen as described in all sections below.
• each of R 1 and R 2 is independently an alkyl group, a haloalkyl group (including perhaloalkyl), or an alkyl ether group and at least one of R 3 and R 4 is an alkyl group, a haloalkyl group (including perhaloalkyl), an alkyl ether group, an acyl group, or a haloacyl group.
• R 3 and R 4 is an alkyl group, a haloalkyl group (including perhaloalkyl), an alkyl ether group, an acyl group, or a haloacyl group.
• each of R 1 , R 2 , R 3 , R 4 , and R 5 are chosen from alkyl groups, alkyl ether groups, acetyl groups, and CF 3 groups.
• Alternative redox shuttles include substituted carbazoles, substituted phenazines, and combinations thereof.
• the substituted phenothiazine typically has the following structure:
• each of R 1 , R 2 , R 3 , R 4 , and R 5 is independently an alkyl group, a haloalkyl group (e.g. mono-, di-, or tri-halo), a perhaloalkyl group, an acyl group, an acyloxy group, an acetyl group, a haloacetyl group, an alkaryl group, an alkoxy group, an acetamido group, an amido group, an aryl group, an aralkyl group, an alkyl carboxyl group, an aryl carboxyl group, an alkylsulfonyl group, a benzoyl group, a carbamoyl group, a carboxy group, a cyano group, a formyl group, a halo group, a haloacetamido group, a haloacyl group, a haloalkylsulfonyl group, a
• each of R 1 and R 2 is independently an alkyl group, a haloalkyl group (e.g. mono-, di-, or tri-halo), a perhaloalkyl group, an acyl group, an acyloxy group, an acetyl group, a haloacetyl group, an alkaryl group, an alkoxy group, an acetamido group, an amido group, an aryl group, an aralkyl group, an alkyl carboxyl group, an aryl carboxyl group, an alkylsulfonyl group, a benzoyl group, a carbamoyl group, a carboxy group, a cyano group, a formyl group, a halo group, a haloacetamido group, a haloacyl group, a haloalkylsulfonyl group, a haloaryl group, a methylsulf
• each of R 3 and R 4 is independently an alkyl group having 1-6 or 1-12 carbon atoms or a haloalkyl group (e.g. mono-, di-, or tri-halo) having 1 to 12 carbon atoms.
• one of R 3 and R 4 is a hydrogen atom.
• one of R 3 and R 4 is a hydrogen atom whereas the other of R 3 and R 4 is not a hydrogen atom.
• R 5 is an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms or 1-12 carbon atoms, a haloalkyl group (e.g.
• each of R 1 and R 2 is independently an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms or 1-12 carbon atoms, a trifluoromethyl group, a halo group, a cyano group, an alkyl ether group having 1 to 12 carbon atoms, an alkyl ether group having 1-12 carbon atoms, or a trialkylammoniumalkyl group having 1 to 12 carbon atoms.
• each of R 3 and R 4 are independently an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms or 1-12 carbon atoms, a haloalkyl group (e.g.
• Suitable alkyl groups are methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, sec-butyl, tert-butyl, neopentyl, n-pentyl, hexyl, octyl, and the like, as appreciated by those of skill in the art.
• all values and ranges of values within those values described above are hereby expressly contemplated in various non-limiting embodiments.
• each of R 3 and R 4 are sterically bulky.
• the terminology “sterically bulky” is appreciated by those of skill in the art.
• each of R 3 and R 4 may be a C 2 -C 4 alkyl group, such as an iso-propyl, butyl, iso-butyl, sec-butyl, tert-butyl group. These types of groups may shift a potential to a more positive value without sacrificing (or at least minimizing an effect on) stability of the compound.
• each of R 3 and R 4 may be a C 2 -C 5 alkyl group and may include those groups described above and neopentyl groups.
• each of R 3 and R 4 may be methyl and/or CF 3 groups.
• a methyl groups, haloalkyl groups (e.g. mono-, di-, or tri-halo), and perhaloalkyl groups are sufficiently sterically bulky to induce a positive shift of the oxidation potential.
• each of R 1 and R 2 is independently an alkyl group, a haloalkyl group (including perhaloalkyl), or an alkyl ether group and at least one of R 3 and R 4 is an alkyl group, a haloalkyl group (including perhaloalkyl), an alkyl ether group, an acyl group, or a haloacyl group.
• each of R 1 , R 2 , R 3 , R 4 , and R 5 are chosen from alkyl groups, alkyl ether groups, acetyl groups, and CF 3 groups. Without intending to be bound by any particular theory, it is believed that substitution at these positions surprisingly increases the oxidation potential through a steric effect.
• the redox shuttle e.g. the substituted phenothiazine
• the substituted phenothiazine may be included in the cell in any amount as determined by one of skill in the art.
• the substituted phenothiazine is present in an amount of from 0.05 to 10, from 1 to 10, from 2 to 9, from 3 to 8, from 4 to 7, or from 5 to 6, parts by weight per 100 parts by weight of the charge-carrying electrolyte.
• all values and ranges of values within those values described above are hereby expressly contemplated in various non-limiting embodiments.
• Amounts of the substituted phenothiazine, substituted carbazole, substituted phenazine (and/or any of the redox shuttles described herein) may be chosen based on solubility, diffusion coefficients, the need for overcharge protection, etc.
• the substituted phenazine typically has one of the following structures:
• phenazines have the lowest baseline oxidation potential
• phenothiazines have a mid-level oxidation potential
• carbazoles have the highest baseline oxidation potential.
• steric effects of ortho substitution at the 1,8 positions of the carbazole may be relatively modest.
• steric effects of ortho substitution at the 1, 4, 6, 9 positions of phenazine may be larger.
• each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 is independently an alkyl group, a haloalkyl group (e.g. mono-, di-, or tri-halo), a perhaloalkyl group, an acyl group, an acyloxy group, an acetyl group, a haloacetyl group, an alkaryl group, an alkoxy group, an acetamido group, an amido group, an aryl group, an aralkyl group, an alkyl carboxyl group, an aryl carboxyl group, an alkylsulfonyl group, a benzoyl group, a carbamoyl group, a carboxy group, a cyano group, a formyl group, a halo group, a haloacetamido group, a haloacyl group, a haloalky
• one of R 3 and R 4 and/or one of R 7 and R 8 is a hydrogen atom whereas the other of R 3 and R 4 and/or R 7 and R 8 is not a hydrogen atom.
• Each of R 9 and R 10 may independently be the same or different from any one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and/or R 8 described above. In other embodiments, any or all of R 1 , R 2 , R 9 , and R 10 can be H.
• one of R 3 and R 4 is a hydrogen atom.
• one of R 3 and R 4 is a hydrogen atom whereas the other of R 3 and R 4 is not a hydrogen atom.
• each of R 1 and R 2 is independently an alkyl group, a haloalkyl group (e.g. mono-, di-, or tri-halo), a perhaloalkyl group, an acyl group, an acyloxy group, an acetyl group, a haloacetyl group, an alkaryl group, an alkoxy group, an acetamido group, an amido group, an aryl group, an aralkyl group, an alkyl carboxyl group, an aryl carboxyl group, an alkylsulfonyl group, a benzoyl group, a carbamoyl group, a carboxy group, a cyano group, a formyl group, a halo group, a haloacetamido group, a haloacyl group, a haloalkylsulfonyl group, a haloaryl group, a methylsulf
• each of R 3 and R 4 is independently an alkyl group having 1 to 12 carbon atoms or a haloalkyl group (e.g. mono-, di-, or tri-halo) having 1 to 12 carbon atoms.
• one of R 3 and R 4 is a hydrogen atom.
• one of R 3 and R 4 is a hydrogen atom whereas the other of R 3 and R 4 is not a hydrogen atom.
• each of R 5 and R 6 is independently an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms or 1-12 carbon atoms, a haloalkyl group (e.g.
• each of R 7 and R 8 are the same or different than R 3 and R 4 , respectively.
• each of R 7 and R 8 can be any group described above relative to R 3 and/or R 4 .
• all values and ranges of values within those values described above are hereby expressly contemplated in various non-limiting embodiments.
• each of R 1 and R 2 is independently an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms or 1-12 carbon atoms, a trifluoromethyl group, a halo group, a cyano group, an alkyl ether group having 1 to 12 carbon atoms, or a trialkylammoniumalkyl group having 1 to 12 carbon atoms.
• each of R 3 and R 4 are independently an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms or 1-12 carbon atoms, a haloalkyl group (e.g.
• each of R 3 and R 4 are sterically bulky.
• the terminology “sterically bulky” is appreciated by those of skill in the art.
• each of R 3 and R 4 may be a C 2 -C 4 alkyl group, such as an iso-propyl, butyl, iso-butyl, sec-butyl, tert-butyl group. These types of groups may shift a potential to a more positive value without sacrificing (or at least minimizing an effect on) stability of the compound.
• each of R 3 and R 4 may be a C 2 -C 5 alkyl group and may include those groups described above and neopentyl groups.
• each of R 3 and R 4 may be methyl and/or CF 3 groups.
• one of R 3 and R 4 is a hydrogen atom.
• one of R 3 and R 4 is a hydrogen atom whereas the other of R 3 and R 4 is not a hydrogen atom.
• a methyl groups, haloalkyl groups (e.g. mono-, di-, or tri-halo) and perhaloalkyl groups are sufficiently sterically bulky to induce a positive shift of the oxidation potential.
• each of R 1 and R 2 is independently an alkyl group, a haloalkyl group (including perhaloalkyl), or an alkyl ether group and at least one of R 3 and R 4 is an alkyl group, a haloalkyl group (including perhaloalkyl), an alkyl ether group, an acyl group, or a haloacyl group.
• each of R′, R 2 , R 3 , R 4 , and R 5 are chosen from alkyl groups, alkyl ether groups, acetyl groups, and CF 3 groups. Without intending to be bound by any particular theory, it is believed that substitution at these positions surprisingly increases the oxidation potential through a steric effect.
• the redox shuttle e.g. the substituted phenazine
• the substituted phenazine may be included in the cell in any amount as determined by one of skill in the art.
• the substituted phenazine is present in an amount of from 0.05 to 10, from 1 to 10, from 2 to 9, from 3 to 8, from 4 to 7, or from 5 to 6, parts by weight per 100 parts by weight of the charge-carrying electrolyte.
• all values and ranges of values within those values described above are hereby expressly contemplated in various non-limiting embodiments.
• the substituted carbazole typically has the following structure:
• X is the covalent bond such that the center ring is a five membered ring, as shown immediately above.
• each of R 1 , R 2 , R 3 , R 4 , and R 5 is independently an alkyl group, a haloalkyl group (e.g.
• a perhaloalkyl group an acyl group, an acyloxy group, an acetyl group, a haloacetyl group, an alkaryl group, an alkoxy group, an acetamido group, an amido group, an aryl group, an aralkyl group, an alkyl carboxyl group, an aryl carboxyl group, an alkylsulfonyl group, a benzoyl group, a carbamoyl group, a carboxy group, a cyano group, a formyl group, a halo group, a haloacetamido group, a haloacyl group, a haloalkylsulfonyl group, a haloaryl group, a methylsulfonyloxyl group, a nitro group, an oxo group, an alkyl ether group, a trialkylam
• each of R 1 and R 2 is independently an alkyl group, a haloalkyl group (e.g. mono-, di-, or tri-halo), a perhaloalkyl group, an acyl group, an acyloxy group, an acetyl group, a haloacetyl group, an alkaryl group, an alkoxy group, an acetamido group, an amido group, an aryl group, an aralkyl group, an alkyl carboxyl group, an aryl carboxyl group, an alkylsulfonyl group, a benzoyl group, a carbamoyl group, a carboxy group, a cyano group, a formyl group, a halo group, a haloacetamido group, a haloacyl group, a haloalkylsulfonyl group, a haloaryl group, a methylsulf
• each of R 3 and R 4 is independently an alkyl group having 1 to 12 carbon atoms or a haloalkyl group (e.g. mono-, di-, or tri-halo) having 1 to 12 carbon atoms.
• one of R 3 and R 4 is a hydrogen atom.
• one of R 3 and R 4 is a hydrogen atom whereas the other of R 3 and R 4 is not a hydrogen atom.
• R 5 is an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms or 1-12 carbon atoms, a haloalkyl group (e.g.
• each of R 1 and R 2 is independently an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms or 1-12 carbon atoms, a trifluoromethyl group, a halo group, a cyano group, an alkyl ether group having 1-6 or 1-12 carbon atoms, or a trialkylammoniumalkyl group having 1-12 carbon atoms.
• each of R 3 and R 4 are independently an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms or 1-12 carbon atoms, a haloalkyl group (e.g.
• each of R 3 and R 4 are sterically bulky.
• the terminology “sterically bulky” is appreciated by those of skill in the art.
• each of R 3 and R 4 may be a C 2 -C 4 alkyl group, such as an iso-propyl, butyl, iso-butyl, sec-butyl, tert-butyl group. These types of groups may shift a potential to a more positive value without sacrificing (or at least minimizing an effect on) stability of the compound.
• the effect of bulky substituents is typically larger for phenothiazine than for carbazole.
• each of R 3 and R 4 may be a C 2 -C 5 alkyl group and may include those groups described above and neopentyl groups. The identity of the groups attached to the nitrogen of the carbazole may be chosen to increase or decrease solubility, by one of skill in the art.
• each of R 3 and R 4 may be methyl and/or CF 3 groups.
• one of R 3 and R 4 is a hydrogen atom. In one embodiment, one of R 3 and R 4 is a hydrogen atom whereas the other of R 3 and R 4 is not a hydrogen atom.
• methyl groups, haloalkyl groups (e.g. mono-, di-, or tri-halo), and perhaloalkyl groups are sufficiently sterically bulky to induce a positive shift of the oxidation potential.
• each of R 1 and R 2 is independently an alkyl group, a haloalkyl group (including perhaloalkyl), or an alkyl ether group and at least one of R 3 and R 4 is an alkyl group, a haloalkyl group (including perhaloalkyl), an alkyl ether group, an acyl group, or a haloacyl group.
• each of R′, R 2 , R 3 , R 4 , and R 5 are chosen from alkyl groups, alkyl ether groups, acetyl groups, and CF 3 groups. Without intending to be bound by any particular theory, it is believed that substitution at these positions surprisingly increases the oxidation potential through a steric effect.
• the redox shuttle e.g. the substituted carbazole
• the substituted carbazole may be included in the cell in any amount as determined by one of skill in the art.
• the substituted carbazole is present in an amount of from 0.05 to 10, from 1 to 10, from 2 to 9, from 3 to 8, from 4 to 7, or from 5 to 6, parts by weight per 100 parts by weight of the charge-carrying electrolyte.
• all values and ranges of values within those values described above are hereby expressly contemplated in various non-limiting embodiments.
• Mixtures of two or more redox shuttles (or substituted phenothiazines, substituted carbazole, substituted phenazine, or other redox shuttle) having different electrochemical potentials vs. Li/Li + may also be employed.
• a first redox shuttle operative at 3.7 V and a second redox shuttle operative at 3.9 V may both be employed in a single cell. If after many charge/discharge cycles the first redox shuttle degrades and loses effectiveness, the second redox shuttle (which would typically not meanwhile have been oxidized while the first redox shuttle was operative) can take over and provide a further (albeit higher E 1/2 ) margin of safety against overcharge damage.
• the redox shuttle can also provide overdischarge protection to a cell or to a battery of series-connected cells.
• Redox shuttles can also be used for cell balancing purposes as well as or even in lieu of overcharge protection.
• redox shuttles could be used to reduce the cost of cell-balancing associated electronics.
• the redox shuttle can be dissolved or dissolvable in the charge-carrying electrolyte in an amount sufficient to provide overcharge protection at the intended charging rate.
• the charge-carrying electrolyte can promote a large diffusion constant D to the redox shuttle and/or support a high redox shuttle concentration C.
• the charge-carrying electrolyte can initially or eventually include a dissolved quantity of the substituted phenothiazine, substituted carbazole, substituted phenazine, and/or the redox shuttle.
• the redox shuttle diffusion constant D typically increases as the viscosity of the charge-carrying electrolyte decreases.
• Non-limiting concentrations of the substituted phenothiazine, substituted carbazole, substituted phenazine, and/or the redox shuttle in the charge-carrying electrolyte are about 0.05 M up to a limit of solubility, more than 0.1 M up to a limit of solubility, about 0.2 M up to a limit of solubility or about 0.3 M up to a limit of solubility.
• concentration of the substituted phenothiazine, substituted carbazole, substituted phenazine, and/or the redox shuttle may be increased by incorporating a suitable cosolvent in the charge-carrying electrolyte.
• Non-limiting co-solvents include acetonitrile, benzene, ethers (e.g. dimethyl ether), esters (e.g. ethyl acetate or methyl acetate), lactones (e.g. gamma-butyrolactone), pyridine, tetrahydrofuran, toluene and combinations thereof.
• the co-solvent is chosen from ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, butylene carbonate, vinylene carbonate, fluoroethylene carbonate, fluoropropylene carbonate, ⁇ -butyrolactone, methyl difluoroacetate, ethyl difluoroacetate, dimethoxyethane, diglyme (bis(2-methoxyethyl)ether), and combinations thereof.
• the co-solvent is chosen from ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, or combinations thereof.
• the redox shuttle may alternatively be described as including one or more sterically bulky groups at sites adjacent to the nitrogen atom(s). Typically, the inclusion of electron-donating groups would be expected to shift the oxidation potential of the redox shuttle to a less positive number. However, in the instant disclosure, it is surprisingly discovered that sterically bulky groups, even if they are electron-donating groups, do precisely the opposite and shift the oxidation potential of the redox shuttle to a more positive number.
• the redox-shuttle may be 1-CF 3 -3,6-bis(t-Bu)carbazole; 1-acetyl-3,6-bis(t-Bu)carbazole; 1-acetyl-8-CF 3 -3,6-bis(t-Bu)carbazole; 1,8-bis(CF 3 )-3,6-bis(t-Bu)carbazole; the phenothiazines analogous to the aforementioned compounds; 1,4,6,9-tetra(t-Bu)phenazine; 1,6-bis(t-Bu)-4,9-bis(CF 3 )phenazine; 1,6-bis(t-Bu)-3,8-bis(CF 3 )phenazine; and/or any analogs having substitution at N such as C 1 -C 20 alkyl, alkyl ether or oligoether, trialkylammonium alkyl, or other solubilizing groups.
• the solubilizing group may be any known in the art.
• solubilizing groups may be as described in U.S. Pat. No. 6,445,486, which is expressly incorporated herein by reference in various non-limiting embodiments.
• any compounds described in the Examples below may be utilized in any embodiments described herein in various non-limiting embodiments.
• the cell may also include a porous cell separator disposed between the positive and negative electrodes and through which charge-carrying species (including the oxidized or reduced substituted phenothiazine, substituted carbazole, or substituted phenazine, and/or redox shuttle) may pass.
• charge-carrying species including the oxidized or reduced substituted phenothiazine, substituted carbazole, or substituted phenazine, and/or redox shuttle
• the redox shuttle provides overcharge protection to the cell after at least 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1,000, 1,500, 2,000, 2,500, 3,000, 3,500, 4,000, 4,500, 5,000, 5,500, 6,000, 6,500, 7,000, 7,500, 8,000, 8,500, 9,000, 9,500, 10,000, or even greater, charge-discharge cycles at a charging voltage sufficient to oxidize the redox shuttle and at an overcharge charge flow equivalent to 100% of the cell capacity during each charge-discharge cycle.
• all values and ranges of values within those values described above are hereby expressly contemplated in various non-limiting embodiments.
• This disclosure also provides an article including the cell and an array of cells.
• the article may be any known in the art that utilizes cells (or batteries), e.g. hand-held devices, flashlights, power tools, or any of those described above.
• the array of cells may also be any known in the art.
• the oxidation potential E 0 of a redox shuttle candidate relative to a lithium-ion cell can be determined by comparing the difference in standard free energies between the B3LYP energy G 0 (in electronvolts) between the shuttle S and its radical cation S + :
• R 1 R 2
• R 3 R 4 R 5 E calc (Li/Li + ) E exp (Li/Li + ) H H H 3.25 3.49 (Commercially Available) H H CH 3 3.36 3.60 (Commercially Available) CH 3 H CH 3 3.22 3.55 H CH 3 CH 3 3.49 — H t-Bu CH 3 3.87 — CH 3 CH 3 CH 3 3.38 — t-Bu t-Bu CH 3 3.79 — CN H CH 3 3.84 4.01 CN CH 3 CH 3 3.96 — CN t-Bu CH 3 4.29 — CF 3 CH 3 CH 3 3.89 — CF 3 t-Bu CH 3 4.15 — CH 3 CF 3 CH 3 3.80 — H H CH(CH 3 ) 2 3.37 — H CH 3 CH(CH 3 ) 2 3.68 — H H (CH 2 ) 3 N(CH 2 CH 3 ) 3 3.56 — CH 3 CH 3 (CH 2 ) 3 N(CH 2 CH 3 ) 3 3.67 — CH 3
• the diethyleneglycolmonomethylether is used for greater solubility in electrolytes. However, and without intending to be bound by any particular theory, it is believed that there is little or no difference in the redox potential between the compounds having the diethyleneglycolmonomethylether and those having the N-methyl groups.
• the crude product was obtained by quenching the reaction with DI water, extracting with dichloromethane, drying over MgSO 4 , filtering to remove the drying agent, and concentrating using rotary evaporation.
• the product was purified by column chromatography on silica using a dichloromethane/hexanes gradient.
• the flask was equipped with a condenser and stir bar, and the reaction was heated to 130° C. for 72 hours. Diethyl ether (200 mL) and DI water (200 mL) were added to the reaction after cooling to room temperature. The organic layer was washed with brine (100 mL), dried over MgSO 4 , filtered to remove the drying agent and any reduced palladium, and concentrated using rotary evaporation. The product was purified by column chromatography on silica using a dichloromethane/hexanes gradient.
• the mixture was stirred overnight, quenched with 150 mL of deionized water, and the crude product was extracted with 150 mL of dichloromethane, dried over MgSO 4 , filtered to remove the drying agent, and concentrated using rotary evaporation.
• the crude product was purified by column chromatography on silica using a dichloromethane/hexanes gradient.
• a round bottom flask was charged with 0.1254 g (1.267 mmol) of CuCl, 0.1439 g (1.282 mmol) of KOt-Bu, 0.2063 g (1.1448 mmol) of 1,10-phenanthroline and 2.5 mL of anhydrous deaerated DMF.
• the reaction mixture was stirred at room temperature for 30 minutes in the glovebox.
• 185 ⁇ L (1.252 mmol) of TMSCF 3 (trifluoromethyltrimethylsilane) was added by micro-syringe to the flask and stirred at room temperature for an additional 60 minutes.
• the phenazine data shows an unexpected a shift from a low oxidation potential (2.71) for a compound with no extra substituents to 2.91 for a compound with methyl substituents to 3.54 for a compound with 4 t-butyl substituents.
• the potential can be further increased by adding electron-withdrawing substituents at the sites not adjacent to the N atoms.
• the phenothiazine data shows the unexpected effects of substituents R 3 and R 4 , especially relevant for methyl and t-butyl, and also shows that the oxidation potential can be further customized by adding electron-withdrawing groups R 1 and R 2 (non-adjacent to nitrogen).
• the carbazole data shows that methyl groups have a smaller steric effect (potentially due to the molecular structure of the ring system, i.e., that is, more “splayed”).
• the oxidation potential of compound II is unexpectedly over 4V, even after addition of four strongly electron-donating groups, and the oxidation is reversible, which is also unexpected.
• One or more of the values described above may vary by ⁇ 5%, ⁇ 10%, ⁇ 15%, ⁇ 20%, ⁇ 25%, etc. so long as the variance remains within the scope of the disclosure. Unexpected results may be obtained from each member of a Markush group independent from all other members. Each member may be relied upon individually and or in combination and provides adequate support for specific embodiments within the scope of the appended claims. The subject matter of all combinations of independent and dependent claims, both singly and multiply dependent, is herein expressly contemplated. It is contemplated that any and all values or ranges of values between those described above may also be utilized.

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