S-linked quinone polymers, carbon sulfide matrices and related complexes, compositions, electrode materials, electrodes, electrochemical cells, batteries, methods and systems

Abstract

Redox-active S-linked polymers, sulfurized matrices, and related composites, compositions, electrode materials, electrodes, and related electrodes, chemical cell batteries, methods, and systems are described. In particular, S-linked polymers and related compositions, composites, electrode materials, and electrodes are described that have redox potentials of up to 3.5 V and capacities of up to 800 mAh / g or higher under standard conditions relative to the Li / Li+ electrode potential. More particularly, the redox-active S-linked polymers, sulfurized matrices, and related composites and compositions are provided as cathode electrode materials for electrochemical cells that further contain a Li anode and a non-aqueous electrolyte.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Application No. 63 / 339,684, entitled "S-linked Quinone Polymers, Sulfurized Carbon Matrices and Related Composites, Compositions, Electrode Material, Electrodes, Electrochemical Cells, Batteries, Methods and Systems," filed May 9, 2022 with Docket No. P2678-USP, the contents of which are incorporated herein by reference. This application is a joint venture between U.S. application Ser. No. 16 / 593,935, filed on October 4, 2019, entitled "Crosslinked Polymers and Related Compositions, Electrochemical Cells, Batteries, Methods and Systems," U.S. Provisional Application No. 62 / 741,519, filed on October 4, 2018, entitled "Quinone-comprising network polymers as stable, high capacity organic electrode materials," Docket No. ALNX_0001, U.S. Provisional Application No. 63 / 116,123, filed on November 19, 2020, entitled "Organic Electrode Materials for Zinc Batteries and Their Applications," Docket No. P2551-USP, and U.S. Provisional Application No. 63 / 116,123, filed on June 28, 2021, entitled "Organic Electrode Materials for Zinc Batteries and Their Applications," Docket No. P2551-USP2. No. 63 / 215,827, entitled "Comparative Application," the contents of each of which are incorporated herein by reference in their entireties.

[0002] The present disclosure relates to electrode active materials and battery systems featuring electrodes incorporating organosulfur redox-active polymers and matrices. In particular, the present disclosure relates to S-linked quinone polymers, carbon sulfide matrices, and related composites, compositions, electrode materials, electrodes, electrochemical cells, batteries, methods, and systems that can be used to improve electrochemical cell and battery performance. [Background technology]

[0003] Performance, economics, and safety are at the heart of various efforts to improve electrode active materials and battery technology. Summary of the Invention [Problem to be solved by the invention]

[0004] Despite advances made in recent years, however, producing highly reliable, high capacity, long-life, inexpensive and / or safe energy storage devices remains challenging, especially for batteries in large-scale applications, such as in electric vehicles, grid storage supporting renewable generation, or in full home backup battery installations. [Means for solving the problem]

[0005] Described herein are S-linked quinone polymers, carbon sulfide matrices and related composites, compositions, electrode materials, electrodes, electrochemical cells, batteries, methods and systems that, in some embodiments, enable the production of high performance redox active materials that can be used as cathode active materials in high capacity, high energy density, safe, good cycling stability and long lasting electrochemical cells and batteries using non-aqueous electrolytes.

[0006] According to a first aspect, there is provided an S-linked quinone polymer having the formula (I): -[M-Sp]- m (I) (In the formula, M is a redox-active monomeric quinone moiety having a redox potential of 0.5 V to 3.5 V relative to the Li / Li+ electrode potential under standard conditions, where the standard conditions under which all potentials are measured are 298 K, 1 atm, and a 1 M solution; p refers to the number of sulfur atoms linking the redox-active monomeric quinone moieties M, p ranges from 1 to 5; S p is a sulfide when p is 1 or a polysulfide when p is 2 to 5; m ranges from 5 to 10,000) is an S-linked quinone homopolymer represented by having a weight average molecular weight of at least 1,000 daltons and a solubility in tetrahydrofuran (THF) of 1.0 micrograms per mL or less at 21° C. and 1 atm; S-linked quinone polymers are described.

[0007] According to a second aspect, there is provided an S-linked quinone polymer having the formula (II) -[M1-S p1 ] m1 -co-[M2-S p2 ]- m2 (II) (In the formula, M1 and M2 are redox-active monomeric quinone moieties, each of which comprises a redox potential between 0.5 V and 3.5 V relative to the Li / Li+ electrode potential under standard conditions; p1 and p2 each independently refer to the number of sulfur atoms linking the redox-active monomeric quinone moiety M1 and the redox-active monomeric quinone moiety M2, respectively, and p1 and p2 each independently range from 1 to 5; S p1 is a sulfide when p1 is 1 or a polysulfide when p1 is 2 to 5; S p2 is a sulfide when p2 is 1 or a polysulfide when p2 is 2 to 5; m1 and m2 are each independently in the range of 5 to 5,000, and optionally the ratio of m1 to m2 is in the range of 1:50 to 1:1, 1:20 to 1:2, 1:6 to 1:3, or 1:5 to 1:4. is represented by the S-linked quinone copolymer of formula (II) has a weight average molecular weight in the range of 1,000 to 2,000,000 daltons and a solubility in tetrahydrofuran (THF) at 1 atm and 21° C. of 1.0 micrograms per mL or less; S-linked quinone polymers are described.

[0008] According to a third embodiment, there is provided a carbon sulfide matrix having the formula (V)

[0009] [ka]

[0010] (wherein Q is the bonded S p2 is a carbon atom (C) or nitrogen (N),

[0011] [ka]

[0012] represents a single bond or a double bond, S p represents a polysulfide, and p ranges from 2 to 8. is represented by having a mass average MW in the range of 2000 Daltons to 2,000,000 Daltons; Sulfided carbon matrices are described having a sulfur content, based on the total weight of the sulfided carbon matrix, of greater than or equal to 5 wt% and less than 20 wt%, greater than or equal to 20 wt% and less than 40 wt%, greater than or equal to 40 wt% and less than 60 wt%, greater than or equal to 60 wt% and less than 70 wt%, or greater than or equal to 70 wt% and less than 80 wt%.

[0013] According to a fourth aspect, a redox-active composition is described that includes one or more S-linked quinone polymers described herein, one or more carbon sulfide matrices described herein, or any combination thereof, together with an additive.

[0014] According to a fifth aspect, a redox-active composite material is described, the composite material comprising at least one S-linked quinone polymer as described herein and at least one carbon sulfide matrix as described herein.

[0015] According to a sixth aspect, a cathode material is described, wherein the cathode material comprises any of the redox active compositions and / or any of the redox active complexes described herein. In some embodiments, among others, the cathode material described herein comprises an S-linked quinone polymer selected from an S-linked quinone homopolymer, an S-linked quinone copolymer, and any combination thereof, and a carbon sulfide matrix as described herein, wherein the mass ratio of the S-linked quinone polymer to the carbon sulfide matrix ranges from 20:1 to 1:20, 10:1 to 1:10, 9:1 to 3:2, or 6:1 to 2:1 or 1:1.

[0016] According to a seventh aspect, a method and system for providing a cathode material is described. The method includes combining at least one of the S-linked quinone polymers described herein, at least one carbon sulfide matrix, or any combination thereof, optionally together with additives, to provide a redox composition and / or redox complex configured to allow sufficient contact and electrical conductivity with a non-aqueous electrolyte of an electrochemical cell. The system includes at least one of the S-linked quinone polymers described herein, at least one carbon sulfide matrix, optionally together with additives that are used in combination to provide a cathode material according to the seventh aspect described herein.

[0017] According to an eighth aspect, a method and system for providing a cathode material is described, the method comprising: providing at least one S-linked quinone polymer selected from one or more S-linked quinone homopolymers, one or more S-linked quinone copolymers, and any combination thereof; providing at least one carbon sulfide matrix; Includes. The method for providing the cathode material described herein includes: The method further includes combining at least one S-linked quinone polymer and at least one carbon sulfide matrix to provide the cathode material described herein. The system comprises: at least one S-linked quinone polymer selected from one or more S-linked quinone homopolymers, one or more S-linked quinone copolymers, and any combination thereof; at least one S-linked quinone polymer selected from at least one carbon sulfide matrix; for use in combination in a method to provide a cathode material according to the eighth aspect described herein. In some embodiments, the at least one S-linked quinone polymer and the at least one carbon sulfide matrix are mixed together. Additionally or alternatively, in some embodiments, the at least one S-linked quinone polymer and the at least one carbon sulfide matrix can be combined in any configuration that allows for electrical connection between the at least one S-linked quinone polymer and the at least one carbon sulfide matrix and allows for contact with a non-aqueous electrolyte when the cathode material is included in an electrochemical cell. In preferred embodiments, the combining step is performed to provide a cathode material described herein having a mass ratio of S-linked quinone polymer to carbon sulfide matrix ranging from 20:1 to 1:20, 10:1 to 1:10, 9:1 to 3:2, or 6:1 to 2:1, or is 1:1.

[0018] According to a ninth aspect, an electrochemical cell is described. The electrochemical cell includes an anode, a cathode, and a non-aqueous electrolyte, where the cathode electrode includes a cathode material described herein. In a preferred embodiment, the anode includes a lithium anode material, or a potassium anode material, or a sodium anode material, or a combination thereof, as will be understood by those skilled in the art.

[0019] In some embodiments, the cathode material as described includes lithium and sodium in a molar ratio of Li to Na ranging from 1:10 to 10:1, 4:6 to 6:4, or 1:1.

[0020] In some embodiments, the cathode material as described includes lithium and potassium in a molar ratio of Li to K ranging from 1:10 to 10:1, 4:6 to 6:4, or 1:1.

[0021] In some embodiments, the cathode material as described includes sodium and potassium in a molar ratio of Na to K ranging from 1:10 to 10:1, 4:6 to 6:4, or 1:1.

[0022] According to a tenth aspect, an electrochemical cell is described herein, the electrochemical cell comprising an anode, a cathode and a non-aqueous electrolyte, wherein the cathode electrode comprises one or more of the S-linked quinone polymers described herein, alone or in combination with a carbon sulfide matrix and / or a redox-active complex described herein.

[0023] According to an eleventh aspect, methods and systems are described for providing an electrochemical cell as described herein, the method comprising combining an anode electrode with any of the cathode materials as described herein, and in particular a cathode electrode comprising one or more of the S-linked quinone polymers as described herein, either alone or in combination with a carbon sulfide matrix and / or a redox-active complex as described herein.

[0024] The systems include any one of the cathode materials described herein in combination with an anode material for use in the methods to provide an electrochemical cell described herein.

[0025] In a preferred embodiment of the method and system according to the eleventh aspect, the anode comprises a lithium material.

[0026] According to a twelfth aspect, a battery is described, the battery including at least one electrochemical cell as described herein.

[0027] According to a thirteenth aspect, a method and system for making S-linked quinone homopolymers is described, the method comprising: Redox-active monomeric quinone monomer X 1 -MX 2 (In the formula, X 1 and X 2 represents a leaving group; Providing a source of sulfide Sp; Redox-active monomeric quinone monomer X 1 -MX 2 with a source of sulfide Sp under suitable conditions and for a sufficient time to produce a sulfide compound of formula (I) -[MS p ]- m (I) (In the formula, M is a redox-active monomeric quinone moiety having a redox potential of 0.5 V to 3.5 V relative to the Li / Li+ electrode potential under standard conditions; p refers to the number of sulfur atoms linking the redox-active monomeric quinone moieties M, p ranges from 1 to 5; S p is a sulfide when p is 1 or a polysulfide when p is 2 to 5; m ranges from 5 to 10,000) providing an S-linked quinone polymer represented by the S-linked quinone polymer having a weight average molecular weight of at least 1,000 Daltons and a solubility in tetrahydrofuran (THF) at 1 atm and 21° C. of 1.0 micrograms per mL or less; Includes. The system comprises a redox-active monomeric quinone monomer X 1 -MX 2 (In the formula, X 1 and X 2 indicates a leaving group) and a source of sulfide Sp for use in the method for making an S-linked quinone polymer.

[0028] According to a fourteenth aspect, a method and system for making an S-linked quinone copolymer is described. The method for making an S-linked quinone copolymer includes: Redox-active monomeric quinone monomer X 1 -M1-X 2 , and redox-active monomeric quinone monomer X 1 -M2-X 2 (wherein X 1 and X 2 represents a leaving group; Sulfide S p1 and S p2 providing a source of Redox-active monomeric quinone monomer X 1 -M1-X 2 and redox-active monomeric quinone monomer X 1 -M2-X 2 , sulfide S p1 and S p2 under suitable conditions and for a sufficient period of time to produce a compound of formula (II) -[M1-S p1 ] m1 -co-[M2-S p2 ]- m2 (II) (In the formula, M1 and M2 are redox-active monomeric quinone moieties, each of which comprises a redox potential between 0.5 V and 3.5 V relative to the Li / Li+ electrode potential under standard conditions; p1 and p2 each independently refer to the number of sulfur atoms linking the redox-active monomeric quinone moiety M1 and the monomeric quinone moiety M2, respectively, and p1 and p2 each independently range from 1 to 5; S p1 is a sulfide when p1 is 1 or a polysulfide when p1 is 2 to 5; S p2 is a sulfide when p2 is 1 or a polysulfide when p2 is 2 to 5; m1 and m2 are each independently in the range of 5 to 5,000, and optionally the ratio of m1 to m2 is in the range of 1:50 to 1:1, 1:20 to 1:2, 1:6 to 1:3, or 1:5 to 1:4. providing an S-linked quinone copolymer represented by Including, The S-linked quinone copolymers of formula (II) have a weight average molecular weight ranging from 1,000 to 2,000,000 daltons and a solubility in tetrahydrofuran (THF) at 21° C. and 1 atm of 1.0 micrograms per mL or less. The system includes a method for producing an S-linked quinone copolymer, comprising: - Redox-active monomeric quinone monomer X 1 -M1-X 2 , and redox-active monomeric quinone monomer X 1 -M2-X 2 (In the formula, X 1 and X 2 indicates a leaving group), and Sulfide S p1 and S p2 Source of Includes.

[0029] The S-linked quinone polymers, carbon sulfide matrices and related compositions, composites, electrode materials, electrodes, electrochemical cells, methods and systems, in some embodiments, are capable of providing batteries with high capacity (at least 50 mAh / g for the active material or redox-active S-linked organosulfur polymer utilized), long life (e.g., at least 4 years) and / or low safety hazards, including low flammability, and low cost.

[0030] The S-linked quinone polymers, carbon sulfide matrices and related compositions, composites, electrode materials, electrodes, electrochemical cells, methods and systems described herein, in some embodiments, enable the provision of batteries with low spatial footprint and low replacement.

[0031] The S-linked quinone polymers, carbon sulfide matrices and related compositions, composites, electrode materials, electrodes, electrochemical cells, methods, and systems described herein, in some embodiments, enable the provision of batteries with higher capacity and longer life over existing polymer / metal and sulfur / metal batteries in non-aqueous electrolytes.

[0032] Additionally, the S-linked quinone polymers, carbon sulfide matrices and related compositions, composites, electrode materials, electrodes, electrochemical cells, methods and systems described herein, in some embodiments, enable the provision of Li batteries in non-aqueous electrolytes with comparable or higher capacity and longer life versus existing batteries based on organic redox-active materials.

[0033] The S-linked quinone polymers, carbon sulfide matrices, and related composites, electrode materials, electrodes, electrochemical cells, methods, and systems described herein can be used in connection with applications where high capacity, long life, low safety hazards, low spatial footprint, and / or low replacement electrochemical cells are desired. Exemplary applications include, but are not limited to, batteries for electric vehicles, grid storage, telecommunications, and automotive start-stop.

[0034] The details of one or more embodiments of the disclosure are set forth in the accompanying drawings and the description below. Other features and objects will be apparent from the description and drawings, and from the claims.

[0035] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate one or more embodiments of the present disclosure and, together with the description of the illustrative embodiments, explain the principles and practice of the present disclosure. [Brief description of the drawings]

[0036] [Figure 1] 1 is a table of exemplary S-linked organosulfur polymers, including PAQS, 36PPAQS, 27PPAQS, and PAQT, as cathode redox active materials, and their theoretical capacity (mAh / g), voltage vs. Li / Li+, and theoretical energy density (Wh / kg) in lithium batteries. The molecular weights of these polymers range from 1,000 Da to 2,000,000 Da. As can be understood by those skilled in the art, the theoretical values ​​consider the amount of charge available for transfer per unit mass or volume in terms of the fundamental electrochemical process in redox reactions (number of electrons, voltage, mass). [Diagram 2] 1 shows the structures of the S-linked quinone polymers PAQS, 36PPAQS, 27PPAQS, PAQT, and PBQS. The molecular weights of these polymers range from 1,000 Da to 2,000,000 Da. [Diagram 3]1 shows the structures of PAQS or copolymers of PAQT and PBQS. The molecular weights of these polymers range from 1,000 Da to 2,000,000 Da. [Figure 4] 1 and 2. SPAN (11), covalent triazine backbone (S-CTF-1) (12), covalent triazine backbone (SF-CTF-1) (13), poly(sulfur random-1,3-diisopropylbenzene) (Poly(Sr-DIB) (14), S-BOP (15), carbon / polymeric sulfur (C / PS) composite (16), covalently grafted polysulfur graphene nanocomposite (PolySGN, 17), graphene-supported crosslinked sulfur copolymer nanoparticles, cp(STTCA)@rGO-80 (18) are examples of carbon sulfide matrices containing polymers, where S is present as, for example, CS, CSS, CSSS, CSSSS, CSSSSS-linkages, as would be understood by one of skill in the art upon reading this disclosure. [Diagram 5] 1 shows the voltage profile (charge and discharge characteristics) of a Li / / 36PPAQS cell in ANA-6 at C / 10. C is the capacity of the cell charged (discharged) for n hours, therefore C / n=total capacity charged (discharged) for n hours, hence C / 10=total capacity discharged (or charged) for 10 hours. [Figure 6] 13 is a graph showing the cycling characteristics of Li / / 36PPAQS cells at C / 10 in ANA-6. [Figure 7] 13 is a graph showing the coulombic efficiency versus cycle number profile of Li / / 36PPAQS cells in ANA-6. [Figure 8] 13 is a graph showing voltage profile (charge and discharge characteristics) of a Li / / PAQT cell in ANA-7 at C / 10. [Figure 9] FIG. 13 is a graph showing cycling characteristics of Li / / PAQT cells at C / 10 in ANA-7. [Figure 10] 13 is a graph showing the coulombic efficiency versus cycle number profile of the Li / / PAQT cell in ANA-7. [Figure 11] 13 is a graph showing voltage profile (charge and discharge characteristics) of Li / / PAQS:SPAN cells in ANA-4 at C / 10. [Figure 12] 13 is a graph showing discharge capacity versus cycle number of Li / / PAQS:SPAN cells in ANA-4 at C / 10. [Figure 13] 13 is a graph showing coulombic efficiency vs. cycle number of Li / / PAQS:SPAN cells in ANA-4 at C / 10. [Figure 14] 13 is a graph showing energy density (kWh / g) versus cycle number for Li / / PAQS:SPAN cells in ANA-4 at C / 10. [Figure 15] FIG. 13 is a graph showing voltage profile (charge and discharge characteristics) of Li / / PAQS:SPAN (48:38) cell in ANA-6 at C / 10. [Figure 16] FIG. 13 is a graph showing discharge capacity versus cycle number of Li / / PAQS:SPAN (48:38) cells in ANA-6 at C / 10. [Figure 17] FIG. 13 is a graph showing coulombic efficiency vs. cycle number for Li / / PAQS:SPAN (48:38) cells in ANA-6 at C / 10. [Figure 18] FIG. 13 is a graph showing voltage profile (charge and discharge characteristics) of Li / / PAQS:SPAN (70:20) cell in ANA-4 at C / 10. [Figure 19] FIG. 13 is a graph showing discharge capacity versus cycle number of Li / / PAQS:SPAN (70:20) cells in ANA-4 at C / 10. [Figure 20] FIG. 13 is a graph showing coulombic efficiency versus cycle number for Li / / PAQS:SPAN (70:20) cells in ANA-4 at C / 10. [Figure 21] FIG. 13 shows the voltage profile (charge and discharge characteristics) of Li / / PAQS0.8-PBQS0.2 cell in ANA-4 at C / 10. [Figure 22] FIG. 13 shows the discharge capacity vs. cycle number of Li / / PAQS0.8-PBQS0.2 cells in ANA-4 at C / 10. [Diagram 23] FIG. 13 is a graph showing coulombic efficiency vs. cycle number of Li / / PAQS0.8-PBQS0.2 cells in ANA-4 at C / 10. [Figure 24] FIG. 13 shows the voltage profile (charge and discharge characteristics) of Li / / PAQS:SC cell in ANA-4 at C / 10. [Diagram 25] FIG. 13 shows the discharge capacity vs. cycle number of Li / / PAQS:SC cells in ANA-4 at C / 10. [Figure 26] 13 is a graph showing coulombic efficiency vs. cycle number of Li / / PAQS:SC cells in ANA-4 at C / 10. [Figure 27] FIG. 13 is a graph showing voltage profile (charge and discharge characteristics) of Li / / PAQS:S cell in ANA-4 at C / 10. [Figure 28] FIG. 13 is a graph showing discharge capacity versus cycle number of Li / / PAQS:S cells in ANA-4 at C / 10. [Figure 29] 13 is a graph showing coulombic efficiency vs. cycle number of Li / / PAQS:S cells in ANA-4 at C / 10. [Diagram 30] FIG. 1 shows a comparison of the structures of element S (S8) and sulfurized polyacrylonitrile (SPAN). [Diagram 31] The top panel of Figure 31 shows a schematic diagram of an exemplary electrochemical cell including a Li anode and a cathode including an organosulfur polymer described herein. The bottom panel of Figure 31 shows a schematic diagram of an exemplary pouch housing electrochemical cell including a Li anode and a cathode including a tricyclic compound described herein. [Diagram 32] FIG. 2 shows an exemplary arrangement of multiple electrochemical cells in a battery as described herein. [Diagram 33] FIG. 1 shows a schematic diagram of an illustrative multiple electrically connected electrochemical cell according to the present disclosure. [Diagram 34] 13 is a graph showing voltage profile (charge and discharge characteristics) of Li / / Gen4 cells in ANA-42 at C / 10. [Diagram 35] FIG. 13 is a graph showing discharge capacity (mAh / g) versus cycle number of Li / / Gen4 cells in ANA-42 at C / 10. [Diagram 36] 1 is a graph showing coulombic efficiency vs. cycle number of Li / / Gen4 cells in ANA-42 at C / 10. [Figure 37] FIG. 13 is a graph showing energy density (Wh / kg) versus cycle number of Li / / Gen4 cells in ANA-42 at C / 10. [Figure 38] 13 is a graph showing voltage profile (charge and discharge characteristics) of Li / / Gen4 cell in ANA-42 at C / 3. [Figure 39] FIG. 13 is a graph showing discharge capacity (mAh / g) versus cycle number of Li / / Gen4 cells in ANA-42 at C / 3. [Diagram 40] 1 is a graph showing coulombic efficiency vs. cycle number of Li / / Gen4 cells in ANA-42 at C / 3. [Diagram 41] 13 is a graph showing voltage profile (charge and discharge characteristics) of Li / / Gen5 cells in ANA-42 at C / 10. [Diagram 42] FIG. 13 is a graph showing discharge capacity (mAh / g) versus cycle number of Li / / Gen5 cells in ANA-42 at C / 10. [Diagram 43] 1 is a graph showing coulombic efficiency vs. cycle number of Li / / Gen5 cells in ANA-42 at C / 10. [Diagram 44] FIG. 13 shows the voltage profile (charge and discharge characteristics) of Li / / PAQS0.8-PBQS0.2 cell in ANA-5 at C / 10. [Diagram 45] FIG. 13 shows the discharge capacity vs. cycle number of Li / / PAQS0.8-PBQS0.2 cells in ANA-5 at C / 10. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0037] Described herein are S-linked quinone polymers, carbon sulfide matrix polymers, and related compositions, electrode materials, electrodes, electrochemical cells, batteries, methods, and systems.

[0038] The term "S-linked quinone polymer" as used herein refers to a sulfur-containing quinone polymer, in which the monomer units are linked through sulfide (-S-) bonds. Thus, an S-linked quinone polymer is a sulfur-containing polymer that contains one or more redox-active quinone moieties, as will be understood by those skilled in the art.

[0039] The term "polymer" as used herein refers to any of a class of natural or synthetic materials composed of very large organic molecules, called macromolecules, which contain many repeating identical and / or different chemical units, called monomers. In particular, the word "polymer" includes any product resulting from the linking of organic repeating units by covalent chemical bonds, including, for example, aromatic moieties, such as benzene, naphthalene, anthracene, and moieties derivable therefrom, such as quinones, and aliphatic monomeric units, such as ethylene, propylene, cyclooctadiene, dienes, olefins, acrylonitrile, methyl methacrylate, vinyl acetate, dichlorodimethylsilane, tetrafluoroethylene, and additional monomers identifiable by one of skill in the art. Monomers as described herein include, for example, F, Cl, Br, I, CF 3 , a linear or branched, substituted or unsubstituted C1-C4 aliphatic group, an aromatic ring, a heteroaromatic ring, a non-aromatic ring, or a non-aromatic heterocyclic ring containing a substituent containing 4 to 12 carbon atoms and 0 to 4 heteroatoms, or any suitable substituent identifiable by one of ordinary skill in the art.

[0040] Thus, an S-linked quinone polymer as described herein includes a polymer within the meaning of the present disclosure, which in turn includes a redox-active quinone monomeric moiety.

[0041] The term "redox-active" as used herein refers to a chemical moiety (e.g., a polymer or monomer or portion thereof) that can be reversibly oxidized or reduced in a non-aqueous electrolyte to generate a detectable redox potential. Redox-active functional groups include ketones, aldehydes, and carboxylic acids, imines, organic sulfides, and additional functional groups identifiable by one of skill in the art.

[0042] In the S-linked quinone polymers described herein, the redox-active moieties have a redox potential of 0.50 V to 3.5 V relative to the Li / Li+ electrode potential under standard conditions. + has a potential of -3.04 V with respect to SHE, and Li / Li + The potential of the redox part relative to the potential of Li / Li is 3.04V. + It should be understood that the potential relative to SHE can be expressed by subtracting the potential relative to SHE, which is converted to the potential of the redox moiety relative to SHE.

[0043] Therefore, the S-linked quinone polymers described herein have charge capacity as understood by those skilled in the art.As used herein, the term "charge capacity" is a measure of the current x time product of the charge that an anode material undergoes until a cutoff voltage is reached.Discharge capacity is the current x time product of the charge that a cathode material undergoes until a cutoff voltage is reached.

[0044]

number

[0045] where Q is the theoretical capacity, n is the number of exchanged electrons, F is the Faraday constant, MW is the molecular weight of the electroactive material.

[0046] Since the S-linked quinone polymers described herein have redox potentials of 0.5 V to 3.5 V relative to the Li / Li+ electrode potential, substituents can be selected based on Hammett sigma constants, such as those shown in Table 1 below, to increase or decrease the redox potential of the starting redox-active monomeric moieties.

[0047] Since the S-linked quinone polymers described herein have redox potentials of 0.50 V to 3.5 V versus the Li / Li+ electrode potential, substituents can be selected based on Hammett sigma constants, such as those shown in Table 1 below, to increase or decrease the redox potential of the starting redox-active monomeric moieties.

[0048] [Table 1A]

[0049] [Table 1B]

[0050] For example, to increase the redox potential of the starting redox-active monomeric moiety having an aromatic ring, a CN group or a CF 3 Groups may be included as may be included in view of the associated Hammett sigma constant. Additional modifications to increase or decrease the redox potential of the starting moiety will be understood by those of skill in the art upon reading this disclosure.

[0051] In some embodiments, where an S-linked quinone polymer is described herein, the redox-active moiety is provided by the quinone portion of the polymer.

[0052] The term "quinone" and related moieties, as used herein, refers to a class of organic compounds that are formally derived from aromatic compounds [such as benzene or naphthalene] by converting the even number of -CH= groups to -C(=O)- groups with any necessary rearrangement of the double bonds, resulting in a fully conjugated cyclic dione structure [1][2][3][4][5]. Illustrative quinones include moieties such as 1,4-benzoquinone or cyclohexadienedione, often simply referred to as "quinones" (hence the name of the class). Other examples are 1,2-benzoquinone (ortho-quinone), 1,4-naphthoquinone, and 9,10-anthraquinone [5]. Other quinones include 2,5-dichloroanthraquinone, 3,6-dibromo-phenanthrenequinone, 2,7-dibromo-phenanthrenequinone, and 1,2,5,6-anthracenetetraone, as described herein, as well as additional quinones as would be understood by one of skill in the art.

[0053] In some embodiments described herein, the S-linked quinone polymer comprises homopolymers of 2,5-S-linked anthraquinone (PAQS), 3,6-S-linked phenanthrenequinone (36PPAQS), 2,7-S-linked phenanthrenequinone (27PPAQS), and 9,10-S-linked 1,2,5,6-anthracenetetraone (PAQT) as described herein, as well as copolymers of structures such as alternating copolymers, random copolymers, block copolymers, and graft copolymers as understood by those skilled in the art. An exemplary random copolymer as described herein is poly-anthraquinone-benzoquinone sulfide (PAQS-BQ) in Example 34. Additional quinone copolymers within the meaning of the disclosure can be identified by those skilled in the art.

[0054] In some cases, S-linked polymers are obtained via the reaction between chlorinated or brominated quinone monomers and Na2S at 120-150°C.

[0055] In some embodiments, the S-linked quinone polymer of the present disclosure has formula (I): -[MSp ]- m (I) (In the formula, M is a redox-active monomeric quinone moiety that contains a redox potential between 0.5 V and 3.5 V relative to the Li / Li+ electrode potential under standard conditions; p refers to the number of sulfur atoms linking the redox-active monomeric quinone moieties M, p ranges from 1 to 5; S p is a sulfide when p is 1 or a polysulfide when p is 2 to 5; m ranges from 5 to 10,000) may be an S-linked homopolymer represented by The S-linked quinone polymer has a weight average molecular weight of at least 1,000 Daltons and a solubility in tetrahydrofuran (THF) at room temperature (i.e., 21° C.) of 1.0 micrograms per mL or less at 1 atm, preferably a solubility in tetrahydrofuran (THF) at room temperature at 1 atm of 0.1 micrograms per mL or less, more preferably a solubility in tetrahydrofuran (THF) at room temperature at 1 atm of 0.01 micrograms per mL or less.

[0056] In some embodiments, at least one redox-active monomeric moiety M of formula (I) has formula (III):

[0057] [ka]

[0058] (In the formula, R 1 , R 2 , R 3 , and R 4 are each independently null (not present), H, or S p (wherein p ranges from 1 to 5), F, Cl, Br, I, CF3, a linear or branched substituted or unsubstituted C1-C4 aliphatic group, an aromatic ring, a heteroaromatic ring, a non-aromatic ring, or a non-aromatic heterocycle containing a substituent containing 4 to 12 carbon atoms and 0 to 4 heteroatoms; In the aromatic ring, heteroaromatic ring, non-aromatic ring, and non-aromatic heterocycle, the heteroatoms are selected from O, N, and S; R 1 and R 2 together and / or R 3 , and R 4 together are part of an aromatic or aliphatic ring structure, The dashed line --- represents null (not present) or the associated R 1 , R 2 , R 3 Or R 4 If is null, it represents a single bond to a quinone ring carbon. It can be expressed as:

[0059] In some embodiments, at least one redox-active monomeric moiety M of formula (I) represented by formula (III) is selected from the group consisting of formula (IIIA) and formula (IIIB):

[0060] [ka]

[0061] The S-linked monomeric moiety -SM may be any one of the following:

[0062] In some embodiments, at least one redox-active monomeric moiety M of formula (I) has formula (IV):

[0063] [ka]

[0064] (In the formula, R 1 , R 2 , R 3 , and R 4 is S p(wherein p ranges from 1 to 5), F, Cl, Br, I, CF3, a linear or branched substituted or unsubstituted C1-C4 aliphatic group, an aromatic ring, a heteroaromatic ring, a non-aromatic ring, or a non-aromatic heterocycle containing a substituent containing 4 to 12 carbon atoms and 0 to 4 heteroatoms; In the aromatic ring, heteroaromatic ring, non-aromatic ring, and non-aromatic heterocycle, the heteroatoms are selected from O, N, and S; R 1 and R 2 together and / or R 3 , and R 4 together are part of an aromatic or aliphatic ring structure, The dashed line --- represents a null or associated R 1 , R 2 , R 3 Or R 4 If is null, it represents a single bond to a quinone ring carbon. It can be expressed as:

[0065] In some embodiments, at least one redox-active monomeric moiety M of formula (I) represented by formula (IV) is selected from the group consisting of formula (IVA), formula (IVB), formula (IVC),

[0066] [ka]

[0067] The monomeric moiety may be any one of the S-linked monomeric moieties as shown in

[0068] In some embodiments, sources of sulfide Sp include, but are not limited to, elemental sulfur S8, N a2 S., Li 2 S., K. 2 S, any other sulfur-containing compound known to one of skill in the art.

[0069] In some embodiments, the S-linked quinone polymer of the present disclosure has the formula (II): -[M1-S p1 ] m1-co-[M2-S p2 ]- m2 (II) (In the formula, M1 and M2 are redox-active monomeric quinone moieties, each of which comprises a redox potential between 0.5 V and 3.5 V relative to the Li / Li+ electrode potential under standard conditions; p1 and p2 each independently refer to the number of sulfur atoms linking the redox-active monomeric quinone moieties M1 and M2, respectively, and p1 and p2 each independently range from 1 to 5; S p1 is a sulfide when p1 is 1 or a polysulfide when p1 is 2 to 5; S p2 is a sulfide when p2 is 1 or a polysulfide when p2 is 2 to 5; m1 and m2 are each independently in the range of 5 to 5,000, and optionally the ratio of m1 to m2 is in the range of 1:50 to 1:1, 1:20 to 1:2, 1:6 to 1:3, or 1:5 to 1:4. may be an S-linked copolymer represented by The S-linked quinone copolymers of formula (II) have a weight average molecular weight of at least 1,000 Daltons and a solubility in tetrahydrofuran (THF) at room temperature and 1 atm of 1.0 micrograms per mL or less, preferably a solubility in tetrahydrofuran (THF) at room temperature and 1 atm of 0.1 micrograms per mL or less, more preferably a solubility in tetrahydrofuran (THF) at room temperature and 1 atm of 0.01 micrograms per mL or less. Formula (II) represents any arrangement of M1 and M2 moieties in S-linked copolymers, including random, block and alternating copolymers.

[0070] In particular, in some embodiments, the redox-active monomer M1, the redox-active monomer M2 in the S-linked copolymer may be a statistically random copolymer, in which the redox-active monomer M1, the redox-active monomer M2 are present in a statistically random manner in the network polymer. An exemplary statistically random copolymer of M1 and M2 is: -M1-S-M2-S-M1-S-M2-S-M1-S-M1-S-M2-S-M1-S-M2-S-M2-S- It can be expressed as:

[0071] In some embodiments, a method for making an S-linked quinone copolymer includes: Redox-active monomeric quinone monomer X 1 -M1-X 2 , and redox-active monomeric quinone monomer X 1 -M2-X 2 (In the formula, X 1 and X 2 represents a leaving group; Sulfide S p1 and S p2 providing a source of Redox-active monomeric quinone monomer X 1 -M1-X 2 and redox-active monomeric quinone monomer X 1 -M2-X 2 , sulfide S p1 and S p2 under suitable conditions and for a sufficient period of time to produce a compound of formula (II) -[M1-S p1 ] m1 -co-[M2-S p2 ]- m2 (II) (In the formula, M1 and M2 are redox-active monomeric quinone moieties each comprising a redox potential between 0.5 V and 3.5 V relative to the Li / Li+ electrode potential under standard conditions; p1 and p2 each independently refer to the number of sulfur atoms linking the redox-active monomeric quinone moiety M1 and the monomeric quinone moiety M2, respectively, and p1 and p2 each independently range from 1 to 5; S p1 is a sulfide when p1 is 1 or a polysulfide when p1 is 2 to 5; S p2 is a sulfide when p2 is 1 or a polysulfide when p2 is 2 to 5; m1 and m2 are each independently in the range of 5 to 5,000, and optionally the ratio of m1 to m2 is in the range of 1:50 to 1:1, 1:20 to 1:2, 1:6 to 1:3, or 1:5 to 1:4. wherein the S-linked quinone copolymer of formula (II) has a weight average molecular weight range of from 1,000 Daltons to 2,000,000 Daltons and a solubility in tetrahydrofuran (THF) of 1.0 micrograms per mL or less at 1 atm and 21° C.; A method is described, comprising:

[0072] In some embodiments, the leaving groups X1 and X2 are Cl. - , Br - , I - , - O.T.s., - OMS, - OTf, or any other leaving group known to one of skill in the art.

[0073] In some embodiments, sulfide S p1 and S p2 Sources of sulfur include, but are not limited to, elemental sulfur S8, N a2 S., Li 2 S., K. 2 S, any other sulfur-containing compound known to one of skill in the art.

[0074] In some embodiments, the redox-active monomer M1 and the redox-active monomer M2 in the S-linked copolymer may be an alternating copolymer, where the redox-active monomer M1 and the redox-active monomer M2 alternate in the S-linked copolymer. An exemplary alternating S-linked copolymer of M1 and M2 is: -M1-S-M2-S-M1-S-M2-S-M1-S-M2-S-M1-S-M2-S-M1-S-M2-S- It can be expressed as:

[0075] In some embodiments, the redox-active monomer M1, the redox-active monomer M2 in the S-linked copolymer may be an M1M2 diblock copolymer, where the redox-active monomer M1, the redox-active monomer M2 are only present in a sequence of at least five moieties in the S-linked copolymer. An exemplary M1M2 diblock S-linked copolymer of M1 and M2 is: -M1-S-M1-S-M1-S-M1-S-M1-S-M1-S-M2-S-M2-S-M2-S-M2-S-M2-S-M2-S- It can be expressed as:

[0076] In some embodiments, the redox-active monomer M1, the redox-active monomer M2 in the S-linked copolymer represent a M1M2M1 triblock copolymer, where one of the redox-active monomers M1 and M2 is present in at least two sequences of at least five moieties separated by a sequence of different moieties in the network polymer. An illustrative M1M2 triblock copolymer of M1 and M2 is: -M1-S-M1-S-M1-S-M1-S-M1-S-M2-S-M2-S-M2-S-M2-S-M2-S-M1-S-M1-S-M1-S-M1-S-M1-S-M1-S- It can be expressed as:

[0077] In some embodiments, the redox-active monomeric quinone moiety M1 and the redox-active monomeric quinone moiety M2 of formula (II) are represented by formula (III) and formula (IIV):

[0078] [ka]

[0079] (In the formula, R 1 , R 2 , R 3 , and R 4 are each independently null (not present), H, or S p (wherein p ranges from 1 to 5), F, Cl, Br, I, CF3, a linear or branched substituted or unsubstituted C1-C4 aliphatic group, an aromatic ring, a heteroaromatic ring, a non-aromatic ring, or a non-aromatic heterocycle containing a substituent containing 4 to 12 carbon atoms and 0 to 4 heteroatoms; In the aromatic ring, heteroaromatic ring, non-aromatic ring, and non-aromatic heterocycle, the heteroatoms are selected from O, N, and S; R 1 and R 2 together and / or R 3 , and R 4 together are part of an aromatic or aliphatic ring structure, The dashed line --- represents null (not present) or the associated R 1 , R 2 , R 3 Or R 4 If is null, it represents a single bond to a quinone ring carbon. It can be represented by one of the following:

[0080] In some embodiments, the S-linked redox active monomeric quinone moiety -S-M1 and the S-linked redox active monomeric quinone moiety -S-M2 of formula (II) are independently selected from the group consisting of formula (IIIA), formula (IIIB), formula (IVA), formula (IVB), and formula (IVC).

[0081] [ka]

[0082] The S-linked monomeric moiety -SM may be any one of the following:

[0083] In some embodiments, the S-linked copolymer has the formula (IIIA):

[0084] [ka]

[0085] S-linked redox active monomeric quinone moieties -S-M1, S-linked monomeric moieties -SM, and S-linked redox active monomeric quinone moieties -S-M2 of formula (II), and S-linked redox active monomeric quinone moieties -S-M3, -S-M4, -S-M5, -S-M6, -S-M7, -S-M8, -S-M9, -S-M10, -S-M11, -S-M12, -S-M13, -S-M14, -S-M15, -S-M16, -S-M17, -S-M18, -S-M19, -S-M21, -S-M22, -S-M23, -S-M24, -S-M25, -S-M26, -S-M27, -S-M28, -S-M29, -S-M3

[0086] [ka]

[0087] and the molar ratio of S-linked monomeric moiety -S-M1 of formula (IIIA) to S-linked monomeric moiety -S-M2 of formula (IIIB), formula (IVA), formula (IVB), or formula (IVC) is in the range of 1:50 to 1:1, 1:20 to 1:2, 1:6 to 1:3, or 1:5 to 1:4; or The molar ratio of S-linked monomeric moiety-S-M1 of Formula (IIIA) to S-linked monomeric moiety-S-M2 of Formula (IIIB), Formula (IVA), Formula (IVB), or Formula (IVC) can be 1:4.

[0088] In some embodiments, the S-linked copolymer as described has formula (III):

[0089] [ka]

[0090] (In the formula, R 1 , R 2 , R 3 , and R 4 are each independently null, H, or Sp (wherein p ranges from 1 to 5), F, Cl, Br, I, CF3, a linear or branched substituted or unsubstituted C1-C4 aliphatic group, an aromatic ring, a heteroaromatic ring, a non-aromatic ring, or a non-aromatic heterocycle containing a substituent containing 4 to 12 carbon atoms and 0 to 4 heteroatoms; In the aromatic ring, heteroaromatic ring, non-aromatic ring, and non-aromatic heterocycle, the heteroatoms are selected from O, N, and S; R 1 and R 2 together and / or R 3 , and R 4 together are part of an aromatic or aliphatic ring structure, The dashed line --- represents a null or associated R 1 , R 2 , R 3 Or R 4 If is null, it represents a single bond to a quinone ring carbon. The compound includes a redox-active monomeric quinone moiety M1 and a redox-active monomeric quinone moiety M2 of formula (II) which can be independently represented by:

[0091] In some embodiments, the S-linked redox-active monomeric quinone moiety -S-M1 and the S-linked redox-active monomeric quinone moiety -S-M2 of formula (II) are represented by formula (IIIA) and formula (IIIB):

[0092] [ka]

[0093] and S-linked monomeric moiety -SM of The molar ratio of S-linked monomeric moiety-S-M1 of formula (IIIA) to S-linked monomeric moiety-S-M2 of formula (IIIB) ranges from 1:50 to 1:1, 1:20 to 1:2, 1:6 to 1:3, or 1:5 to 1:4.

[0094] In some embodiments, the redox-active S-linked copolymer PAQS 0.8 BQ 0.2wherein the S-linked redox active monomeric quinone moiety -S-M1 and the S-linked redox active monomeric quinone moiety -S-M2 of formula (II) are independently represented by the formula (IIIA) and the formula (IIIB)

[0095] [ka]

[0096] and S-linked monomeric moieties -SM of The molar ratio of S-linked monomeric moiety-SM of formula (IIIA) to S-linked monomeric moiety-SM of formula (IIIB) can be 1:4; Redox-active S-linked copolymers are described.

[0097] In some embodiments, the redox-active monomeric quinone moiety M1 and the redox-active monomeric quinone moiety M2 of formula (II) are represented by the formula (IV):

[0098] [ka]

[0099] (In the formula, R 1 , R 2 , R 3 , and R 4 are each independently null, H, or S p (wherein p ranges from 1 to 5), F, Cl, Br, I, CF3, a linear or branched substituted or unsubstituted C1-C4 aliphatic group, an aromatic ring, a heteroaromatic ring, a non-aromatic ring, or a non-aromatic heterocycle containing a substituent containing 4 to 12 carbon atoms and 0 to 4 heteroatoms; In the aromatic ring, heteroaromatic ring, non-aromatic ring, and non-aromatic heterocycle, the heteroatoms are selected from O, N, and S; R 1 and R 2 together and / or R 3 , and R 4 together are part of an aromatic or aliphatic ring structure, The dashed line --- represents a null or associated R 1 , R 2 , R 3 Or R 4 If is null, it represents a single bond to a quinone ring carbon. It can be expressed as:

[0100] In some embodiments, the S-linked redox-active monomeric quinone moiety -S-M1 and the S-linked redox-active monomeric quinone moiety -S-M2 of formula (II) represented by formula (IV) are represented by formula (IVA), formula (IVB), formula (IVC),

[0101] [ka]

[0102] The monomeric moiety may be any one of the S-linked monomeric moieties as shown in

[0103] In some embodiments, one or more S-linked polymers described herein, either alone or in various combinations identifiable by one of skill in the art, are included in a composite material along with one or more carbon sulfide matrices.

[0104] The term "sulfurized carbon matrix" or "sulfur-incorporated carbon matrix" as used herein refers to a carbon-based matrix in which elemental sulfur is embedded in the carbon-based matrix, where the elemental sulfur is linked to the C atoms of the matrix material in structures such as CS, CSS, CSSS, CSSSS, CSSSSS bonds or other higher polysulfides. The term "carbon matrix" as used herein refers to a solid carbon-based material in which the inorganic graphite or organic monomeric portion of the polymeric matrix is ​​configured to link to C atoms, group 16 elements, and especially S, in the surrounding organic mass as described herein in the form of CS, CSS, CSSS, CSSSS, CSSSSS bonds. For example, any configuration of aromatic monomers described herein linked to each other in any configuration results in the presentation of CS, CSS, CSSS, CSSSS, CSSSSS bonds on the resulting organic portion for electrochemical reaction with other molecules or compounds, such as the electrolytes and / or S-linked polymers described herein. Illustrative carbon-based matrices include graphite, polyacrylonitrile, as well as additional carbon-based matrices as understood by those skilled in the art.

[0105] The sulfurized carbon matrix described herein can be provided by sulfurizing elemental sulfur at elevated temperatures in the presence of a polymer containing aromatic moieties to form a carbon-based matrix, where the sulfur atoms are bonded into the matrix and carbonized at a suitable temperature, which can be, for example, greater than 300°C, preferably greater than 500°C, or in the range of 300°C to 1000°C, or 500°C to 800°C.

[0106] Sulfur-incorporated carbon matrices can deliver relatively high theoretical capacity based on the reversible breaking and formation of disulfide (SS) bonds. Three types of organosulfur cathodes have been used: (i) small organosulfur molecules, (ii) high sulfur content polymers, and (iii) sulfurized polymers. Small organosulfur molecules are soluble in organic electrolytes, which limits their use as cathode active materials. Although high sulfur content polymers and sulfurized polymers are not soluble in organic solvents, they still form small amounts of soluble polysulfides during deep discharge and, as a result, overcharge these soluble sulfides during the charging process through a shuttle mechanism. Even though significant progress has been made over the years to realize organosulfur polymers as cathode active materials for practical batteries, significant hurdles must be overcome due to the shuttle effect, high electrolyte loading, high conductive carbon loading, and low tap density.

[0107] In some embodiments, the sulfur-incorporated carbon matrix may be SPAN (sulfurized poly[acrylonitrile]), a sulfurized carbon matrix polymer of elemental sulfur and polyacrylonitrile, which exhibits high capacity (>200 mAh / g at 3.0 to 0.500 V) with better cycling stability compared to standard sulfur cathodes in electrochemical cells with lithium anodes; however, most capacity is reached at lower potentials (e.g., below 2.0 V) than conventional Li / S cells, making it unfavorable in comparison to Li / S compositions. The overall S content in SPAN is about 30% to 50%, and its capacity can vary from 300 to 800 mAh / g of SPAN. These features can be found in other sulfurized carbon matrix polymers, which can have an overall S content of about 30 to 50 w / w% relative to the total mass of the sulfurized carbon matrix polymer, and a capacity ranging from 300 to 800 mAh / g of active polymer, as will be understood by those skilled in the art.

[0108] In some embodiments, the redox active complex as described herein has the formula (V):

[0109] [ka]

[0110] where Q is a bonded sp2 carbon atom (C) or nitrogen (N);

[0111] [ka]

[0112] represents a single bond or a double bond, S p represents a polysulfide, and p ranges from 2 to 8. wherein the carbon sulfide matrix is ​​represented by The carbon sulfide matrix has a mass average MW ranging from 2000 Daltons to 2,000,000 Daltons, 10,000 Daltons to 1,500,000 Daltons, 100,000 Daltons to 1,000,000 Daltons.

[0113] In some embodiments, the sulfurized carbon matrix has a sulfur content, based on the total weight of the sulfurized carbon matrix, of greater than or equal to 5 wt% and less than 20 wt%, greater than or equal to 20 wt% and less than 40 wt%, greater than or equal to 40 wt% and less than 60 wt%, greater than or equal to 60 wt% and less than 70 wt%, or greater than or equal to 70 wt% and less than 80 wt%.

[0114] In some embodiments, a redox active complex as disclosed herein comprises a carbon sulfide matrix represented by formula (V) where Q is N.

[0115] In some embodiments, a redox-active complex as disclosed herein comprises a carbon sulfide matrix represented by formula (V) where Q is C.

[0116] In some embodiments, the carbon sulfide matrix of formula (V) can be selected from any one of the examples shown in FIG. 4 including carbon sulfide matrix polymer SPAN (11), covalent triazine backbone (S-CTF-1) (12), covalent triazine backbone (S-CTF-1) (13), poly(sulfur random-1,3-diisopropylbenzene) (poly((Sr-DIB) (14), S-BOP (15), carbon / polymeric sulfur (C / PS) composite (16), covalently grafted polysulfur graphene nanocomposite (PolySGN, 17), and graphene-supported crosslinked sulfur copolymer nanoparticle, cp(S-TTCA)@rGO-80 (18), or any combination thereof.

[0117] In some embodiments, the redox active complex as disclosed herein has the formula (I): -[MS p ]- m (In the formula, M is a redox-active monomeric quinone moiety that contains a redox potential between 0.5 V and 3.3 V relative to the Li / Li+ electrode potential under standard conditions; p refers to the number of sulfur atoms linking the redox-active monomeric quinone moieties M, p ranges from 1 to 5; S p is a sulfide when p is 1 or a polysulfide when p is 2 to 5; m ranges from 5 to 10,000) and a solubility in tetrahydrofuran (THF) at room temperature and at 1 atm of 1.0 micrograms per mL or less, preferably a solubility in tetrahydrofuran (THF) at room temperature and at 1 atm of 0.1 micrograms per mL or less, more preferably a solubility in tetrahydrofuran (THF) at room temperature and at 1 atm of 0.01 micrograms per mL or less, and Formula (V)

[0118] [ka]

[0119] where Q is a bonded sp2 carbon atom (C) or nitrogen (N);

[0120] [ka]

[0121] represents a single bond or a double bond, S p represents a polysulfide, and p ranges from 2 to 8. and having a weight average MW of at least 2000, 10,000, 100,000, or 1,000,000, and a weight average MW ranging from 2000 Daltons to 2,000,000 Daltons, 10,000 Daltons to 1,500,000 Daltons, or 100,000 Daltons to 1,000,000 Daltons. Including, The weight ratio of the S-linked quinone polymer represented by formula (I) to the sulfurized polymer represented by formula (V) ranges from 20:1 to 1:20, from 10:1 to 1:10, from 9:1 to 3:2, or from 6:1 to 2:1.

[0122] In some embodiments, the redox-active material as described herein further comprises a binder and a conductive additive, wherein the binder is selected from one of poly(vinylidene-fluoride), poly(tetrafluoroethylene), sodium carboxymethylcellulose, lithium carboxymethylcellulose, potassium carboxymethylcellulose, styrene-butadiene rubber, polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyethylene oxide (PEO), and polyamideimide (PAI), or any combination thereof, and the conductive additive is selected from one of graphite, carbon black, acetylene black, Super-P carbon, graphite, carbon nanotubes, vapor grown carbon fiber, graphene, nickel powder, KB, and SP65, or any combination thereof.

[0123] As used herein, a conductive additive is a solid material that, when present in an electrode composition, enhances the electrical conductivity of the resulting electrode composition.

[0124] In some embodiments, in a redox-active composite as described herein, the binder is present in an amount from 1% to 20% by weight of the total electrode composition, and the conductive additive is present in an amount from 5% to 70% by weight of the total electrode composition.

[0125] In some embodiments, the redox active complex as disclosed herein has the formula (II): -[M1-S p1 ] m1 -co-[M2-S p2 ]- m2 (II) (In the formula, M1 and M2 are redox-active monomeric quinone moieties, each of which comprises a redox potential between 0.5 V and 3.5 V relative to the Li / Li+ electrode potential under standard conditions; p1 and p2 each independently refer to the number of sulfur atoms linking the redox-active monomeric quinone moieties M1 and M2, respectively, and p1 and p2 each independently range from 1 to 5; S p1 is a sulfide when p1 is 1 or a polysulfide when p1 is 2 to 5; S p2 is a sulfide when p2 is 1 or a polysulfide when p2 is 2 to 5; m1 and m2 are each independently in the range of 5 to 5,000, and optionally the ratio of m1 to m2 is in the range of 1:50 to 1:1, 1:20 to 1:2, 1:6 to 1:3, or 1:5 to 1:4. wherein the S-linked quinone copolymer of formula (II) has a weight average molecular weight of at least 1000 Daltons or a weight average MW in the range of 2000 Daltons to 2,000,000 Daltons, 10,000 Daltons to 1,500,000 Daltons, 100,000 Daltons to 1,000,000 Daltons, and a solubility in tetrahydrofuran (THF) at room temperature and 1 atm of 1.0 micrograms per mL or less, preferably a solubility in tetrahydrofuran (THF) at room temperature and 1 atm of 0.1 micrograms per mL or less, more preferably a solubility in tetrahydrofuran (THF) at room temperature and 1 atm of 0.01 micrograms per mL or less, and Formula (V)

[0126] [ka]

[0127] (wherein Q is the bonded S p2 is a carbon atom (C) or nitrogen (N),

[0128] [ka]

[0129] represents a single bond or a double bond, S p represents a polysulfide, and p ranges from 2 to 8. and having a weight average MW of at least 2000, 10,000, 100,000, or 1,000,000, or in the range of 2000 Daltons to 2,000,000 Daltons, 10,000 Daltons to 1,500,000 Daltons, 100,000 Daltons to 1,000,000 Daltons, The weight ratio of the S-linked quinone copolymer represented by formula (II) to the sulfurized polymer represented by formula (V) ranges from 20:1 to 1:20, from 10:1 to 1:10, from 9:1 to 3:2, or from 6:1 to 2:1, or is 1:1.

[0130] In some embodiments, the S-linked polymers, carbon sulfide matrices, and / or composites described herein can be included in a redox-active composition that further comprises one or more additives described herein.

[0131] As used herein, "additive" refers to any component, other than the redox active polymer or carbon sulfide matrix, that enhances the mechanical, physical, electrical or electrochemical properties of the electrode material. Illustrative additives include binders and conductive additives.

[0132] In some embodiments, the S-linked polymers, carbon sulfide matrices, composite materials, and / or redox compositions described herein can be included in a cathode material, particularly a cathode material configured to allow contact with a non-aqueous electrolyte of an electrochemical cell.

[0133] In the embodiments described herein, the disclosed S-linked polymers and / or composites can be included in an electrochemical cell.

[0134] As used herein, "electrochemical cell" refers to a device that can generate electrical energy through a chemical reaction, or that can use electrical energy to drive a chemical reaction, or both.

[0135] Electrochemical cells that generate electric current are called voltaic or galvanic cells, and those that generate chemical reactions via, for example, electrolysis are called electrolytic cells.

[0136] In particular, a voltaic cell (galvanic cell) is an electrochemical cell that generates electrical energy through a redox (reduction-oxidation) reaction in the cell. Electrochemical cells can also use externally applied electrical energy to drive redox reactions within the cell, called electrolytic cells. A fuel cell is an electrochemical cell that generates electrical energy from a fuel through the electrochemical reaction of hydrogen with an oxidant.

[0137] A voltaic cell or redox generating electrochemical cell can include a permeability barrier between two electrodes that allows anions and / or cations to pass from an electrolyte in contact with one electrode to an electrolyte in contact with the other electrode.

[0138] As used herein, "electrode" refers to a conductive material in contact with a non-conductive element. In the case of an electrochemical cell, the non-conductive element is the electrolyte in which the chemical reaction occurs. The two types of electrodes in a cell are the anode and the cathode. The anode is the electrode where oxidation occurs as electrons leave the electrochemical cell. The cathode is the electrode where reduction occurs as electrons enter the cell. By convention, the anode is considered "negative" and the cathode is considered "positive" when producing electrical energy. When the cell is using electrical energy to drive a reaction (e.g., when a rechargeable battery is charging), the cathode is negative with respect to the polarity of the anode, and the convention is usually (but not always) reversed. The cell can be changed between energy production (voltaic) and redox production (electrolytic) by changing the externally applied voltage between the electrodes (changing the direction of the current through the cell).

[0139] "Current" or "electrical flow" in the sense of the description can be described as a flow of positive charge or an equal flow of negative charge in the opposite direction. By convention, electrical flow goes from the cathode to the anode (opposite the flow of electrons) outside the cell, regardless of the method of operation (voltaic versus electrolytic).

[0140] An electrochemical cell as described herein can contain a cathode on a metal substrate with a current collector and an anode on a metal substrate with a current collector, separated by a semi-permeable insulating film. The cell contains a non-aqueous salt solution that conducts ions. These components are placed in a container. Either the cathode or the anode can include a redox-active composition as described herein.

[0141] In particular, in some embodiments, an electrochemical cell is described that includes an anode, a cathode, and a non-aqueous electrolyte, where the anode electrode includes a network polymer of Formula (I) and / or a network dendrimer of Formula (II) as described herein.

[0142] As used herein, "electrolyte" refers to a liquid or a mixture of liquids and solids that contains at least cations and counterions to conduct ions during an electrochemical reaction in an electrochemical cell. In some embodiments, as described herein, the cations of the electrolyte can be lithium ions.

[0143] The electrolyte as described herein can have a mixture of cyclic carbonate, ethyl methyl carbonate (EMC), a flame retardant additive, a lithium salt, and an electrolyte additive with ethylene carbonate (EC) or mono-fluoroethylene carbonate (FEC) co-solvent, which improves compatibility and performance in lithium-ion batteries.

[0144] The lithium salt of the electrolyte as described herein is lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium bis(oxalato)borate (LiBOB), lithium hexafluoroarsenate (LiAsF 6 ), lithium perchlorate (LiClO 4 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium bispentafluoroethanesulfonyl imide (LiN(SO 2 CF 3 ) 2 ), LiFSI, and mixtures thereof.

[0145] The electrolyte additives as described herein include lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiODFB), lithium tetrafluorooxalatophosphate (LiPF 4 (C 2 O 4 )), and mixtures thereof.

[0146] The flame retardant additive of the electrolyte as described herein may be selected from the group consisting of triphenyl phosphate (TPhPh / TPP / TPPa), tributyl phosphate (TBP / TBuPh), triethyl phosphate (TEP / TEtPh), bis(2,2,2-trifluoroethyl)methylphosphonate (BTFEMP / TFMPo), tris(2,2,2-trifluoroethyl)phosphate, diethyl ethylphosphonate, diethyl phenylphosphonate, and mixtures thereof.

[0147] In some embodiments of the disclosed electrochemical cell, the redox-active monomeric moiety contains a thiophene or anthraquinone and the electrolyte is 1.0 M LiPF in EC:DEC (50:50 v / v). 6 EC and DEC stand for ethylene carbonate and diethyl carbonate, respectively.

[0148] In an alternative embodiment, these electrochemical cells contain one or more salts of lithium, sodium and / or potassium, such as lithium hexafluorophosphate (LiPF ), at a concentration of, for example, 0.01 to 1 M. 6 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium trifluoroacetate (LiCF 3 CO 2 ), lithium tetrachloroaluminate (LiAlCl 4 ), lithium bis(trifluoromethanesulfonyl)imide (Li[CF 3 SO 2 ] 2 N, LiTFSI), lithium bis(fluorosulfonyl)imide (Li[FSO 2 ] 2 N, LiFSI), lithium bis(oxalato)borate (Li[CO 4 ] 2The non-aqueous electrolytes may feature lithium iodide (LiB, LiBOB), lithium iodide (LiI), lithium bromide (LiBr), lithium chloride (LiCl) and lithium fluoride (LiF), as well as organic solvents such as propylene carbonate, ethylene carbonate, dialkyl carbonates, DME, dioxolanes, ethers, fluorinated ethers, glymes, acetonitrile, etc. In particular, the electrodes as described in this disclosure may function as cathodes in such non-aqueous cells, and as anodes in low potential metal or alloy species such as, but not limited to, lithium metal, lithiated graphite, lithium-silicon alloys, magnesium or sodium or potassium.

[0149] In such non-aqueous cell embodiments as described above featuring Li metal as the anode, the open circuit voltage of the cell (and therefore the cathode vs. Li + / Li) can be 2.0 to 3.5V.

[0150] A schematic illustration of a possible configuration of an electrochemical cell is illustrated in FIG.

[0151] In particular, the top panel of Figure 31 shows an illustrative electrochemical cell including an anode, a cathode, and an electrolyte disposed between the anode and the cathode, with an optional permeation barrier separating the electrolyte into two ionically communicating portions. The bottom panel of Figure 31 shows an illustrative electrochemical cell in a pouch housing including an anode, a cathode and their respective current collectors, and an electrolyte disposed between the anode and the cathode, with an optional separator separating the electrolyte into two ionically communicating portions. In some embodiments of the present disclosure, one or more electrochemical cells may be included within a battery.

[0152] As used herein, a "battery" is a device consisting of one or more electrical energy generating electrochemical cells arranged in parallel (to increase capacity) or in series (to increase voltage). Battery types include redox active polymer-metal, zinc-carbon, alkaline, nickel-oxyhydroxide, lithium, mercuric oxide, zinc-air, Zamboni pile, silver-oxide, magnesium, nickel-cadmium, lead-acid, nickel-metal hydride, nickel-zinc, silver-zinc, lithium-iron-phosphate, lithium ion, and others that may be understood by those skilled in the art.

[0153] In particular, a battery according to this disclosure can include one or more electrochemical cells as described herein, and can additionally include a first electrode coupled to an anode of the one or more electrochemical cells, a second electrode coupled to a cathode of the one or more electrochemical cells, and a casing or housing that contains the one or more electrochemical cells.

[0154] In some embodiments, a battery within the meaning of the disclosure is composed of one or more electrochemical cells connected in either parallel, series, or series-parallel patterns. In some embodiments, a battery can include multiple electrochemical cells that can be linked in series or parallel based on performance demands, including voltage requirements, capacity requirements.

[0155] In some embodiments, electrochemical cells as described can be electrically connected in series to increase the voltage of the battery.

[0156] In some embodiments, electrochemical cells as described can be electrically connected in parallel to increase the charge capacity of the battery.

[0157] In some embodiments, the batteries as described herein can be in the shape of a pouch, a prism, a cylinder, or a coin.

[0158] Schematic illustrations of the arrangement of electrochemical cells in the battery of the disclosure are illustrated in FIGS.

[0159] FIG. 32 shows an exemplary arrangement of multiple electrochemical cells in a battery. The top panel of FIG. 32 shows multiple electrically connected electrochemical cells electrically connected in parallel, while the bottom panel of FIG. 32 shows multiple electrically connected electrochemical cells electrically connected in series. A battery of three cells connected in parallel has three times the capacity of an individual cell. A battery of three cells connected in series has three times the voltage of an individual cell.

[0160] The top panel of FIG. 33 shows multiple electrically connected electrochemical cells electrically connected in parallel in an overlapping configuration, while the bottom panel of FIG. 33 shows multiple electrically connected electrochemical cells electrically connected in series.

[0161] The battery can be configured as a primary battery, in which the electrochemical reaction between the anode and cathode is substantially irreversible, or as a secondary battery, in which the electrochemical reaction between the anode and cathode is substantially reversible.

[0162] The battery comprising the S-linked quinone polymer, electrode material, electrode and electrochemical cell of the disclosure is a long-life battery. As used herein, long life for a battery refers to a battery that can be charged / discharged for more than 1,000 cycles while retaining 70% of its charge capacity. In some embodiments, the battery as described herein can have a life of at least 4 years. In some embodiments, the battery as described herein can be charged / discharged for more than 1,200 cycles while retaining 70% of its charge capacity.

[0163] The S-linked polymers described herein, sulfurized matrices described herein, and related composites, electrode materials and / or electrodes to be included in electrochemical cells and batteries according to the present disclosure may be provided according to methods identifiable by those of skill in the art upon reading the present disclosure.

[0164] The S-linked polymers described herein to be included in electrochemical cells and batteries according to the present disclosure may be provided according to methods identifiable by those of skill in the art upon reading the present disclosure.

[0165] In some embodiments, a method for making an S-linked quinone polymer includes: Redox-active monomeric quinone monomer X 1 -MX 2 (In the formula, X 1 and X 2 represents a leaving group; Providing a source of sulfide Sp; Redox-active monomeric quinone monomer X 1 -MX 2 with a source of sulfide Sp under suitable conditions and for a sufficient period of time to produce a sulfide compound represented by formula (I) -[MS p ]- m (I) (In the formula, M is a redox-active monomeric quinone moiety having a redox potential of 0.5 V to 3.5 V relative to the Li / Li+ electrode potential under standard conditions; p refers to the number of sulfur atoms linking the redox-active monomeric quinone moieties M, p ranges from 1 to 5; S p is a sulfide when p is 1 or a polysulfide when p is 2 to 5; m ranges from 5 to 10,000) providing an S-linked quinone polymer represented by the S-linked quinone polymer has a weight average molecular weight of at least 1500 Daltons, or a weight average MW in the range of 2000 Daltons to 2,000,000 Daltons, 10,000 Daltons to 1,500,000 Daltons, 100,000 Daltons to 1,000,000 Daltons, and a solubility in tetrahydrofuran (THF) at 1 atm and 21° C. of 1.0 micrograms per mL or less; A method is described, comprising:

[0166] In some embodiments, the leaving groups X1 and X2 are Cl. - , Br - , I - , - O.T.s., - OMS, - OTf, or any other leaving group known to one of skill in the art.

[0167] In some embodiments, the source of sulfide Sp includes, but is not limited to, elemental sulfur S 8 , Na 2 S., K. 2 S., Li 2 S, any other sulfur-containing compound known to one of skill in the art.

[0168] In some embodiments, a method for making an S-linked quinone copolymer includes: Redox-active monomeric quinone monomer X 1 -M1-X 2 , and redox-active monomeric quinone monomer X 1 -M2-X 2 (wherein X 1 and X 2 represents a leaving group; Sulfide S p1 and S p2 providing a source of Redox-active monomeric quinone monomer X 1 -M1-X 2 and redox-active monomeric quinone monomer X 1 -M2-X 2 , sulfide S p1 and S p2 under suitable conditions and for a sufficient period of time to produce a compound of formula (II) -[M1-S p1 ] m1 -co-[M2-S p2 ]- m2 (In the formula, M1 and M2 are redox-active monomeric quinone moieties each comprising a redox potential between 0.5 V and 3.5 V relative to the Li / Li+ electrode potential under standard conditions; p1 and p2 each independently refer to the number of sulfur atoms linking the redox-active monomeric quinone moiety M1 and the monomeric quinone moiety M2, respectively, and p1 and p2 each independently range from 1 to 5; S p1 is a sulfide when p1 is 1 or a polysulfide when p1 is 2 to 5; S p2 is a sulfide when p2 is 1 or a polysulfide when p2 is 2 to 5; m1 and m2 are each independently in the range of 5 to 5,000, and optionally the ratio of m1 to m2 is in the range of 1:50 to 1:1, 1:20 to 1:2, 1:6 to 1:3, or 1:5 to 1:4. providing an S-linked quinone copolymer represented by the S-linked quinone copolymer of formula (II) having a weight average molecular weight in the range of 1,000 to 2,000,000 daltons, or a weight average MW in the range of 2000 to 2,000,000 daltons, 10,000 to 1,500,000 daltons, 100,000 to 1,000,000 daltons, and a solubility in tetrahydrofuran (THF) at 1 atm and 21° C. of 1.0 micrograms per mL or less; A method is described, comprising:

[0169] In some embodiments, the leaving groups X1 and X2 are Cl. - , Br - , I - , - O.T.s., - OMS, - OTf, or any other leaving group known to one of skill in the art.

[0170] In some embodiments, sulfide S p1 and S p2Sources of sulfur include, but are not limited to, elemental sulfur, S 8 , Na 2 S., Li 2 S., K. 2 S, any other sulfur-containing compound known to one of skill in the art.

[0171] Particular chemical moieties, groups and substituents can be selected to provide the desired redox activity, as would be understood by one of skill in the art.

[0172] The term "chemical moiety," as used herein, refers to an atom or group of atoms that, when included in a molecule, participates in the characteristic chemical reaction of that molecule, or that is retained after reaction to become part of the reaction product. Chemical moieties that contain at least one carbon atom are also referred to as organic moieties as understood by those of skill in the art.

[0173] In particular, as used herein, the term "organic moiety" refers to a carbon-containing portion of an organic molecule. For example, within an organic polymer, an organic moiety may be formed by a specific portion of the polymer, such as a specific portion of a monomer that is retained in the polymer following polymerization as part of the monomer unit of the polymer. An exemplary organic moiety is provided by 1,5-dichloroanthraquinone or an anthraquinone moiety that is retained in an S-linked polymer as disclosed herein.

[0174] Illustrative chemical moieties within the meaning of the disclosure are provided by functional groups such as hydrocarbon groups containing double or triple bonds, halogen-containing groups, oxygen-containing groups, nitrogen-containing groups, and phosphorus- and sulfur-containing groups, all identifiable by one of ordinary skill in the art.

[0175] One of skill in the art would be able to identify moieties that can be used in the disclosed methods to provide the disclosed redox-active polycyclic compounds.

[0176] The S-linked polymers, carbon sulfide matrices, redox compositions, redox complexes, and associated electrode materials, electrodes, and electrochemical cells can be included in systems that include the polymers, matrices, compositions, complexes, electrode materials, electrodes, and / or electrochemical cells in various combinations, where they are interconnected in configurations where they work together as part of a mechanism and / or interconnected network according to the methods described herein.

[0177] In summary, electrode materials including S-linked polymers and carbon sulfide matrices are described herein, along with functional electrodes incorporating these species and electrochemical cells and batteries including such electrodes. In certain embodiments, the electrode materials described herein exhibit high mechanical strength and excellent processability into functional electrodes due to their unique composition. Advantageously, in certain embodiments, the electrodes support batteries that charge and recharge for hundreds of cycles without material loss due to the insoluble nature and stability of these organosulfur polymers in the non-aqueous electrolytes used.

[0178] In particular, the S-linked quinone polymers, carbon sulfide matrices, and related compositions, composites, electrode materials, electrodes, electrochemical cells, and related methods and systems can be used in connection with applications where the demand for high energy, high performance, safe and long lasting batteries is growing rapidly due, for example, to environmental concerns, among other things.

[0179] The S-linked quinone polymers, carbon sulfide matrices, and related compositions, composites, electrode materials, electrodes, electrochemical cells, and related methods and systems can be used in conjunction with lithium-ion battery technologies using a variety of cathodes, including NMC, LFP, LMO, and NCA, which are now widely applied in electric vehicle applications.

[0180] In this regard, in some embodiments, the sulfurized carbon matrices and related compositions, composites, electrode materials, electrodes, electrochemical cells, and related methods and systems may be used in conjunction with Li anodes in place of inorganic cathodes, which may be preferable, for example, in light of the cost of Li-ion battery technology, which has been steadily declining over the past 30 years with the adoption of improved processing and manufacturing practices; and in particular, in those embodiments, the S-linked quinone polymers described herein, such as PAQT and 36PPAQS, 27PPAQS, etc., are expected to improve the overall capacity and performance of batteries, as well as composite cathodes of hybrid mixtures of various sulfurized carbon matrix polymers in various proportions, including but not limited to PAQS, PAQT, 36PPAQS, 27PPAQS, PBQS, and SPAN.

[0181] Generally, further details regarding organosulfur polymers, and related compositions, electrochemical cells, batteries, methods and systems, including the manufacture and packaging of organosulfur polymer compositions, electrochemical cells and / or batteries, can be identified by those of skill in the art upon reading this disclosure. EXAMPLES

[0182] The S-linked polymers, carbon sulfide matrices, and related compositions, composites, electrode materials, electrodes, electrochemical cells, batteries, and related methods and systems described herein are further illustrated in the following examples, which are provided by way of illustration and are not intended to be limiting.

[0183] Those of skill in the art will be able to identify additional S-linked polymers, carbon sulfide matrices, and related compositions, compositions, electrode materials, electrodes, electrochemical cells, batteries, methods, and systems in light of the present disclosure. The following specific examples are presented to illustrate the practice of the invention, but should not be construed as limiting the invention in any way.

[0184] In particular, the illustrative redox-active S-linked polymers, carbon sulfide matrices, composites, metals, and related electrode materials, electrodes, devices, compositions, methods, and systems are described with reference to specific experimental tests and procedures. Those skilled in the art will be able to understand and identify the modifications required to adapt the results illustrated in the illustrative embodiments in this section to additional embodiments of the organosulfur polymers, and related electrodes, devices, compositions, methods, and systems according to the present disclosure.

[0185] As can be seen from the examples described herein, the features and performance of these organosulfur polymers described herein support their use as organic electrode materials suitable for a wide range of primary or rechargeable applications, such as batteries for electric vehicles, emergency power sources, local energy storage, starters or ignitions, remote relay stations, communication base stations, uninterruptible power supplies (UPS), stationary batteries for operation reserve, peak shaving, or load leveling, or other grid storage or optimization applications. Small format or miniature battery applications are contemplated, including watch batteries, implantable medical device batteries, or sensing and monitoring system batteries (including gas or electric metering), as well as other portable applications such as flashlights, toys, power tools, portable radios and televisions, mobile phones, video cameras, laptop computers, tablet computers or handheld computers, portable devices, cordless devices, wireless peripherals, or emergency signs. Military or extreme environment applications are also possible, including use in satellites, munitions, robots, unmanned aerial vehicles, or for military emergency power or communications.

[0186] Materials and Methods The following materials and methods can be used for all compounds and their precursors exemplified herein.

[0187] Electrochemical measurements of all S-linked polymers, carbon sulfide matrices and lithium systems were performed using a Biologic SP-150 Potentiostat, a Neware tester or an Arbin tester.

[0188] For all cyclic voltammetry measurements of organosulfur polymers, a beaker-type cell (or interchangeably, as used herein, a beaker cell) was used here. The beaker cell includes a glass container that holds the electrolyte, and the cathodic organosulfur polymer material mixed with conductive carbon and additives is used as the working electrode (WE), and Li / Li + is used as the reference electrode and a Pt wire is used as the counter electrode (CE).

[0189] All polymers of this disclosure were filtered and washed with deionized water and acetone until the solvent passing through the filter was clear.

[0190] Different additives are also used to aid in cell formation as well as electrode conductivity, including but not limited to bismuth oxide, carbon black powder, graphite, carbon fiber, graphene, carbon nanofibers, and carbon fibers.

[0191] Carbon fibers, zirconium fibers, alumina fibers or silicon fibers have all been incorporated into the anode formulation to enhance the adhesion, cohesion and structural features of the cathode or anode.

[0192] Some form of binder is used to hold the cathode or anode to the substrate. Preferred binders can be PTFE, SBR, PVDF, HEC, CMC, gum arabic, xanthan gum, HPMC, and chitosan.

[0193] The cathode or anode can be applied using a wet process by mixing all the active materials and additives and binders with water and then coated or used as a dry powder and pressed onto the aforementioned substrate.

[0194] Example 1 PAQS-SPAN composites representing carbon sulfide matrix polymers Sulfur-linked quinone polymers such as PAQS (poly[anthraquinonyl-sulfide]) have a theoretical capacity of 225 mAh / g, but even with good cycling stability (capable of over 1000 cycles), they deliver only about 160 mAh / g in usable practical cells with lithium anodes at material loadings >60% active cathode (necessary for cells with energy densities for significant commercial applications). Discharge potentials are typically 0.1 to 0.5% for Li + / Li is about 2.5 to 2.0 V.

[0195] Sulfurized carbon matrices such as SPAN (sulfurized poly[acrylonitrile]) exhibit high capacity (over 200 mAh / g at 3.0 to 0.50 V) with better cycling stability compared to standard sulfur cathodes in electrochemical cells with lithium anodes; however, most of the capacity is reached at lower potentials than in conventional Li / S cells, making comparisons with Li / S compositions unfavorable. The overall S content in SPAN is about 25% to 50%, and its capacity can vary from 400 to 800 mAh / g of the total mass of SPAN. Sulfurized carbon matrix polymers typically have the same features of an S content of about 25 w / w% to 50 w / w% relative to the total mass of the sulfurized carbon matrix polymer, and its capacity can vary from 400 to 800 mAh / g of the total mass of the polymer, as will be understood by those skilled in the art.

[0196] The combination of organosulfur polymer and sulfurized polymeric materials, such as PAQS and SPAN, in a hybrid cathode material combination according to the features of the present disclosure is expected to provide an active material that exhibits both the good cycling stability of the constituent PAQS and SPAN, as well as the combined discharge capacity of both materials. In particular, the mixture exhibits excellent cycling stability, for example, for over 100 cycles, as well as excellent discharge capacity of Li + It can provide a capacity of over 250 mAh / g at 3.2 to 1.0 V vs. .mu.l / Li.

[0197] In particular, exemplary organosulfur polymers known or anticipated to be included in the composites of the disclosure include Li +The present invention includes redox active polymers that can undergo reversible redox processes at high potentials vs. Li / Li, increasing the overall energy density of the battery. Exemplary polymers having the above referenced properties include S-linked quinone polymers including 36PPAQS, 27PPAQS and PAQT. Both 36PPAQS and 27PPAQS have capacities of 225 mAh / g each, however, they give 2.8 V batteries when coupled with metallic lithium as the anode in a non-aqueous electrolyte, compared to PAQS at 2.2. V. PAQT has a theoretical capacity of 400 mAh / g and a Li / Li + These new polymers have a redox potential of 2.8 V vs. . Overall, the energy density of these new polymers is higher than that of PAQS alone, as shown in the table in Figure 1.

[0198] An additional exemplary organosulfur polymer usable in the disclosed composites includes an S-linked copolymer of two quinone moieties as a cathode active material for use in non-aqueous rechargeable batteries. PAQS is selected as the major component, and poly-1,4-benzoquinone sulfide (PBQS) is selected as the minor component of the copolymer. A further exemplary organosulfur polymer is a PAQS configured to increase the capacity of PAQS by 20%. 0.8 BQ 0.2 and the like -S linked copolymers.

[0199] Further encompassed in the present disclosure are hybrid mixtures of S-linked quinone polymers containing PAQS and sulfurized carbon matrices such as, but not limited to, sulfurized polyacrylonitrile (SPAN). Even though non-aqueous batteries with PAQS as the cathode active material exhibit excellent cyclability, the energy density is limited by two carbonyl redox active centers resulting in only 225 mAh / g of theoretical capacity. In this disclosure, we contemplate adding high capacity sulfur-containing polymers to PAQS to create hybrid mixtures of cathode materials that provide higher overall capacity and therefore higher energy density batteries. In some embodiments, the energy density can be increased by 20-60% by combining 10-60 wt% of a sulfurized carbon matrix, e.g., SPAN polymer, with an organosulfur polymer, e.g., PAQS material. In some embodiments, the energy density can be increased by 20-250% by combining 10-90 wt% of SPAN or other sulfurized carbon matrix polymer with an organosulfur-S-polymer, e.g., PAQS material.

[0200] In particular, the S-linked quinone polymers described in this disclosure include S-linked condensation polymers based on anthraquinone (AQ), phenanthrenequinone (PAQ), anthracenetetraone (AQT) and 1,4-benzoquinone (BQ), and have a redox potential range of 1.0 V to 3.5 V relative to the Li / Li+ electrode potential under standard conditions. Figure 2 shows exemplary structures of the S-linked quinone polymers.

[0201] Additionally, copolymers of sulfur-linked quinone polymers are useful and can be formed by condensation of appropriate monomers with sulfur materials under typical conditions described below. For example, copolymers of PAQS or PAQT and PBQS can be formed. PAQS is a robust polymer, providing 1000 cycles with >80% active material, but only delivers 160 mAh / g capacity at low rates. This can be improved in a series of PAQS-PBQS or copolymers (e.g., random copolymers) by varying the ratio of monomers. We have achieved a 20% improvement in capacity from PAQS by incorporating up to 20 mol% of PBQS into the copolymer (Figure 3). Similar results can be achieved by using PAQT monomer with PBQS.

[0202] FIG. 3 shows the structure of a PAQS or copolymer of PAQT and PBQS encompassed by this disclosure.

[0203] In particular, embodiments of the present disclosure typically use either high sulfur content polymers or carbon sulfide matrices as one of the components to S-linked quinone polymers (as shown in FIG. 4). The redox potential characteristics of these carbon sulfide matrices are slightly lower but very close to those of quinone-based sulfide (-S-) polymers. The high sulfur content carbon sulfide matrices described in this disclosure were n-type and had redox potential ranges of 1.0V to 2.5V or 11.0V to 3.5V relative to the Li / Li+ electrode potential under standard conditions.

[0204] Figure 4 shows the structure of a carbon sulfide matrix used as one of the components in the -S linked organic quinone polymer. The following description of the properties of the carbon sulfide matrix of the present disclosure is made with reference to a representative sulfurized polyacrylonitrile (SPAN). Related features apply to other carbon sulfide matrices, as will be understood by those skilled in the art upon reading this disclosure.

[0205] Sulfurized polyacrylonitrile (SPAN) is one such material, first reported by Wang et al. in 2002.[6][7][8][9]

[10] SPAN is chemically and electrochemically distinct from elemental sulfur and any elemental sulfur-based composite cathodes. Elemental sulfur is an insulating material with an eight-membered ring structure, whereas SPAN is a conductive material in which active sulfur is chemically embedded in a conductive matrix of carbonized PAN polymer, as shown in Figure 30.

[0206] FIG. 30 shows a comparison of the structures of elemental S and sulfurized polyacrylonitrile (SPAN).

[0207] During discharge, elemental sulfur or sulfur complexes with elemental sulfur are converted to cyclic S-type ions that are soluble in the electrolyte. 8 SPAN forms long linear lithium polysulfides through ring opening of , whereas SPAN has active sulfur moieties covalently attached to the carbon backbone and therefore such long linear lithium polysulfides are not formed. Since there is no long linear polysulfide formation with SPAN, there is therefore no lithium polysulfide dissolution and therefore no shuttle mechanism.

[0208] Additionally, the sulfur content in elemental sulfur is 100%, while the sulfur content in SPAN varies from 30-60% depending on the synthesis. The lower the temperature for synthesis, the lower the sulfur content in the polymer matrix. The synthesis procedure for SPAN used in this disclosure is described in Example 37. The sulfur content is found to be 40% based on TGA and elemental analysis.

[0209] Many examples of modified SPAN and SPAN-like materials are known in the literature and are summarized in FIG.

[0210] Both S and SC cathodes form soluble long-chain polysulfides during discharge. These lithium salts of polysulfides are nucleophilic in nature and can react with any electron-deficient species. In the presence of quinone polymers as co-active materials in hybrid cathodes, the soluble polysulfides react with the carbonyl groups of the polymers, destroying their ability to dissolve Li during cycling. + can be inserted and removed. However, when SPAN is used herein, SC means carbon and S can be written as SC. CS refers to a premix of conductive carbon and sulfur, optionally with additives, since there is no soluble polysulfide formation and therefore no such deleterious reactions occurring during cycling.

[0211] Elemental sulfur is an insulating material. Conductive carbon and additives can be added to elemental sulfur for electronic conduction during battery cycling. Furthermore, elemental sulfur forms polysulfides during discharge, which are soluble in organic electrolytes. The solubility of polysulfide discharge products in the electrolyte causes a shuttling effect that is detrimental to battery performance. To address both challenges, the thermal conductivity of elemental sulfur (S) at various temperatures was investigated. 8 Sulfurized polyacrylonitrile (SPAN) was synthesized through the thermal treatment of sulphuric acid and polyacrylonitrile (PAN).[6] Elemental sulphur is embedded in the framework of the pyrolyzable PAN polymer as C-S bonds in SPAN, as confirmed by FTIR, Raman spectroscopy and XPS.

[11] The conjugated nature of SPAN improves the electrical conductivity of the material, and the C-S bonds throughout the structure prevent the formation of soluble polysulfides. The amount of sulphur in SPAN is about 25-60 wt%.

[0212] Exemplary polymers are described, including PAQT, 36PPAQS, and a random copolymer of PAQS-PBQS. PAQT has a higher voltage and capacity than PAQS. PAQT has a redox voltage and capacity of 2.80 V and 400 mAh / g, respectively, compared to 2.20 V and 225 mAh / g for PAQS. Similarly, 36PPAQS has an improved redox voltage of 2.70 V and capacity of 225 mAh / g, respectively.

[0213] In the experimental data presented here, we found that SPAN acts as a co-active material with PAQS. Both SPAN and PAQS have their signature voltage profiles in the discharge-charge curves. On the other hand, S or SC do not act as co-active materials in the same electrolyte, and the signature voltage profile of PAQS is not evident in the discharge-charge profile when the batteries are assembled and cycled under the same conditions.

[0214] Example 2 anode Anode active materials of the present disclosure include, but are not limited to, metallic lithium in the form of lithium, lithium alloys, e.g., lithium-aluminum alloys, lithium-tin alloys, deposited on a conductive or non-conductive substrate, such as lithium foil, powdered lithium, copper foil, etc. In some embodiments, the anode active material may be metallic sodium, metallic potassium, graphite, hard carbon, silicon-based materials. In some embodiments, the anode may be coated with carbon, graphite, or a non-redox active polymer to prevent dendrite formation during cycling.

[0215] Example 3 Cathode The cathode electrode composition includes PAQS:SPAN active material, one or more conductive carbons, and one or more binder materials. The PAQS and SPAN or other sulfurized polymer composition can vary from 90 wt% to 20 wt% PAQS, or can be lower than 5 wt% PAQS, with the remaining amount of each cathode being 5 wt% to 10 wt% to 80 wt% SPAN material or any other sulfurized polymeric material. In some embodiments, 36PPAQS, PAQT, modified PAQS can be used as the cathode active material or in combinations thereof in various ratios from 20 mol% to 80 mol%, respectively. In some embodiments, various combinations of 36PPAQS:SPAN, PAQT:SPAN, BQ:SPAN, PAQS in 90 wt% down to 20 wt% or 5 wt% 0.8 -BQ 0.2 :SPAN hybrid mixtures may be used in the cathode active material. In some embodiments, an electrode composition may be used that includes an n-type redox polymer, a carbon sulfide matrix polymer, a binder, and a conductive additive.

[0216] Example 4 binder The binder may be one or more selected from the group consisting of 0.5-15% by weight of polytetrafluoroethylene (PTFE), styrene-butadiene or styrene-butadiene rubber (SBR), poly(vinylidene-fluoride) (PVDF), poly(tetrafluoroethylene), sodium or lithium carboxymethylcellulose (CMC), styrene-butadiene rubber, polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyethylene glycol or oxide (PEG or PEO), polyamide-imide (PAI), polyacrylonitrile (PAN), xanthan gum, gum arabic, agar, and any combination thereof. In some embodiments, the electrode composition including the redox polymer and the carbon sulfide matrix polymer may be present at 20% to 80% or 20% to 95% by weight percent of the total electrode composition. With increasing conductivity of the active material or network polymer, the amount of conductive additive in the electrode may be appropriately reduced while maintaining the same degree of conductivity for the electrode composition. With increased stability of the active material or network polymer, the amount of binder in the electrode can be reduced according to the physical stability of the electrode composition. In some embodiments, an electrode composition comprising an n-type redox polymer, a carbon sulfide matrix polymer, and a binder can be used.

[0217] Example 5 Conductive Additives The conductive additive may be one selected from the group consisting of 5-25% by weight of carbon black (Acetylene Black, Super P Li, C-energy, Ketjen Black-300, Ketjen Black-600), Imerys (Super P, Super P C65, C-Nergy), carbon nanotubes (Cnano, Tuball), graphene (xGnP Grade R, xGnP Grade H, xGnP Grade C, xGnP Grade M) and graphite (KS-4, KS-8, KC-4, KC-8), and nickel powder or any combination thereof. As used herein, binder, as used herein, refers to a polymeric material that is non-redox active under the battery working environment but enhances the adhesion of the electrodes.

[0218] Example 6 Mixing Process In the embodiments described herein, the n-type polymer and carbon sulfide matrix polymer of the present disclosure can be incorporated into a functional electrode by mixing with a suitable binder and conductive additive. Mixing methods include planetary mixing and high shear mixing. Electrode coating methods include drop casting, doctor blade casting, spin coating, comma-roll coating, and extrusion. In some embodiments, the composition of the electrode can vary from 30-100 wt% active material, 5-70 wt% conductive additive, and 1-20 wt% binder, with the total wt% of all species being 100%. After such mixing and coating and drying of the electrode, the electrode is pressed through a calendaring process and subsequently heated at a temperature above 50°C. The calendaring can be accomplished using heated or unheated rollers.

[0219] Example 7 Separator The electrochemical cell described in the present invention is composed of an anode, a cathode, an electrolyte, and a separator. The separator is placed between the cathode and the anode, and can be any porous non-conductive polymeric material that is non-reactive and can insulate the anode active material and the cathode active material, but can conduct ions between them. Typical examples of separators include, but are not limited to, polyolefins, such as polyethylene and polypropylene, glass fiber paper, and ceramic materials. In some embodiments, Celgard 2400 is used as the separator. In some embodiments, Celgard 3501 is used as the separator. In some embodiments, Celgard 2325 is used as the separator. In other embodiments, Polypropylene SH2214 is used as the separator. Separators of different thicknesses ranging from 5 microns to 50 microns can be used in the present invention.

[0220] Example 8 electrolyte The non-aqueous electrolytes used in the present invention include, but are not limited to, acyclic ethers, cyclic ethers, glymes, polyethers, sulfolane, sulfone, acetals, ketals, carbonates, dioxolanes, and mixtures thereof. Examples of acyclic ethers include, but are not limited to, 1,2-dimethoxyethane (DME), trimethoxyethane (TME), diethyl ether (DEE), partially fluorinated ethers such as bis(trifluoroethyl)ether (BTFE), perfluorinated ethers, dimethoxypropane, and diethoxyethane. Examples of cyclic ethers include, but are not limited to, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, and 2-methyltetrahydrofuran. Examples of polyethers include, but are not limited to, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), higher molecular weight glymes, diethylene glycol divinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether. Examples of sulfones and sulfolanes include, but are not limited to, 3-methylsulfolane, 3-sulfolene, dimethylsulfone, diethylsulfone, sulfolane, 3-flurosulfolane. Examples of carbonate solvents include, but are not limited to, dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate (PC), ethylene carbonate (EC), vinylene carbonate (VC).

[0221] Examples of lithium salts that may be used in this disclosure include, but are not limited to, LiTFSI, LiOTf, LiClO 4 , LiBF 4 , LiPF 6 , LiSCN, LiI, LiAsF 6 , LiFSI, LiNO 3, LiF, LiOAc, Lithium formate, LiSO 3 CH 3 The concentration of the lithium salt used ranges from 0.5M to 6M.

[0222] Example 9 S-linked polymer (PAQS) cathode The cathodes consisted of various ratios of PAQS active material, conductive carbon, and PVDF binder. A typical cathode consisted of 70 wt% PAQS, 20 wt% SP carbon, and 10 wt% PVDF. First, the PAQS and SP powders were mixed in a coffee mixer. Then, a calculated amount of a 3 wt% PVDF solution in NMP was added to the PAQS:SP mix in a screw-cap cup. The entire mix was then placed in a Thinky centrifugal mixer and mixed three times for 30 seconds at 2000 rpm. The honey-like material was coated onto the carbon-coated aluminum foil using an automated coater. The coated material was then dried under vacuum at 100° C. overnight. The typical thickness of the electrode was about 40-100 microns, and the typical loading of the active material was 3-10 mg / cm. 2 The range is.

[0223] Example 10 36PPAQS cathode The 36PPAQS cathode was prepared by mixing 36PPAQS, SP, KB (Ketjen black) in a mortar using a pestle. A 3 wt% solution of PVDF in NMP was added into the mixed powders in a plastic cup that can be sealed using a screw cap. The entire mixture was then placed in a Thinky centrifugal mixer and spun them at 2000 rpm for 30 seconds three times. The thick solution was coated onto carbon-coated aluminum foil using an automatic coater. The coated foil was then dried under vacuum at 120° C. overnight. The final composition of the electrode was 36PPAQS:SP:KB:PVDF (70:18:2:10).

[0224] Example 11 27PPAQS cathode The 27PPAQS cathode was prepared by mixing 27PPAQS, SP in a mortar using a pestle. A 3 wt% solution of PVDF in NMP was added to the mixed powders in a plastic cup that can be sealed using a screw cap. The entire mixture was then placed in a Thinky centrifugal mixer and spun them at 2000 rpm for 30 seconds three times. The thick solution was coated onto carbon-coated aluminum foil using an automatic coater. The coated foil was then dried under vacuum at 120° C. overnight. The final composition of the electrode was 27PPAQS:SP:PVDF (70:20:10).

[0225] Example 12 PAQT cathode PAQT, SP, PTFE 2 A typical PAQT cathode was prepared by first mixing 100% PVDF in NMP:EtOH (50:50). The solvent was dried at 80° C. overnight. The PAQT:SP:PTFE mixture was then compressed and granulated. A 3 wt% solution of PVDF in NMP was added into the compressed and granulated mixture in a plastic cup that can be sealed using a screw cap. The entire mixture was then placed in a Thinky centrifugal mixer and spun at 2000 rpm for 30 seconds three times. The thick solution was coated onto a carbon-coated aluminum foil using an automatic coater. The coated foil was then dried under vacuum at 120° C. overnight. The final composition of the electrode was PAQT:SP:PTFE:PVDF (70:20:2:8).

[0226] Example 13 PAQS:SPAN cathode Composite hybrid cathodes with various ratios of S-linked quinone polymer to carbon sulfide matrix polymer were prepared. The amount of S-linked quinone polymer PAQS varied from 5 wt% to 80 wt% or 60 wt% to 80 wt% based on the total mass of S-linked quinone polymer and carbon sulfide matrix polymer, with the remainder of the active material being SPAN. A typical procedure for making PAQS:SPAN hybrid cathodes is as follows: First, a specific ratio of SPAN:SP mixture was ball milled for 10 minutes. The SPAN:SP mixture was then added to the PAQS and mixed well using a coffee mixer. A calculated amount of 3 wt% solution of PVDF in NMP was added to the powder mixture of PAQS:SPAN:SP in a cup sealed using a screw cap. The entire mixture was then placed in a Thinky centrifugal mixer and then mixed at least three times for 30 seconds at 2000 rpm. The thick honey-like material was coated onto a carbon-coated aluminum foil. The NMP was dried at 80°C. By following the procedure above, the following PAQS:SPAN cathodes were prepared: (1) PAQS:SPAN:SP:PVDF (45:22:23:10wt%) (2) PAQS:SPAN:SP:PVDF (50:30:10:10wt%) (3) PAQS:SPAN:SP:PVDF (75:15:5:5wt%) (4) PAQS:SPAN:SP:PVDF (75:17:5:3wt%) (5) PAQS:SPAN:SP:PVDF (70:20:5:5wt%) (6) PAQS:SPAN:SP:PVDF (65:25:5:5wt%) (7) PAQS:SPAN:SP:PVDF (60:30:5:5wt%).

[0227] Example 14 PAQS 0.8 BQ 0.2 Electrode preparation Using a Mortar and Pestle, PAQS 0.8 BQ 0.2The copolymer was mixed with Super P (SP) carbon. A 3 wt% solution was added to the mixture. The 3 wt% solution of PVDF in NMP was added into a plastic cup that could be sealed using a screw cap, inside the mixture powder. The whole mixture was then put into a Thinky centrifugal mixer and rotated 3 times at 2000 rpm for 30 seconds. An automatic coater was used to coat the thick solution onto carbon-coated aluminum foil. The coated foil was then dried under vacuum at 100 °C overnight. The final composition of the electrode was PAQS 0.8 BQ 0.2 :SP:PVDF (70:20:10 wt%).

[0228] (Example 15) Electrolyte preparation Appropriate lithium salts and solvents were mixed as described in the following table, inside a glove box with H 2 O and O 2 levels less than 10 ppm. All electrolytes were prepared. The H 2 O content of the electrolytes was measured by a Karl Fischer titrator. The H 2 O level was found to be less than 25 ppm in all electrolytes.

[0229]

Table 2A

[0230]

Table 2B

[0231] (Example 16) Coin cell preparation H 2 O and O 2All 2032 coin cells were assembled inside a glove box with levels below 10 ppm. Lithium foil (0.02 mm thick, MTI) was used as the anode. Celgard 2400 and 2325 polypropylene membranes were used as separators. Typical thicknesses of the electrodes range from 50 to 100 mm. Typical mass loadings are 3 to 10 mg / cm. 2 Typical electrolyte loads range from 50 to 100 mL.

[0232] (Example 17) Li / / 36PPAQS coin cell In this example, 36PPAQS polymer (also referred to herein as Gen 2) was used as the cathode active material. The cathode was prepared by mixing 1.35 g of 36PPAQS polymer:SP:KB (wt ratio of 70:18:2) in a mortar using a pestle. A 3 wt% solution of PVDF in NMP (5.0 g) was added into the mixed powder in a plastic cup. An additional 2.0 g of NMP was added to improve the texture and viscosity of the slurry. The entire mixture was then placed in a Thinky centrifugal mixer and centrifuged three times for 30 seconds at 2000 rpm. The homogeneous viscous solution was coated onto a carbon-coated aluminum foil using an automatic coater. The coated foil was then dried under vacuum at 120° C. overnight and stored in an argon glove box. The final composition of the electrode was 36PPAQS:SP:KB:PVDF (wt ratio of 70:18:2:10).

[0233] Lithium chip (0.02mm, 1.54cm 2 ) as the anode and 36PPAQS:SP:SP:KB:PVDF (2.9 mg, 1.13 cm) as described above. 2 Electrochemical testing was performed using a two-electrode CR2032 coin cell using a 18 mm diameter (2.54 cm) Cr2O3 as the cathode. 2) Celgard 2400 was used as the separator. Various electrolyte formulations were tested, but in this example, 50 μL of 2M LiTFSI (ANA-6) in DME:13DOL (1:1 vol) electrolyte formulation was used. The cell was cycled at a C / 10 rate with a voltage cutoff of 1.6 V to 3.6 V. The C / 10 charge and discharge characteristics of the cell are presented in FIG. 5. This polymer gave a 2.70 V battery when coupled with metallic lithium anodes with mass average MW ranging from 1,000 Da to 2,000,000 Da.

[0234] [ka]

[0235] The cycling performance of the cells assembled in ANA-6 is presented in FIG. 6. A low specific capacity (about 50 mAh / g) was obtained in the initial cycles, which improved with cycling to reach a maximum capacity of 152 mAh / g, about 68% of the theoretical capacity of the polymer. No appreciable capacity loss was observed up to 60 cycles, and then a slight capacity loss was observed up to 100 cycles. The coulombic efficiency was found to be greater than 99.5% for the cells up to 100 cycles (FIG. 7).

[0236] (Example 18) Li / / PAQT coin cell In this example, an S-linked PAQT polymer named Gen3 was used as the cathode active material with a mass average MW ranging from 1,000 Da to 2,000,000 Da. The synthesis of this S-linked quinone polymer is presented in Scheme 4. 1.5 mL of EtOH:H 2 The cathode was prepared by mixing an aqueous suspension of PAQT (0.52 g), SP carbon (0.15 g), and 60% PTFE (0.015 g) in O (1:1). The mixture was mixed in a Thinky centrifugal mixer at 2000 rpm for 30 seconds. EtOH:H 2The O-solvent mixture was dried at 80° C. overnight and the remaining powder was then compressed and granulated to a fine powder. A 3 wt % solution of PVDF in NMP (2.0 g) was added to the granulated powder (0.72 g) in a plastic cup. The entire mixture was then placed in a Thinky centrifugal mixer and centrifuged three times for 30 seconds at 2000 rpm. To obtain the appropriate slurry viscosity and texture, an additional amount of pure NMP was added to the mixture, which was then subsequently centrifuged at 2000 rpm for 30 seconds. A total of 3.0 g of NMP was added to the mixture. The homogenous viscous slurry was coated onto carbon-coated aluminum foil using an automated coater. The coated foil was then dried under vacuum at 120° C. overnight and spun into a 100% aqueous solution of 100% PVDF. 2 O and O 2 It was stored in an argon glove box with levels below 10 ppm.The final composition of the electrode was PAQT:SP:PTFE:PVDF (wt ratio of 70:20:2:8).

[0237] [ka]

[0238] Lithium chip (thickness 0.02mm, 1.54cm 2 ) as the anode and the PAQT:SP:PTFE:PVDF (4.57 mg, 1.13 cm) described above. 2 Electrochemical testing was performed using a two-electrode CR2032 coin cell using a 18 mm diameter (2.54 cm) Cr2O3 as the cathode. 2 Celgard 2400 was used as the separator. Various electrolyte formulations were tested, but in this example, DME:13DOL (1:1 vol) + 100 mM LiNO 3 60 μL of 2M LiTFSI (ANA-7) in the electrolyte formulation was found to give the best cycling data. The C / 10 charge and discharge characteristics of the cell are presented in FIG. 8. This PAQT polymer gave a 2.80 V battery when coupled to a metallic lithium anode.

[0239] The voltage profile (charge and discharge characteristics) of the Li / / PAQT cell in ANA-7 at C / 10 is shown in FIG.

[0240] The galvanostatic cycling profile of the Li / / PAQT cell in ANA-7 electrolyte at C / 10 is presented in FIG. 9. PAQT is a sulfide polymer with four carbonyl groups in its structure that can exchange 4e- during cycling, which is equivalent to a theoretical specific capacity of 400 mAh / g. In our experiments, the Li / / PAQT2032 coin cell shows 162 mAh / g of capacity at C / 10 as shown in FIG. 8. A low specific capacity (about 50 mAh / g) was obtained in the early cycles, suggesting reorganization and wetting of the electrodes, which is probably related to the high viscosity of the applied electrolyte. The specific capacity improved with cycling, reaching a maximum capacity of 162 mAh / g after 50 cycles, which is about 40% of the theoretical capacity of the polymer. No capacity loss was observed up to 124 cycles. The coulombic efficiency was found to be greater than 99.8% for up to 124 cycles of the cell (FIG. 10).

[0241] Li / / PAQS:SPAN coin cell example (Example 19) Li / / PAQS:SPAN:SP:PVDF (45:22:23:10) coin cell In this example, a hybrid mixture of PAQS and sulfurized organic sulfur polymer (SPAN) was used as the cathode active material. First, the cathode was prepared by ball milling a 1:1 mixture of SPAN and SP in a high energy ball grinder for 30 minutes. Then, 0.22 g of the SPAN:SP (1:1) mixture was taken in a mortar, and then PAQS (0.24 g) was added to it, and they were mixed well using a pestle. The entire mixture was taken in a plastic cup, and a 3 wt% solution of PVDF in NMP (1.70 g) was added. The closed cup with the mixture was then placed in a Thinky centrifugal mixer and centrifuged three times for 30 seconds at 2000 rpm. A homogeneous looking viscous slurry was obtained, which was coated onto a carbon-coated aluminum foil using an automatic coater. The coated foil was then dried under vacuum at 80° C. overnight and heated at 1000° C. for 30 minutes. The mixture was then ... 2 O and O 2 It was stored in an argon glove box with levels below 10 ppm. The final composition of the electrode was PAQS:SPAN:SP:PVDF (wt ratio of 45:22:23:10).

[0242] FIG. 11 shows the voltage profile (charge and discharge characteristics) of the Li / / PAQS:SPAN cell in ANA-4 at C / 10.

[0243] Lithium chip (thickness 0.02mm, 1.54cm 2 ) as the anode and PAQS:SPAN:SP:PVDF (2.90 mg, 1.13 cm 2 Electrochemical testing was performed using a two-electrode CR2032 coin cell using a 18 mm diameter (2.54 cm) Cr2O3 as the cathode. 2) Celgard 2400 was used as the separator. Various electrolyte formulations were tested, but in this example, 80 μL of 1M LiTFSI (ANA-4) in DME:13DOL (1:1 vol) electrolyte formulation was found to give the best cycling data (FIG. 11). The cells were cycled at C / 10 with a voltage cutoff of 3.1 V to 1.1 V. This PAQS:SPAN hybrid mix of polymers gave an average 2.0 V battery when coupled to a metallic lithium anode (FIG. 11). The overall discharge capacity of the cell was found to be 285 mAh / g, which is more than 75% higher than the cathode with the PAQS polymer alone.

[0244] FIG. 12 shows the discharge capacity vs. cycle number of Li / / PAQS:SPAN cells in ANA-4 at C / 10. The discharge capacity vs. cycle number is presented in FIG. 12. The data shows remarkable stability of the discharge capacity up to 82 cycles. The coulombic efficiency vs. cycle number is presented in FIG. 13, which shows excellent coulombic efficiency up to 81 cycles. FIG. 13 shows the coulombic efficiency vs. cycle number of Li / / PAQS:SPAN cells in ANA-4 at C / 10.

[0245] The overall energy density (kWh / kg) of the system versus cycle number is presented in Figure 14. The overall energy density was found to be over 550Wh / kg and was surprisingly stable up to at least 82 cycles.

[0246] FIG. 14 shows the energy density (kWh / g) versus cycle number of Li / / PAQS:SPAN cells in ANA-4 at C / 10.

[0247] (Example 20) PAQS:SPAN:SP:PTFE:PVDF (48:38:10:1:4) In this example, a PAQS:SPAN hybrid mixture of polymers was used as the cathode active material. First, 0.34 g of PAQS polymer, 1.0 mL of EtOH:H 2The cathode was prepared by mixing 0.27 g of SPAN and SP carbon + PTFE (0.07 g) in O (1:1). The mixture was mixed in a Thinky centrifugal mixer at 2000 rpm for 30 seconds. EtOH:H 2 The 0-solvent mixture was dried at 80° C. overnight and the remaining powder was then compressed and granulated into a fine powder. A 3 wt % solution of PVDF in NMP (0.9 g) was added to the granulated powder (0.72 g) in a plastic cup. The entire mixture was then placed in a Thinky centrifugal mixer and centrifuged three times for 30 seconds at 2000 rpm. To obtain the appropriate slurry viscosity and texture, an additional amount of pure NMP was added to the mixture, which was then subsequently centrifuged at 2000 rpm for 30 seconds. A total of 0.2 g of NMP was added to the mixture. The homogenous viscous slurry was coated onto carbon-coated aluminum foil using an automated coater. The coated foil was then dried under vacuum at 100° C. overnight and spun into a 100° C. spun ... 2 O and O 2 It was stored in an argon glove box with levels below 10 ppm. The final composition of the electrode was PAQS:SPAN:SP:PTFE:PVDF (wt ratio of 48:38:9:1:4).

[0248] FIG. 15 shows the voltage profile (charge and discharge characteristics) of the Li / / PAQS:SPAN (48:38) cell in ANA-6 at C / 10.

[0249] Lithium chip (thickness 0.02mm, 1.54cm 2 ) as the anode and the PAQS:SPAN:SP:PTFE:PVDF (3.23 mg, 1.13 cm) described above. 2 Electrochemical testing was performed using a two-electrode CR2032 coin cell using a 18 mm diameter (2.54 cm) Cr2O3 as the cathode. 2) Celgard 2400 was used as the separator. Various electrolyte formulations were tested, but in this example, 80 μL of 2M LiTFSI (ANA-6) in DME:13DOL (1:1 vol) electrolyte formulation was found to give the best cycling data (FIG. 16). The cell was cycled at C / 10 with a voltage cutoff of 3.1 V to 1.1 V. The C / 10 charge and discharge characteristics of the cell are presented in FIG. 15. The overall discharge capacity of the cell was found to be 235 mAh / g, which is more than 47% higher than the cathode with PAQS polymer alone. The discharge capacity is slightly lower than the cell described in the previous example, which may be due to the addition of 1% PTFE in the cathode.

[0250] FIG. 16 shows the discharge capacity vs. cycle number of Li / / PAQS:SPAN (48:38) cells in ANA-6 at C / 10. The discharge capacity vs. cycle number is presented in FIG. 16. The data shows a remarkable stability of the discharge capacity up to 18 cycles. The coulombic efficiency vs. cycle number is presented in FIG. 17, which shows 100% coulombic efficiency up to 18 cycles. FIG. 17 shows the coulombic efficiency vs. cycle number of Li / / PAQS:SPAN (48:38) cells in ANA-6 at C / 10.

[0251] Example 21 PAQS:SPAN:SP:PVDF (70:20:5:5) In this example, a hybrid mixture of PAQS and sulfurized polyacrylonitrile polymer (SPAN) was used as the cathode active material. The cathode was prepared by first mixing PAQS (0.70 g), SPAN (0.20 g) and SP (0.05 g) together in a mortar and pestle. The entire mixture was taken in a plastic cup and a 3 wt% solution of PVDF in NMP (1.70 g) was added. The cup with the mixture was then placed in a Thinky centrifugal mixer and centrifuged three times for 30 seconds at 2000 rpm. To obtain the appropriate slurry viscosity and texture, additional amounts of pure NMP were added sequentially to the mixture, which was then subsequently centrifuged at 2000 rpm for 30 seconds. A total of 0.5 g of pure NMP was added to the mixture. A homogeneous looking viscous slurry was obtained, which was then coated onto a carbon-coated aluminum foil using an automatic coater. The coated foil was then dried under vacuum at 80° C. overnight and centrifuged at 2000 rpm for 30 seconds. 2 O and O 2 It was stored in an argon glove box with levels below 10 ppm. The final composition of the electrode was PAQS:SPAN:SP:PVDF (70:20:5:5 wt ratio).

[0252] FIG. 18 shows the voltage profile (charge and discharge characteristics) of the Li / / PAQS:SPAN (70:20) cell in ANA-4 at C / 10.

[0253] Lithium chip (thickness 0.02mm, 1.54cm 2 ) as the anode and PAQS:SPAN:SP:PTFE:PVDF (6.70 mg, 1.13 cm) as described above. 2 Electrochemical testing was performed using a two-electrode CR2032 coin cell using a 18 mm diameter (2.54 cm) Cr2O3 as the cathode. 2) Celgard 2400 was used as the separator. Various electrolyte formulations were tested, but in this example, 80 μL of 1M LiTFSI (ANA-4) in DME:13DOL (1:1 vol) electrolyte formulation was found to give the best cycling data (FIG. 18). The cell was cycled at C / 10 with a voltage cutoff of 3.1 V to 1.1 V. The C / 10 charge and discharge characteristics of the cell are presented in FIG. 18. The overall discharge capacity of the cell was found to be 225 mAh / g, which is more than 40% higher than the cathode with the PAQS polymer alone.

[0254] FIG. 19 shows the discharge capacity vs. cycle number of Li / / PAQS:SPAN (70:20) cells in ANA-4 at C / 10. The discharge capacity vs. cycle number is presented in FIG. 19. The data shows a remarkable stability of the discharge capacity up to 10 cycles. The coulombic efficiency vs. cycle number is presented in FIG. 20, which shows 100% coulombic efficiency up to 10 cycles. FIG. 20 shows the coulombic efficiency vs. cycle number of Li / / PAQS:SPAN (70:20) cells in ANA-4 at C / 10.

[0255] Example 22 PAQS-PBQS Random Copolymers as Cathode Active Materials The overall capacity of PAQS can be improved by incorporating lower molecular weight monomers, such as benzoquinone (BQ), into the polymer backbone. The synthesis of PAQS-PBQS copolymers is described in Scheme 5, reported in Example 34.

[0256] In this example, a copolymer having 80 mol % PAQS and 20 mol % PBQS was used as the cathode active material. First, 0.35 g of PAQS was mixed using a mortar and pestle. 0.8 -PBQS 0.2The cathode was prepared by mixing the copolymer and 0.10 g of SP carbon. A 3 wt% solution of PVDF in NMP (1.70 g) was added to the mixed powder (0.45 g) in a plastic cup. The entire mixture was then placed in a Thinky centrifugal mixer and centrifuged three times for 30 seconds at 2000 rpm. To obtain the appropriate slurry viscosity and texture, an additional amount of pure NMP was added to the mixture, which was then subsequently centrifuged at 2000 rpm for 30 seconds. A total of 0.2 g of NMP was added to the mixture. The homogenous viscous slurry was coated onto carbon-coated aluminum foil using an automated coater. The coated foil was then dried under vacuum at 100° C. overnight and centrifuged at 2000 rpm for 30 seconds. 2 O and O 2 The electrodes were stored in an argon glove box with levels below 10 ppm. The final composition of the electrodes was determined using the PAQS 0.8 -PBQS 0.2 :SP:PVDF (wt ratio of 70:20:10).

[0257] Figure 21 shows the Li / / PAQS for ANA-4 at C / 10. 0.8 -PBQS 0.2 The voltage profile (charge and discharge characteristics) of the cell is shown.

[0258] Lithium chip (thickness 0.02mm, 1.54cm 2 ) as the anode and the PAQS described above. 0.8 -PBQS 0.2 :SP:PVDF (2.9mg, 1.13cm 2 Electrochemical testing was performed using a two-electrode CR2032 coin cell using a 18 mm diameter (2.54 cm) Cr2O3 as the cathode. 2) Celgard 2400 was used as the separator. Various electrolyte formulations were tested, but in this example, 80 μL of 1M LiTFSI (ANA-4) in DME:13DOL (1:1 vol) electrolyte formulation was found to give the best cycling data (FIG. 21). The cell was cycled at C / 10 with a voltage cutoff of 3.2V to 1.6V. The C / 10 charge and discharge characteristics of the cell are presented in FIG. 22. The overall discharge capacity of the cell was found to be 205 mAh / g, which is more than 25% higher than the cathode with the PAQS polymer alone.

[0259] Figure 22 shows the Li / / PAQS for ANA-4 at C / 10. 0.8 -PBQS 0.2 The discharge capacity of the cells versus cycle number is shown.

[0260] Discharge capacity versus cycle number is presented in Figure 22. The data shows a slight fade in discharge capacity up to cycle 78. Coulombic efficiency versus cycle number is presented in Figure 23, which shows 98% coulombic efficiency up to cycle 78.

[0261] Figure 23 shows the Li / / PAQS for ANA-4 at C / 10. 0.8 -PBQS 0.2 The coulombic efficiency of the cell versus cycle number is shown.

[0262] Example 23 PAQS:Sulfur Composite (SC) as Cathode Active Material Sulfur cathodes in non-aqueous lithium-sulfur batteries are known to form lithium polysulfides during discharge. The dissolution of polysulfides into the electrolyte and their migration from the cathode to the anode, which causes the shuttling phenomenon during charging, is one of the major obstacles for lithium-sulfur batteries to become a practical rechargeable battery technology. To demonstrate the advantage of choosing the PAQS:SPAN hybrid cathode, we prepared a PAQS:SC hybrid cathode and cycled the Li / / PAQS:SC cell by following the same protocol as the Li / / PAQS:SPAN cell in the same electrolyte.

[0263] Sulfur-carbon (SC) composite was purchased from MSE supplies (product number PO5018). The sulfur content of the composite was reported to be 75 wt%. The cathode was prepared by first mixing the SC composite (0.29 g), PAQS (0.57 g), SP (0.08 g) and KB (0.02 g) together in a mortar and pestle. The entire mixture was taken in a plastic cup and a 3 wt% solution of PVDF in NMP (1.30 g) was added. The cup with the mixture was then placed in a Thinky centrifugal mixer and centrifuged three times for 30 seconds at 2000 rpm. A homogeneous looking viscous slurry was obtained, which was then coated onto carbon-coated aluminum foil using an automatic coater. The coated foil was then dried under vacuum at 80° C. overnight and heated at 1000° C. for 1 hour. 2 O and O 2 It was stored in an argon glove box with levels below 10 ppm.The final composition of the electrode was PAQS:SC:SP:KB:PVDF (wt ratio of 57:29:8:2:4).

[0264] FIG. 24 shows the voltage profile (charge and discharge characteristics) of the Li / / PAQS:SC cell in ANA-4 at C / 10.

[0265] Lithium chip (thickness 0.02mm, 1.54cm 2) as the anode and PAQS:SC:SP:KB:PVDF (6.15 mg, 1.13 cm 2 Electrochemical testing was performed using a two-electrode CR2032 coin cell using a 18 mm diameter (2.54 cm) Cr2O3 as the cathode. 2 ) Celgard 2400 was used as the separator. 80 μL of 1M LiTFSI (ANA-4) in DME:13DOL (1:1 vol) electrolyte formulation was used. The cell was cycled at C / 10 with a voltage cutoff of 3.2 V to 1.1 V. The C / 10 charge and discharge characteristics of the cell are presented in FIG. 24. The cycling data showed significant overcharging during charging, indicating a shuttling mechanism.

[0266] FIG. 25 shows the discharge capacity versus cycle number of Li / / PAQS:SC cells in ANA-4 at C / 10.

[0267] The discharge capacity of the cells versus cycle number is presented in Figure 25. The data shows a significant fade in discharge capacity up to cycle 17. The coulombic efficiency versus cycle number is presented in Figure 26. The data shows a significant fade in coulombic efficiency with cycling, which is mainly due to the polysulfide shuttling mechanism.

[0268] FIG. 26 shows the coulombic efficiency vs. cycle number of the Li / / PAQS:SC cell in ANA-4 at C / 10.

[0269] (Example 24) PAQS: Elemental Sulfur as Cathode Active Material In this example, the cathode was prepared by first mixing PAQS (0.57 g), elemental S (0.29 g), SP (0.08 g), and KB (0.02 g) together in a mortar and pestle. The entire mixture was taken into a plastic cup and a 3 wt% solution of PVDF in NMP (1.30 g) was added. The cup with the mixture was then placed in a Thinky centrifugal mixer and centrifuged three times for 30 seconds at 2000 rpm. To obtain the appropriate slurry viscosity and texture, an additional amount of pure NMP was added to the mixture, which was then subsequently centrifuged at 2000 rpm for 30 seconds. A total of 0.25 g of NMP was added to the mixture. A homogeneous looking viscous slurry was obtained, which was then coated onto a carbon-coated aluminum foil using an automated coater. The coated foil was then dried under vacuum at 80° C. overnight and centrifuged at 2000 rpm for 30 seconds. 2 O and O 2 It was stored in an argon glove box with levels below 10 ppm. The final composition of the electrode was PAQS:S:SP:KB:PVDF (wt ratio of 57:29:8:2:4).

[0270] FIG. 27 shows the voltage profile (charge and discharge characteristics) of the Li / / PAQS:S cell in ANA-4 at C / 10.

[0271] Lithium chip (thickness 0.02mm, 1.54cm 2 ) as the anode and PAQS:S:SP:KB:PVDF (6.0 mg, 1.13 cm 2 Electrochemical testing was performed using a two-electrode CR2032 coin cell using a 18 mm diameter (2.54 cm) Cr2O3 as the cathode. 2 ) Celgard 2400 was used as the separator. 80 μL of 1M LiTFSI (ANA-4) in DME:13DOL (1:1 vol) electrolyte formulation was used. The cell was cycled at C / 10 with a voltage cutoff of 3.2 V to 1.1 V. The C / 10 charge and discharge characteristics of the cell are presented in FIG. 27. The cycling data showed significant overcharge during charging, indicating a polysulfide shuttling mechanism.

[0272] FIG. 28 shows the discharge capacity versus cycle number of Li / / PAQS:S cells in ANA-4 at C / 10.

[0273] The discharge capacity of the cell versus cycle number is presented in Figure 28. The data shows a significant fade in discharge capacity at just four cycles. The coulombic efficiency data shows a significant fade in coulombic efficiency at only four cycles (Figure 29), which is primarily due to the polysulfide shuttling mechanism.

[0274] FIG. 29 shows the coulombic efficiency versus cycle number of the Li / / PAQS:S cell in ANA-4 at C / 10.

[0275] (Example 25) Comparison between the PAQS:SPAN system and the PAQS:SC or PAQS:S system A comparison between SPAN / PAQS and SC composite / PAQS shows the advantage of SPAN. Electrochemical performance data for cells (ANA-4) with PAQS:SPAN, PAQS:SC and PAQS:S hybrid cathodes with metallic lithium anodes in the same non-aqueous electrolyte are shown in Figures 11-14 and 24-29, respectively. It is evident from the voltage profiles (Figures 11, 24, 27) and cycling data (Figures 12, 25, 28) that the cells with PAQS:SPAN hybrid cathodes performed significantly better than the cells with PAQS:SC and PAQS:S cathodes. The PAQS:SPAN hybrid cathode of the present invention exhibits the highest discharge capacity (286 mAh / g) as shown in Figure 11, compared to the PAQS:SC composite (Figure 24) and PAQS:S (Figure 27) hybrid cathodes. The SPAN materials used in this disclosure are high sulfur content (up to 40 wt% or higher). The conductive material with -S- is embedded in the conductive matrix of pyrolyzed polyacrylonitrile. Because the active sulfur is embedded in the matrix of the polymer, the cells with PAQS:SPAN cathodes showed superior cycling stability (Figure 12) and superior coulombic efficiency (Figure 13) compared to the SC and elemental sulfur cathodes. Both the PAQS:SC and PAQS:S cathodes showed significant overcharge, as shown in Figures 24 and 27, respectively, and poor coulombic efficiency, as shown in Figures 26 and 29, respectively. The high overcharge and low coulombic efficiency are believed to be due to the formation of soluble polysulfides during discharge. The present PAQS:SPAN hybrid cathodes provide stable high energy density systems (greater than 500 Wh / kg) as shown in Figure 14. Additional data reported in Example 4 and Figure 37 show that in some cases, the PAQS:SPAN hybrid cathodes can provide stable high energy density systems of greater than 650 Wh / kg.

[0276] (Example 26) Synthesis of PAQS

[0277] [ka]

[0278] A solution of 2,5-dichloroanthraquinone (25.00 g, 90.22 mmol) in NMP (200 mL) was added to a 1 L round-bottom flask under argon with Na 2 S.xH 2 O (60%, 11.73 g, 90.22 mmol) was slowly added. The mixture was stirred at room temperature under argon atmosphere for 15 min and then heated to 150° C. for 6 h. Heating was turned off and the mixture was allowed to cool to room temperature. The precipitate was then filtered off and washed with NMP, then water and then acetone. The brown solid product of PAQS (22.0 g) was dried at 120° C. overnight. The formation of PAQS polymer and its purity were verified by elemental analysis and TGA analysis. The data showed that the measured values ​​of C, H, and S in PAQS were found to be 67.08%, 2.55%, and 12.95%, respectively, which indicates that the C 14 H 6 The empirical formula for C corresponds to 70.57%, 2.54%, and 13.43% for S. Approximate calculations for C, H, and S are 70.57%, 2.54%, and 13.43%, respectively. The measured and calculated values ​​are within close agreement. The TGA data shows no mass loss up to 420°C.

[0279] Example 27 Synthesis of 36PPAQS

[0280] [ka]

[0281] In an argon-filled glove box, a solution of 3,6-dibromo-phenanthrenequinone (2.0 g, 5.46 mmol) in NMP (15 mL) in a 40 mL vial was added with Na 2 S.xH 2O (60%, 0.71 g, 5.46 mmol) was slowly added. The mixture was stirred at room temperature under argon atmosphere for 15 min, then the reaction vial was removed from the glove box and heating to 110° C. was started. The reaction mixture was heated at 110° C. for 16 h. It was then turned off the heat and allowed to cool to room temperature, and a brown solution was observed with some precipitate. 5 mL of EtOH was added to the solution and stirred for 3 h. A brown precipitate appeared. The precipitate was then filtered off and washed with NMP, then water, and then acetone. The brown solid product of 36PPAQS (1.10 g) was dried at 120° C. overnight. The product was characterized by elemental analysis and by TGA. The data showed that the measured values ​​of C, H, and S in 36PAQS were found to be 66.55%, 2.68%, and 13.21%, respectively, which indicates that C 14 H 6 The empirical formula for C corresponds to 69.98%, 3.36%, and 13.35% for S. Approximate calculations for C, H, and S are 69.98%, 3.36%, and 13.35%, respectively. The measured and calculated values ​​are within close agreement. The TGA data shows no mass loss up to 400 °C.

[0282] 36PPAQS was further synthesized following the same procedures and conditions described above using different reaction solvents such as sulfolane, DMA, DMF, DMSO, and sulfolane / NMP mixtures.

[0283] (Example 28) Synthesis of 27PPAQS

[0284] [ka]

[0285] In an argon-filled glove box, a solution of 2,7-dibromo-phenanthrenequinone (2.0 g, 5.46 mmol) in NMP (15 mL) in a 40 mL vial was added with Na 2 S.xH 2O (60%, 0.71 g, 5.46 mmol) was added slowly. The mixture was stirred at room temperature under argon atmosphere for 20 min, then the reaction vial was removed from the glove box and heating to 120° C. was started. The reaction mixture was heated at 120° C. for 15 h. It was then turned off the heat and allowed to cool to room temperature, and a brown solution was observed with some precipitate. 6 mL of EtOH was added to the solution and stirred for 3 h. A brown precipitate appeared. The precipitate was then filtered off and washed with NMP, then water, and then acetone. The brown solid product of 27PPAQS (1.0 g) was dried at 110° C. overnight. The product was characterized by elemental analysis and by TGA. The data showed that the measured values ​​of C, H, and S in 27PAQS were found to be 66.75%, 2.98%, and 13.10%, respectively, which indicates that C 14 H 6 The empirical formula for C corresponds to 69.98%, 3.36%, and 13.35% for S. Approximate calculations for C, H, and S are 69.98%, 3.36%, and 13.35%, respectively. The measured and calculated values ​​are within close agreement. The TGA data shows no mass loss up to 400 °C.

[0286] (Example 29) Synthesis of PAQT Poly(1,2,5,6-anthracenetetrarone sulfide) (PAQT) was synthesized in four steps:

[0287] [ka]

[0288] (Example 30) Synthesis of 2,6-dihydroxyanthracene (1)

[0289] [ka]

[0290] In a 250 mL two-neck round bottom flask equipped with a stir bar and headspace blanketed with inert gas, sodium borohydride (3.54 g, 93.5 mmol) in 1 M sodium carbonate solution (78 mL) was added. Anthraflavic acid (1, 1.50 g, 6.54 mmol) was then added in batches to the reaction mixture, which was then allowed to stir at room temperature overnight. The reaction mixture was poured into cold 6 M hydrochloric acid (13 mL). The aqueous layer was extracted three times with ethyl acetate. The combined organic layers were then washed with saturated sodium bicarbonate solution and anhydrous Na 2 SO 4 The solution was filtered and concentrated under reduced pressure to give a light brown powder. The solid was dried under vacuum at 60° C. overnight to give 1.3 g solid (2), 99% yield.

[0291] 1 H-NMR (DMSO-d6, 300 MHz): δ: 9.67 (s, 2H), 8.15 (s, 2H), 7.84 (d, J = 9 Hz, 2H), 7.14 (s, 2H) and 7.09 (d, J = 6.9 Hz).

[0292] (Example 31) Synthesis of 1,2,5,6-anthracenetetraone (3)

[0293] [ka]

[0294] 2,6-Dihydroxyanthracene (2, 0.5 g, 2.38 mmol) was dissolved in dry THF (48 mL) and purged with argon. The solution was then added portionwise under argon (in a three-necked round-bottom flask equipped with an argon balloon and a reflux condenser with a thermometer) to a stirred solution of benzeneseleninic anhydride (1.71 g, 4.76 mmol) in dry THF (100 mL). The reaction was heated to 50° C. for 3 hours and then allowed to cool to room temperature. After overnight storage, the solvent and volatile by-products were removed in vacuo using a rotary evaporator and placed in a fume hood to prevent inhalation of the volatile selenium by-products. The crude material was stirred overnight in 1,4-dioxane and filtered to give 460 mg of a red solid (3), 81% yield.

[0295] 1 HNMR (DMSO-d6, 300 MHz): δ: 8.20 (s, 2H), 7.89 (d, J = 9 Hz, 2H), 6.58 and (d, J = 10.2 Hz, 2H)

[0296] Example 32 Synthesis of 9,10-dibromo-1,2,5,6-anthracenetetraone (4)

[0297] [ka]

[0298] To a solution of 1,2,5,6-anthracenetetraone (3, 0.25 g, 1.05 mmol) in acetonitrile (16 mL) in a round bottom flask equipped with a stir bar, N-bromosuccinimide (0.75, 4.20 mmol) was added in one portion. The resulting mixture was allowed to stir at room temperature overnight. The reaction was allowed to come to room temperature and poured into 30 mL of ice water. The precipitate was filtered, washed with water (3x) and hexanes (3x), and dried under high vacuum at 100 C to give 310 mg of a dark green solid (4), 75% yield.

[0299] 1 H-NMR (DMSO-d6, 300 MHz): δ: 8.26 (d, J = 6.3 Hz, 2H) and 8.05 (d, J = 6.3 Hz, 2H).

[0300] (Example 33) Synthesis of polyanthracenetetrarone sulfide (PAQT) (5)

[0301] [ka]

[0302] To a solution of 4,8-dibromo-1,2,5,6-anthracenetetraone (0.10 g, 0.25 mmol) in anhydrous NMP (0.6 mL) in a round bottom flask was added sodium sulfide (anhydrous) (0.020 g, 0.25 mmol). The reaction mixture was heated to 100° C. overnight. The resulting mixture was allowed to reach room temperature and the precipitate was filtered. The precipitate was washed with hot water (3×) and acetone (3×). The precipitate was dried overnight under high vacuum at 110° C. to give 80 mg of a dark grey solid (PAQT), 100% yield. The product was characterized by elemental analysis. The data show that the measured values ​​of C, H, and S in PAQT are found to be 65.12%, 2.74%, and 16.10%, respectively. The approximate calculated values ​​of C, H, and S are 63.48%, 2.66%, and 16.95%, respectively. The measured and calculated values ​​are within close agreement.

[0303] (Example 34) Synthesis of poly-anthraquinone-benzoquinone sulfides

[0304] [ka]

[0305] Under argon, 1,5-dichloroanthraquinone (1.0 g, 3.6 mmol), 2,5-dichloro-1,4-benzoquinone (0.2 g, 1.1 mmol), anhydrous NMP (17 mL), and sodium sulfide (0.4 g, 4.7 mmol) were added to the vial. The reaction was allowed to stir under argon at 150° C. for 16 hours. Upon completion, the reaction mixture was cooled to room temperature and the precipitate was filtered. The precipitate was washed three times with hot water and three times with acetone until the washings were clear. The precipitate was dried under vacuum at 120° C. to give 0.65 g of an orange-brown solid.

[0306] Example 35 Synthesis of poly-anthraquinone-benzoquinone trisulfides.

[0307] [ka]

[0308] Under argon, 1,5-dichloroanthraquinone (1.0 g, 3.6 mmol), 2,5-dichloro-1,4-benzoquinone (0.13 g, 0.7 mmol), sulfur (0.28 g, 8.7 mmol), anhydrous NMP (17 mL), and sodium sulfide (0.34 g, 4.3 mmol) were added to the vial. The reaction was allowed to stir under argon at 150° C. for 16 hours. Upon completion, the reaction mixture was cooled to room temperature and the precipitate was filtered. The precipitate was washed three times with hot water and three times with acetone until the washings were clear. The precipitate was dried under vacuum at 120° C. to give 1.13 g of a dark green solid.

[0309] (Example 36) Synthesis of poly-anthraquinone-benzoquinone pentasulfides.

[0310] [ka]

[0311] Under argon conditions, 1,5-dichloroanthraquinone (1.0 g, 3.6 mmol), 2,5-dichloro-1,4-benzoquinone (0.13 g, 0.7 mmol), sulfur (0.53 g, 16.6 mmol), anhydrous NMP (17 mL), and sodium sulfide (0.34 g, 4.3 mmol) were added to the vial. The reaction was allowed to stir under argon at 150° C. for 16 hours. Upon completion, the reaction mixture was cooled to room temperature and the precipitate was filtered. The precipitate was washed three times with hot water and three times with acetone until the washings were clear. The precipitate was dried under vacuum at 120° C. to give 1.23 g of a light green solid.

[0312] (Example 37) Synthesis of sulfurized polyacrylonitrile (SPAN) An exemplary synthesis of a carbon sulfide matrix polymer from polyacrylonitrile is reported in

[0313] The carbon sulfide matrix polymer was synthesized in two steps. First, polyacrylonitrile (PAN, Mw 150,000) was mixed with dry elemental S in a 1:4 mass ratio and ball milled for 1 hour, or in some cases up to 3 hours to ensure homogeneous mixing. The S:PAN (4:1) mixture was then cooled to 100° C. for 1 hour. 2 The elemental S was first melted and mixed with the PAN polymer by heating at 155°C for 2 hours in a packed furnace. The furnace temperature was increased up to 450°C at a heating rate of 5°C / min and isothermal at 450°C for 6 hours to obtain a sulfurized PAN composite. The SPAN was characterized by elemental analysis, which shows that the sulfurized polymer (SPAN) has 35.36 wt% S, 48.67 wt% C, 1.08 wt% H, and 7.34 wt% N.

[0314] (Example 38) Batteries made from Li / organosulfur polymer cathode cells FIG. 32 shows an illustrative arrangement of multiple electrochemical cells in a battery described herein.

[0315] FIG. 33 shows a schematic diagram of an illustrative multiple electrically connected electrochemical cell according to the disclosure.

[0316] (Example 39) S-Linked Polymers: An Illustrative Procedure for Preparing Carbon Sulfide Matrix Polymer Cathodes S-Linked Polymers: Illustrative procedures for preparing carbon sulfide matrix polymer cathodes are provided below and can be applied to SPAN or additional carbon sulfide matrix polymers.

[0317] First, a specific ratio of the carbon sulfide matrix polymer:SP C65 carbon mixture was mixed with a mortar and pestle for 10 minutes. The carbon sulfide matrix polymer:SP C65 mixture was then added to the S-linked quinone polymer PAQS and mixed well using a coffee mixer. 2 A calculated 3 wt% solution of PVDF or Na-CMC (vehicle) in 200 was added to the powder mixture of S-linked quinone polymer:carbon sulfide matrix polymer:SP C65 in a cup sealed using a screw cap. The entire mixture was then placed in a Thinky and the mixture was centrifuged and then mixed at 2000 rpm for 30 seconds to 5 minutes at least three times. The thick honey-like material was coated onto carbon-coated aluminum foil. The mixture was then cooled to 30°C for 30 minutes at 2000 rpm. The mixture was then cooled to 30°C for 30 minutes at 2 ... 2 O was dried under vacuum at 80°C.

[0318] Li / / S linked quinone polymers: further examples of carbon sulfide matrix polymer coin cells

[0319] (Example 40) Li / / S linked quinone polymer: carbon sulfide matrix polymer: SP-C65: CMC (35:47:11:7) coin cell In this example, a hybrid mixture of S-linked quinone polymer (PAQS) and sulfurized carbon matrix polymer (sulfurized organic sulfur polymer (SPAN)) was used as the cathode active material. The cathode was prepared by first mixing the sulfurized carbon matrix polymer and SP-C65 using a mortar and pestle. Then, the S-linked quinone polymer was added into the mortar and mixed using a pestle. 2 A 3% CMC (vehicle) solution in 20 was added to the hybrid mix of S-linked polymer, carbon sulfide matrix polymer and SP-C65. The entire mixture was spin-mixed twice for 30 seconds at 2000 rpm using a Thinky. A homogeneous looking viscous slurry was obtained, which was coated onto carbon-coated aluminum foil using an automated coater. The coated foil was then dried under vacuum at 80° C. overnight and cooled to 30° C. for 10 min. 2 O and O 2 The electrodes were stored in an argon glove box with levels below 10 ppm. The final composition of the electrodes was S-linked quinone polymer: carbon sulfide matrix: SP C65:CMC (35:47:11:7). This hybrid polymer combination is named Gen4 polymer.

[0320] FIG. 34 shows the voltage profile (charge and discharge characteristics) of Li / / Gen4 in ANA-42 at C / 10.

[0321] Lithium chip (thickness 0.02mm, 1.54cm 2 Electrochemical testing was carried out using a two-electrode CR2032 coin cell using 18 mm diameter (2.54 cm) as the anode and the Gen4 described above as the cathode. 2) Celgard 2400 was used as the separator. Various electrolyte formulations were tested, but 80 μL of 1.2 M LiFSI in BTFE:TEP (1:3 mol) electrolyte formulation, designated in this example as ANA-42, was found to give the best cycling data (FIG. 34). The cells were cycled at C / 10 with a voltage cutoff of 3.2 V to 1.0 V. This Gen4 hybrid mix of polymers gave an average of about 1.9 V battery when coupled to a metallic lithium anode (FIG. 34). The overall discharge capacity of the cell was found to be 350 mAh / g, which is more than 100% higher than the cathode with the PAQS polymer alone. This is a significant improvement in capacity when a hybrid mix of S-linked polymer and carbon sulfide matrix polymer is used as the cathode active material.

[0322] FIG. 35 shows the discharge capacity vs. cycle number of the Li / / Gen4 hybrid polymer cell in ANA-42 at C / 10. The data shows a surprising stability of the discharge capacity up to 110 cycles. The coulombic efficiency vs. cycle number is presented in FIG. 36 showing excellent coulombic efficiency up to 110 cycles. The overall energy density (Wh / kg) of the system vs. cycle number is presented in FIG. 37. The overall energy density was found to be greater than 550 Wh / kg or greater than 640 Wh / kg, and was surprisingly stable up to at least 110 cycles.

[0323] (Example 41) Gen4 polymers cycled at higher rates (C / 3) The Gen4 hybrid mix of polymer cathode was coated onto carbon-coated aluminum foil as described in Example 40. The coated foil was then dried under vacuum at room temperature overnight and then at 100° C. overnight, and then heated at 100° C. for 24 hours. 2 O and O 2 It was stored in an argon glove box with levels below 10 ppm. The final composition of the electrode was Gen4:SP C65:CMC (wt ratio of 82:11:7).

[0324] FIG. 38 shows the voltage profile (charge and discharge characteristics) of the Li / / Gen4 hybrid polymer cathode in ANA-42 at C / 3.

[0325] The cell was cycled at C / 3 with a voltage cutoff of 3.2 V to 1.0 V. Charge and discharge characteristics at C / 3 in Figure 38. The total discharge capacity of the cell was found to be 340 mAh / g, which is also more than 100% higher than the cathode with the PAQS polymer alone.

[0326] Figure 39 shows the discharge capacity vs. cycle number of Li / / Gen4 hybrid polymer mixed cells in ANA-42 at C / 3. The data shows a remarkable stability of the discharge capacity up to 210 cycles. The coulombic efficiency vs. cycle number is presented in Figure 40, which shows 100% coulombic efficiency up to 210 cycles.

[0327] (Example 42) S-linked quinone polymer: carbon sulfide matrix polymer: SP-C65: CMC (8:76:10:6) In this example, a hybrid mixture of S-linked quinone polymer and carbon sulfide matrix polymer with a mass ratio of 10:90 was used as the cathode active material. The combined mass ratio of S-linked quinone polymer and carbon sulfide matrix polymer from 20:80 to 5:95 is named Gen5 polymer cathode. The Gen5 hybrid cathode was prepared as described in Example 40. The coated foil was then dried under vacuum at room temperature overnight and then at 100° C. overnight, and then heated at 100° C. for 10 min. to 30 min. 2 O and O 2 It was stored in an argon glove box with levels below 10 ppm. The final composition of the electrode was S-linked quinone polymer:carbon sulfide matrix polymer:SP-C65:CMC (wt ratio of 8:76:10:6).

[0328] FIG. 41 shows the voltage profile (charge and discharge characteristics) of the Li / / Gen5 hybrid polymer cathode cell in ANA-42 at C / 10.

[0329] Lithium chip (thickness 0.02mm, 1.54cm 2 Electrochemical testing was carried out using a two-electrode CR2032 coin cell using 18 mm diameter (2.54 cm) as the anode and the Gen5 cathode described above. 2 ) Celgard 2400 was used as the separator. Various electrolyte formulations were tested, but in this example, 80 uL of 1.2 M LiFSI (ANA-42) in BTFE:TEP (1:3 mol) electrolyte formulation was found to give the best cycling data (Figures 41, 42, and 43). The cell was cycled at C / 10 with a voltage cutoff of 3.2 V to 1.0 V. The overall discharge capacity of the cell was found to be 598 mAh / g, which is about 240% higher than PAQS polymer alone as the cathode active material.

[0330] FIG. 42 shows the discharge capacity vs. cycle number of Li / / Gen5 polymer in ANA-42 at C / 10. The data shows a remarkable stability of the discharge capacity up to 110 cycles. The coulombic efficiency vs. cycle number is presented in FIG. 43 which shows 100% coulombic efficiency up to 110 cycles. FIG. 43 shows the coulombic efficiency vs. cycle number of Li / / Gen5 cell in ANA-42 at C / 10.

[0331] (Example 43) PAQS-PBQS Random Copolymers as Cathode Active Materials In this embodiment, the PAQS 0.8 -PBQS 0.2 A random copolymer of the formula (I) was used as the cathode active material similar to the active material described in Example 22. First, the PAQS was dissolved in water by using a mortar and pestle. 0.8 -PBQS 0.2The cathode was prepared by mixing the copolymer and SP-C65 carbon. A 3 wt% solution of PVDF in NMP was added to the mixed powders in a plastic cup. The entire mixture was then placed in a Thinky centrifugal mixer and centrifuged at 2000 rpm for 30 seconds three times. The homogenous viscous slurry was coated onto carbon-coated aluminum foil using an automated coater. The coated foil was then dried under vacuum at 100° C. overnight and quenched with H 2 O and O 2 The electrodes were stored in an argon glove box with levels below 10 ppm. The final composition of the electrodes was determined using the PAQS 0.8 -PBQS 0.2 The mixture was SP-C65:PVDF (wt ratio of 70:20:10). The lithium chip (thickness 0.02 mm, 1.54 cm 2 ) as the anode and the PAQS described above. 0.8 -PBQS 0.2 :SP-C65:PVDF (2.5mg, 1.13cm 2 Electrochemical testing was performed using a two-electrode CR2032 coin cell using a 18 mm diameter (2.54 cm) Cr2O3 as the cathode. 2 Celgard 2400 was used as the separator. Various electrolyte formulations were tested, but in this example, DME:13DOL (1:1 vol) + 100 mM LiNO 3 80uL of 1M LiTFSI (ANA-5) in the electrolyte formulation was found to give the best cycling data. The cell was cycled at C / 10 with a voltage cutoff of 3.2V to 1.6V. The voltage profile of the cell is presented in Figure 44. The charge and discharge characteristics and stability at C / 10 of the cell are presented in Figure 45. The total discharge capacity of the cell was found to be 225mAh / g, which is more than 40% higher than the cathode with PAQS polymer alone. The cell was cycled for 608 cycles with no significant capacity fade, as shown in Figure 45. The higher capacity and surprising cycling stability are due to the superior conductivity over traditional SP carbon and the use of LiNO in the electrolyte. 3This is due to better coating with SP-C65 carbon with additives.

[0332] Figure 44 shows the Li / / PAQS for ANA-5 at C / 10. 0.8 -PBQS 0.2 The voltage profile (charge and discharge characteristics) of the cell is shown.

[0333] Figure 45 shows the Li / / PAQS for ANA-5 at C / 10. 0.8 -PBQS 0.2 The discharge capacity of the cell versus cycle number is shown. The cell was cycled up to 608 cycles without significant capacity fade.

[0334] In summary, redox-active organosulfur polymers and related electrode materials, electrodes, electrochemical cells, batteries, methods and systems are described herein. In particular, tricyclic compounds having redox potentials of 0.20V to 3.3V relative to the Li / Li+ electrode potential under standard conditions. The redox-active organosulfur polymers can be used as cathodes for electrochemical cells containing Li anodes and non-aqueous electrolytes. Thus, the redox-active organosulfur polymers and related electrode materials, electrodes, electrochemical cells, batteries, methods and systems can be used in some embodiments to provide inexpensive, environmentally friendly, safe and / or high-rate batteries that can be a good replacement for current batteries for grid storage and other stationary applications.

[0335] In particular, redox-active S-linked polymers, sulfurized matrices, and related composites, compositions, electrode materials, electrodes, and related electrode chemical cell batteries, methods, and systems are described, in which the S-linked polymers, sulfurized matrices, and related composites, compositions, and electrode materials have redox potentials of up to 3.5 V relative to the Li / Li+ electrode potential under standard conditions, and capacities of at least 50 mAh / g, possibly up to 300 mAh / g, up to 400 mAh / g, up to 800 mAh / g, or higher. For example, the S-linked polymers, sulfurized matrices, and related composites, compositions, and electrode materials have capacities of 400 mAh / g to 800 mAh / g, or higher. More particularly, the redox-active S-linked polymers, sulfurized matrices, and related composites, and compositions are provided as cathode electrode materials for electrochemical cells further containing a Li anode and a non-aqueous electrolyte.

[0336] The examples set forth above are provided to give those of ordinary skill in the art a complete disclosure and description of how to make and use the disclosed organosulfur polymers, materials, compositions, systems and method embodiments, and are not intended to limit the scope of what the inventors consider their disclosure to be. All patents and publications mentioned herein are indicative of the level of skill of those skilled in the art to which the disclosure pertains.

[0337] The entire disclosure of each document cited in the Background Art, Abstract, Detailed Description, and Examples (including patents, patent applications, academic papers, including related supplementary and / or reference information sections, abstracts, experimental manuals, books, or other disclosures) is hereby incorporated by reference into this specification.All references cited in this disclosure are incorporated by reference to the same extent as if each reference was individually incorporated by reference in its entirety.However, if any inconsistency occurs between a cited reference and this disclosure, this disclosure shall prevail.

[0338] The terms and expressions used in this specification are used as terms of description and not as terms of limitation, and there is no intention in the use of such terms and expressions to exclude any equivalents or portions of the features shown and described, but it is recognized that various modifications are possible within the scope of the present disclosure as claimed. Therefore, even if the disclosure is specifically disclosed by preferred embodiments, illustrative embodiments, and optional features, it should be understood that modifications and variations of the disclosed inventive concepts may be made by those skilled in the art, and such modifications and variations are considered to be within the scope of this disclosure as defined by the appended claims.

[0339] It should also be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used in this specification and the appended claims, the singular forms "a", "an" and "the" include plural referents unless the content clearly dictates otherwise. The term "plurality" includes two or more referents unless the content clearly dictates otherwise. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosure pertains.

[0340] The term "alkyl" as used herein refers to linear, branched or cyclic saturated hydrocarbon groups typically, but not necessarily, containing 1 to about 15 carbon atoms, or 1 to about 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl, and the like. Generally, again but not necessarily, alkyl groups herein contain 1 to about 15 carbon atoms. The term "cycloalkyl" contemplates cyclic alkyl groups, typically having 4 to 8, or 5 to 7 carbon atoms. The term "substituted alkyl" refers to an alkyl substituted with one or more substituents, and the terms "heteroatom-containing alkyl" and "heteroalkyl" refer to an alkyl in which at least one carbon atom has been replaced with a heteroatom. Unless otherwise indicated, the terms "alkyl" and "lower alkyl" include linear, branched, cyclic, unsubstituted, substituted, and / or heteroatom-containing alkyl and lower alkyl, respectively.

[0341] The term "heteroatom-containing" as in "heteroatom-containing alkyl group" refers to an alkyl group in which one or more carbon atoms are replaced with an atom other than carbon, such as nitrogen, oxygen, sulfur, phosphorus, or silicon, typically nitrogen, oxygen, or sulfur. Similarly, the term "heteroalkyl" refers to an alkyl substituent that is heteroatom-containing, the term "heterocyclic" refers to a cyclic substituent that is heteroatom-containing, the terms "heteroaryl" and "heteroaromatic" refer to "aryl" and "aromatic" substituents, respectively, that are heteroatom-containing, and the like. It should be noted that a "heterocyclic" group or compound may or may not be aromatic, and further, a "heterocycle" may be monocyclic, bicyclic, or polycyclic, as described above for the term "aryl". Examples of heteroalkyl groups include alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylated aminoalkyl, and the like. Examples of heteroaryl substituents include pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, and the like; examples of heteroatom-containing alicyclic groups are pyrrolidino, morpholino, piperazino, piperidino, and additional substituents identifiable by one of ordinary skill in the art.

[0342] The term "alkoxy" as used herein contemplates an alkyl group bound through a single, terminal ether linkage; i.e., an "alkoxy" group can be represented as -O-alkyl, where alkyl is as defined above. A "lower alkoxy" group contemplates an alkoxy group containing 1 to 6 carbon atoms. Similarly, "alkenyloxy" and "lower alkenyloxy" refer to alkenyl and lower alkenyl groups, respectively, bound through a single, terminal ether linkage, and "alkynyloxy" and "lower alkynyloxy" refer to alkynyl and lower alkynyl groups, respectively, bound through a single, terminal ether linkage.

[0343] The term "aryl", as used herein, and unless otherwise specified, refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that different aromatic rings are bonded to a common group, such as a methylene or ethylene moiety). The aryl group can contain 5 to 24 carbon atoms, or the aryl group contains 5 to 14 carbon atoms. Illustrative aryl groups contain one aromatic ring or two fused or linked aromatic rings, such as phenyl, naphthyl, biphenyl, diphenyl ether, diphenylamine, benzophenone, and the like. "Substituted aryl" refers to an aryl moiety that is substituted with one or more substituents, and the terms "heteroatom-containing aryl" and "heteroaryl" refer to an aryl substituent in which at least one carbon atom is replaced with a heteroatom, as described in more detail below.

[0344] The terms "cyclic", "cyclo-", and "ring" refer to alicyclic or aromatic groups which may or may not be substituted and / or heteroatom-containing and which may be monocyclic, bicyclic, or polycyclic. The term "alicyclic" is used in the conventional sense to refer to aliphatic cyclic moieties, as opposed to aromatic cyclic moieties, which may be monocyclic, bicyclic, or polycyclic.

[0345] The term "isomers", when used, refers to heteroaromatic groups that have the same core molecule but may differ in atom connectivity and / or position of unsaturation, and is meant to include all possible structural variants. For example, as shown below, "pyrrole isomers" refers to all possible substitution variants of 1H-pyrrole and 2H-pyrrole; "indole isomers" refers to all possible substitution variants of 3H-indole, 1H-indole, and 2H-isoindole, etc.:

[0346] [ka]

[0347] Similarly, as shown below, "triazole isomers" refer to all possible substituted variants of 1,2,4-triazole and 1,2,3-triazole; "oxadiazole isomers" refer to all possible substituted variants of 1,2,5-oxadiazole and 1,2,3-oxadiazole, etc.:

[0348] [ka]

[0349] The terms "halo," "halogen," and "halide" are used in the conventional sense to refer to chloro, bromo, fluoro or iodo substituents or ligands.

[0350] The term alkylene, as used herein, refers to an alkanediyl group, which is a divalent saturated aliphatic group having two carbon atoms as points of attachment, a straight or branched cyclo, cyclic or acyclic structure. Illustrative alkylenes include the propane-1,2-diyl group (-CH(CH3)CH2-) or the propane-1,3-diyl group (-CH2CH2CH2-).

[0351] The term alkenylene refers to an alkenediyl group, which is a divalent unsaturated aliphatic group having two carbon atoms as points of attachment, a linear or branched cyclo, cyclic or acyclic structure, and at least one non-aromatic carbon-carbon double bond. An illustrative alkylene includes the 2-butene-1,4-diyl group (-CHCH=CHCH-).

[0352] The term alkynylene refers to an alkynediyl group, which is a divalent unsaturated aliphatic group having two carbon atoms as points of attachment, a linear or branched cyclo, cyclic or acyclic structure, and at least one non-aromatic carbon-carbon triple bond. An illustrative alkylene includes the 2-butyne-1,4-diyl group (-CH2C≡CCH2-).

[0353] The term "substituted," as in "substituted alkyl," "substituted aryl," etc., means that at least one hydrogen atom bonded to a carbon (or other) atom in an alkyl, aryl, or other moiety, is replaced with one or more non-hydrogen substituents.

[0354] Examples of such substituents include, without limitation, the following: halo, hydroxyl, sulfhydryl, C1-C24 alkoxy, C2-C24 alkenyloxy, C2-C24 alkynyloxy, C5-C24 aryloxy, C6-C24 aralkyloxy, C6-C24 alkaryloxy, acyl (including C2-C24 alkylcarbonyl (-CO-alkyl) and C6-C24 arylcarbonyl (-CO-aryl)), acyloxy (-O-acyl, C2-C24 alkylcarbonyloxy ( C2-C24 alkoxycarbonyl (-(CO)-O-alkyl), C6-C24 aryloxycarbonyl (-(CO)-O-aryl), halocarbonyl (-CO)-X, where X is halo, C2-C24 alkylcarbonato (-O-(CO)-O-alkyl), C6-C24 arylcarbonato (-O-(CO)-O-aryl), carboxy (-COOH), carboxylato (COO -), carbamoyl (-(CO)-NH2), mono-(C1-C24 alkyl) substituted carbamoyl (-(CO)-NH(C1-C24 alkyl)), di-(C1-C24 alkyl) substituted carbamoyl (-(CO)-N(C1-C24 alkyl)2), mono-(C5-C24 aryl) substituted carbamoyl (-(CO)-NH-aryl), di-(C5-C24 aryl) substituted carbamoyl (-(CO)-N(C5-C24 aryl)2), di-N-(C1-C24 alkyl), N-(C5-C24 aryl) substituted carbamoyl, thiocarbamoyl (-(C S)-NH2), mono-(C1-C24 alkyl) substituted thiocarbamoyl (-(CO)-NH(C1-C24 alkyl)), di-(C1-C24 alkyl) substituted thiocarbamoyl (-(CO)-N(C1-C24 alkyl)2), mono-(C5-C24 aryl) substituted thiocarbamoyl (-(CO)-NH-aryl), di-(C5-C24 aryl) substituted thiocarbamoyl (-(CO)-N(C5-C24 aryl)2), di-N-(C1-C24 alkyl), N-(C5-C24 aryl) substituted thiocarbamoyl, carbamide (-NH-(CO)- NH2), cyano (-C≡N), cyanato (-OC≡N), thiocyanato (-SC≡N), formyl (-(CO)-H), thioformyl ((CS)-H), amino (-NH2), mono-(C1-C24 alkyl) substituted amino, di-(C1-C24 alkyl) substituted amino, mono-(C5-C24 aryl) substituted amino, di-(C5-C24 aryl) substituted amino, C2-C24 alkylamido (-NH-(CO)-alkyl), C6-C24 arylamido (-NH-(CO)-aryl), imino (-CR=NH, where R=hydrogen, C1-C24 aryl alkyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), C2-C20 alkylimino (CR=N(alkyl), where R=hydrogen, C1-C24 alkyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), arylimino (-CR=N(aryl), where R=hydrogen, C1-C20 alkyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), nitro (-NO2), nitroso (-NO), sulfo (-SO2-OH), sulfonato (-SO2-O- ), C1-C24 alkylsulfanyl (-S-alkyl; also termed "alkylthio"), C5-C24 arylsulfanyl (-S-aryl; also termed "arylthio"), C1-C24 alkylsulfinyl (-(SO)-alkyl), C5-C24 arylsulfinyl (-(SO)-aryl), C1-C24 alkylsulfonyl (-SO2-alkyl), C5-C24 arylsulfonyl (-SO2-aryl), boryl (-BH2), borono (-B(OH)2), boronato (-B(OR)2, where R is alkyl or other hydrocarbyl), phosphono (-P(O)(OH)2), phosphonato (-P(O)(O - )2), phosphinato (-P(O)(O - )), phospho (-PO2), phosphino (-PH2), silyl (-SiR3, where R is hydrogen or hydrocarbyl), and silyloxy (-O-silyl); and functional groups such as hydrocarbyl moieties C1-C24 alkyl (e.g., C1-C12 alkyl and C1-C6 alkyl), C2-C24 alkenyl (e.g., C2-C12 alkenyl and C2-C6 alkenyl), C2-C24 alkynyl (e.g., C2-C12 alkynyl and C2-C6 alkynyl), C5-C24 aryl (e.g., C5-C14 aryl), C6-C24 alkaryl (e.g., C6-C16 alkaryl), and C6-C24 aralkyl (e.g., C6-C16 aralkyl).

[0355] The term "acyl" refers to a substituent having the formula -(CO)-alkyl, -(CO)-aryl, or -(CO)-aralkyl, and the term "acyloxy" refers to a substituent having the formula -O(CO)-alkyl, -O(CO)-aryl, or -O(CO)-aralkyl, where "alkyl", "aryl", and "aralkyl" are defined above.

[0356] The term "alkaryl" refers to an aryl group having an alkyl substituent, and the term "aralkyl" refers to an alkyl group having an aryl substituent, where "aryl" and "alkyl" are defined above. In some embodiments, the alkaryl and aralkyl groups contain 6 to 24 carbon atoms, and in particular the alkaryl and aralkyl groups contain 6 to 16 carbon atoms. Alkaryl groups include, for example, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-1,4-diene, and the like. Examples of aralkyl groups include, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like. The terms "alkaryloxy" and "aralkyloxy" refer to a substituent of the formula -OR, where R is alkaryl or aralkyl, respectively, as just defined.

[0357] The term "periodic table" refers to the version of the IUPAC Periodic Table of the Elements dated November 28, 2016.

[12]

[0358] When a Markush group or other grouping is used herein, all individual members of the group, and all combinations and possible subcombinations of the group, are intended to be individually included in the disclosure. Any combination of components or materials described or illustrated herein can be used to practice the disclosure unless otherwise specified. Those skilled in the art will recognize that methods, device elements, and materials other than those specifically illustrated can be used to practice the disclosure without resorting to undue experimentation. All art-known functional equivalents of any such methods, device elements, and materials are intended to be included in this disclosure. Whenever a range is given in this specification, for example, a temperature range, frequency range, time range, or composition range, all intermediate ranges and all subranges, and all individual values ​​included in the given range are intended to be included in the disclosure. Any one or more individual members of a range or group disclosed herein may be excluded from the claims of this disclosure. The disclosure illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations not specifically disclosed herein.

[0359] "Optional" or "optionally" means that the subsequently described situation may or may not occur, and the description includes examples where the situation occurs and examples where it does not occur, according to the guidance provided in this disclosure. For example, the phrase "optionally substituted" means that a non-hydrogen substituent may or may not be present on a given atom, and thus the description includes structures where a non-hydrogen substituent is present and structures where a non-hydrogen substituent is not present. It will be recognized that the phrase "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted." Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituents may be either the same or different at every position. The combinations of substituents envisioned can be identified in terms of the desired characteristics of the compound, in terms of the present disclosure, and in terms of the characteristics that result in the formation of a stable or chemically feasible compound. The term "stable," as used herein, refers to compounds that are not substantially altered when subjected to conditions that enable their production, detection, and, in certain embodiments, their recovery, purification, and use for one or more of the purposes disclosed herein.

[0360] A number of embodiments of the present disclosure have been described. The specific embodiments provided herein are examples of useful embodiments of the present disclosure, and it will be apparent to those skilled in the art that the disclosure can be implemented using a number of variations of the devices, device components, and method steps described in this description. As will be apparent to those skilled in the art, the methods and devices useful for the present methods can include a number of optional compositions and processing elements and steps.

[0361] In summary, described herein, in some embodiments, are organosilicon compounds that enable the performance of fluorocarbon or olefin-based reactants, related composites, and in particular the polymerization of olefins to produce polyolefin polymers, and related methods and systems.

[0362] In particular, it is to be understood that various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, other embodiments are within the scope of the following claims. (References) TIFF2025515818000043.tif220151

Claims

1. At least one S-linked quinone polymer, and At least one carbon sulfide matrix A redox active complex comprising: at least one of the S-linked quinone polymers (i) Formula (I): -[MS p ]- m (I) (In the formula, M is a redox-active monomeric quinone moiety having a redox potential of 0.5 V to 3.5 V relative to the Li / Li+ electrode potential under standard conditions; p refers to the number of sulfur atoms linking the redox-active monomeric quinone moieties M, and p ranges from 1 to 5; S p is a sulfide when p is 1 or a polysulfide when p is 2 to 5; m ranges from 5 to 10,000) and one or more S-linked quinone homopolymers represented by One or more S-linked quinone homopolymers having a weight average molecular weight of at least 1,000 daltons and a solubility in tetrahydrofuran (THF) at 1 atm (101.33 kPa) and 21° C. of 1.0 micrograms per mL or less; and / or (ii) Formula (II): -[M1-S p1 ] m1 -co-[M2-S p2 ]- m2 (II) (In the formula, M1 and M2 are each redox-active monomeric quinone moieties having a redox potential of 0.5 V to 3.5 V referenced to the Li / Li+ electrode potential under standard conditions; p1 and p2 each independently refer to the number of sulfur atoms connecting the redox-active monomeric quinone moiety M1 and the monomeric quinone moiety M2, respectively, and p1 and p2 each independently range from 1 to 5; S p1 is a sulfide when p1 is 1 or a polysulfide when p1 is 2 to 5; S p2 is a sulfide when p2 is 1 or a polysulfide when p2 is 2 to 5; m1 and m2 each independently range from 5 to 5,000. and one or more S-linked quinone copolymers represented by One or more S-linked quinone copolymers having a weight average molecular weight ranging from 1,000 to 2,000,000 daltons and a solubility in tetrahydrofuran (THF) at 1 atm (101.33 kPa) and 21° C. of 1.0 micrograms per mL or less Including, At least one of the carbon sulfide matrices is Formula (V): 【Chemistry 10】 wherein Q is a bonded sp 2 carbon atom (C) or nitrogen (N); 【Chemistry 11】 represents a single or double bond, S p represents a polysulfide, and p ranges from 2 to 8. is represented by having a weight average molecular weight in the range of 2000 Daltons to 2,000,000 Daltons; and A redox-active composite having a sulfur content, relative to the total mass of the sulfurized carbon matrix, of greater than or equal to 5 wt.% and less than 80 wt.%.

2. The redox-active complex of claim 1, wherein the mass ratio of S-linked quinone polymer to carbon sulfide matrix is ​​from 20:1 to 1:

20.

3. The S-linked quinone homopolymer, wherein the redox-active monomeric quinone moiety is of formula (III): 【Chemical 1】 wherein R 1 , R 2 , R 3 , and R 4 are each independently null (absent), H, S p (wherein p ranges from 1 to 5), F, Cl, Br, I, CF 3 , a linear or branched, substituted or unsubstituted C1-C4 aliphatic group, an aromatic ring, a heteroaromatic ring, a non-aromatic ring, or a non-aromatic heterocyclic ring, wherein the aromatic ring, heteroaromatic ring, non-aromatic ring, or non-aromatic heterocyclic ring contains a substituent containing 4 to 12 carbon atoms and 0 to 4 heteroatoms, the heteroatoms being selected from O, N, and S; and R 1 and R 2 together, and / or R 3 and R 4 together, are part of an aromatic or aliphatic ring structure; The dashed line represents either null (absent) or a single bond to a quinone ring carbon if the associated R 1 , R 2 , R 3 or R 4 is null.

2. The redox-active complex of claim 1, comprising a structure represented by:

4. The redox-active monomeric quinone moiety of the S-linked quinone homopolymer is S-linked, and the S-linked redox-active monomeric quinone is represented by the formula (IIIA) and the formula (IIIB): 【Chemistry 2】 4. The redox-active complex of claim 3, wherein:

5. The S-linked quinone homopolymer, wherein the redox-active monomeric quinone moiety is of formula (IV): 【Chemistry 3】 wherein R 1 , R 2 , R 3 , and R 4 are each independently null (absent), H, S p (wherein p ranges from 1 to 5), F, Cl, Br, I, CF 3 , a linear or branched, substituted or unsubstituted C1-C4 aliphatic group, an aromatic ring, a heteroaromatic ring, a non-aromatic ring, or a non-aromatic heterocyclic ring, wherein the aromatic ring, heteroaromatic ring, non-aromatic ring, or non-aromatic heterocyclic ring contains a substituent containing 4 to 12 carbon atoms and 0 to 4 heteroatoms, wherein the heteroatoms are selected from O, N, and S; and R 1 and R 2 together and / or R 3 and R 4 together are part of an aromatic or aliphatic ring structure; The dashed line represents either null (absent) or a single bond to a quinone ring carbon if the associated R 1 , R 2 , R 3 or R 4 is null.

2. The redox-active complex of claim 1, comprising a structure represented by:

6. The redox-active monomeric quinone moiety of the S-linked quinone homopolymer is S-linked, and the S-linked redox-active monomeric quinone is represented by formula (IVA), formula (IVB), or formula (IVC): 【Chemistry 4】 6. The redox-active complex of claim 5, represented by any one of the S-linked monomeric moieties:

7. 2. The redox-active complex of claim 1, wherein the S-linked quinone homopolymer is selected from the group consisting of 2,5-S-linked polyanthraquinone (PAQS), 3,6-S-linked polyphenanthrenequinone (36PPAQS), 2,7-S-linked polyphenanthrenequinone (27PPAQS), and 9,10-S-linked 1,2,5,6-polyanthracenetetraone (PAQT).

8. The redox-active complex of claim 1, wherein in the one or more S-linked quinone copolymers represented by formula (II), the ratio of m1 to m2 ranges from 1:50 to 1:

1.

9. The redox-active complex described in claim 1, wherein the redox-active monomeric quinone moieties M1 and M2 of the S-linked quinone copolymer are arranged in a random copolymer, a block copolymer, or an alternating copolymer.

10. The redox-active complex of claim 9, wherein the redox-active monomeric quinone moieties M1 and M2 of the S-linked quinone copolymer are arranged in a random copolymer.

11. The S-linked quinone copolymer wherein the redox-active monomeric quinone moiety M1 and the redox-active monomeric quinone moiety M2 are independently selected from the group consisting of formula (III) and formula (IV): 【Chemistry 5】 wherein R 1 , R 2 , R 3 , and R 4 in formula (III) and formula (IV) are each independently null (absent), H, S p (wherein p is in the range of 1 to 5), F, Cl, Br, I, CF 3 , a linear or branched, substituted or unsubstituted C1-C4 aliphatic group, an aromatic ring, a heteroaromatic ring, a non-aromatic ring, or a non-aromatic heterocyclic ring, wherein the aromatic ring, heteroaromatic ring, non-aromatic ring, and non-aromatic heterocyclic ring contain a substituent containing 4 to 12 carbon atoms and 0 to 4 heteroatoms, the heteroatoms being selected from O, N, and S; R 1 and R 2 together, and / or R 3 and R 4 together, are part of an aromatic or aliphatic ring structure; The dashed line represents either null (absent) or a single bond to a quinone ring carbon if the associated R 1 , R 2 , R 3 or R 4 is null.

2. The redox-active complex of claim 1, represented by any one of:

12. The S-linked quinone copolymer, wherein the redox-active monomeric quinone moiety M1 and the redox-active monomeric quinone moiety M2 are S-linked, and the S-linked redox-active monomeric quinone moiety M1 and the S-linked redox-active monomeric quinone moiety M2 are represented by Formula (IIIA), Formula (IIIB), Formula (IVA), Formula (IVB), and Formula (IVC): 【Chemistry 6】 12. The redox-active complex of claim 11, wherein the S-linked monomeric moiety is independently selected from any one of 13. The S-linked quinone copolymer, wherein the S-linked redox-active monomeric quinone moiety M1 is a compound of formula (IIIA): 【Chemistry 7】 and the S-linked redox-active monomeric quinone moiety M2 of the S-linked quinone copolymer is represented by Formula (IIIB), Formula (IVA), Formula (IVB), and Formula (IVC): 【Chemistry 8】 and is represented by any one of the S-linked monomeric moieties 13. The redox-active complex of claim 12, wherein the molar ratio of the S-linked monomeric moiety of Formula (IIIA) to any one of the S-linked monomeric moieties of Formula (IIIB), Formula (IVA), Formula (IVB), and Formula (IVC) ranges from 1:50 to 1:

1.

14. The redox-active complex of claim 13, wherein in the S-linked quinone copolymer, the molar ratio of S-linked monomeric moiety M1 of formula (IIIA) to S-linked monomeric moiety M2 of formula (IIIB), formula (IVA), formula (IVB), or formula (IVC) is 1:

4.

15. The S-linked quinone copolymer, wherein the S-linked redox-active monomeric quinone moiety M2 has the formula (IIIB): 【Chemistry 9】 14. The redox-active complex of claim 13, wherein:

16. The redox-active complex of claim 15, wherein the molar ratio of S-linked monomeric moieties of formula (IIIA) to S-linked monomeric moieties of formula (IIIB) in the S-linked quinone copolymer is 1:

4.

17. The redox-active composite of claim 1, wherein the carbon sulfide matrix of formula (V) is selected from the group consisting of sulfurized poly(acrylonitrile) (SPAN) (11), covalently bonded triazine backbone (S-CTF-1) (12), covalently bonded triazine backbone (S-CTF-1) (13), poly(sulfur random-1,3-diisopropylbenzene) (poly(Sr-DIB) (14), S-BOP (15), carbon / polymeric sulfur (C / PS) composite (16), covalently grafted polysulfur graphene nanocomposite (PolySGN) (17), and graphene-supported cross-linked sulfur copolymer nanoparticles (cp(S-TTCA)@rGO-80) (18), or any combination thereof.

18. 18. The redox-active complex of claim 17, wherein the carbon sulfide matrix is ​​SPAN.

19. The redox-active complex of claim 1, further comprising an additive.

20. 20. The redox-active complex of claim 19, wherein the additive comprises a binder.

21. The redox-active complex of claim 20, wherein the binder is selected from one of poly(vinylidene fluoride) (PVDF), poly(tetrafluoroethylene) (PTFE), sodium carboxymethylcellulose (NaCMC), lithium carboxymethylcellulose (LiCMC), styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyethylene oxide (PEO), and polyamideimide (PAI), or any combination thereof.

22. The redox-active complex of claim 20, wherein the binder is present in an amount of from 1% to 20% by weight of the redox-active complex.

23. The redox-active complex of claim 20, wherein the additive comprises a conductive additive.

24. The redox-active composite of claim 23, wherein the conductive additive is selected from one of graphite, carbon black, acetylene black, Super-P carbon (e.g., Super-P, Super-P C65), carbon nanotubes, nickel powder, Ketjen black (KB), or any combination thereof.

25. The redox-active complex of claim 23, wherein the conductive additive is present in an amount of from 5% to 70% by weight of the redox-active complex.

26. A cathode material comprising a redox-active complex according to any one of claims 1 to 25.

27. 27. The cathode material of claim 26, wherein the mass ratio of the S-linked quinone polymer to the carbon sulfide matrix ranges from 20:1 to 1:

20.

28. 26. An electrochemical cell comprising an anode, a cathode and a non-aqueous or aqueous electrolyte, wherein the cathode electrode comprises the redox-active complex of any one of claims 1 to 25.

29. 30. A battery comprising one or more electrochemical cells according to claim 28.

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