WO2017031062A1 - Structures organiques covalentes modifiées par un polymère conducteur et procédés de fabrication de celles-ci - Google Patents

Structures organiques covalentes modifiées par un polymère conducteur et procédés de fabrication de celles-ci Download PDF

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WO2017031062A1
WO2017031062A1 PCT/US2016/047046 US2016047046W WO2017031062A1 WO 2017031062 A1 WO2017031062 A1 WO 2017031062A1 US 2016047046 W US2016047046 W US 2016047046W WO 2017031062 A1 WO2017031062 A1 WO 2017031062A1
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cof
tfp
daaq
pedot
aryl
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William Dichtel
Catherine MULZER
Ryan BISBEY
Luxi SHEN
Hector ABRUNA
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Cornell University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the disclosure generally relates to conducting-polymer modified covalent organic frameworks. BACKGROUND OF THE DISCLOSURE
  • EES Electrical energy storage
  • supercapacitors store electricity through two distinct processes: the non- faradaic processes associated with the electrochemical double layer and faradaic processes arising from electrode-bound reversible redox processes, a phenomenon known as pseudocapacitance.
  • the electrochemical double layer consists of ions adsorbed to an electrode surface in response to an applied potential and is maximized in high surface area electrodes, such as porous carbons.
  • Redox-active groups may be covalently attached or adsorbed onto these electrodes.
  • these materials are typically not well defined, which complicates their characterization and rational efforts to improve their performance. Modular and reliable strategies to access high-surface-area electrodes with control over their porosity and surface area, as well as the placement and identity of redox-active groups are desirable.
  • Two-dimensional covalent organic frameworks (2D COFs) predictably organize redox-active groups into crystalline, high-surface area polymer networks with uniform micropores. Electrodes functionalized with 2D COFs might achieve both high theoretical energy density by exhibiting high capacity and high potentials, and high power density because their continuous, ordered pores facilitate ion transport. Many early 2D COFs featured boron-containing linkages, which are oxidatively and hydrolytically unstable, limiting their utility as electrode materials; especially at high potentials.
  • High surface area electrodes will provide sensing platforms, electrocatalyst supports, and improved energy storage and conversion devices, including batteries, supercapacitors, and fuel cells.
  • framework materials such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs)
  • MOFs metal-organic frameworks
  • COFs covalent organic frameworks
  • COFs which are crystalline polymer networks comprised of light elements, adopt two-dimensional (2D) layered structures with high spectroscopic charge-carrier mobilities.
  • 2D two-dimensional
  • Pseudocapacitors can combine the high energy density of batteries and superior power densities of double-layer capacitors by storing electricity through both the non-faradaic formation of an electrochemical double layer (EDL) and reversible faradaic redox processes of surface bound/immobilized species.
  • EDL electrochemical double layer
  • Nanoporous electrodes often carbon- based materials, feature high specific surface areas that maximize electrochemical double- layer formation.
  • redox-active groups have been covalently bonded or adsorbed to these electrodes, their performance is often compromised by charge transfer and counter ion transport limitations. In addition, their poorly defined structures complicate characterization and rational improvement.
  • 2D COFs address these limitations by predictably and deliberately organizing redox-active groups into insoluble, high-surface area polymer networks with uniform micropores.
  • the modest conductivity of existing 2D COFs has limited devices to thin films of the active material (50-250 nm) grown on Au or carbon nanotube electrodes that only operate at slow charge/discharge rates, limiting high power performance.
  • the present disclosure provides conducting-polymer modified covalent organic frameworks (COFs), methods of making conducting-polymer modified covalent organic frameworks, and uses thereof.
  • COFs conducting-polymer modified covalent organic frameworks
  • the present disclosure also provides materials and devices comprising conducting-polymer modified covalent organic frameworks.
  • Such frameworks provide materials which have properties that make them useful for applications such as, for example, incorporation in electronic devices.
  • the present disclosure provides conducting-polymer modified covalent organic frameworks.
  • the conducting-polymer modified COFs comprise one or more COF layers and one or more conducting polymers.
  • the conducting polymers at least partially fill a portion of or all of the COF pores and/or at least partially coat the exposed surfaces of the COFs (e.g., COF layers or COF films).
  • the COFs are redox active COFs.
  • compositions comprising one or more conducting polymer modified COFs.
  • a thin film comprises one or more conducting polymer modified COFs (e.g., one or more conducting polymer modified COF layers).
  • the present disclosure provides a method for making conducting- polymer modified COFs as described herein.
  • the method comprises electropolymerizing a conducting-polymer in the presence of a COF (e.g., COF layer or COF layers) such that a conducting-polymer modified COF layer or layers are formed.
  • a COF e.g., COF layer or COF layers
  • the method comprises multiple electropolymerization steps (e.g., two to 20 electropolymerization steps, including all integer number of electropolymerization steps and ranges therebetween).
  • the method comprises electropolymerizing a conducting-polymer onto a COF-modified substrate.
  • the present disclosure provides devices comprising at least one conducting polymer modified COF of the present disclosure.
  • the conducting polymer modified COFs can be incorporated in electrical devices such as, for example, electrical energy storage systems (e.g., in an electrical energy storage device such as a super capacitor).
  • an electrochemical supercapacitor comprises a conducting polymer modified COF of the present disclosure.
  • Figure 1 shows the reaction scheme of the DAAQ-TFP COF film synthesis followed by electropolymerization of 3,4-ethylenedioxythiophene (EDOT) at 20 mV s "1 in 0.1 M EDOT / 0.1 M Bu 4 NC10 4 .
  • EDOT 3,4-ethylenedioxythiophene
  • Figure 2 shows characterization of PEDOT / DAAQ-TFP COF
  • A eQCM data showing separate polymerization cycles (1 st , 2 nd , 3 rd , 4 th , and 5 th ) showing a consistent uptake of 30 ⁇ g cm "2 except for the first cycle which shows an increase of 15 ⁇ g cm -2 .
  • B FTIR spectra of DAAQ-TFP COF film, 2 cycle PEDOT polymerization, 9 cycle PEDOT polymerization, and PEDOT.
  • C GIXD of various polymerized DAAQ-TFP COF films.
  • D XPS depth profile using an Ar ion beam etch.
  • Figure 3 shows (A) CV response in 0.5 M H 2 S0 4 of a PEDOT modified 1 ⁇ DAAQ-TFP COF film and the same DAAQ-TFP COF film before EDOT polymerization (B) Oxidative charge from PEDOT modified DAAQ-TFP COF (top line) and unmodified DAAQ-TFP COF (bottom line) over various scan rates.
  • Figure 4 shows (A) average capacitances calculated from 10 cycles of galvanostatic charge-discharge experiments at various C rates (error bars show ⁇ 1 standard deviation). (B) Extended cycling of a PEDOT / DAAQ-TFP COF thin film showing stability over 2250 cycles.
  • Figure 5 shows incorporation of PEDOT within a DAAQ-TFP COF film.
  • Figure 6 shows modification of a DAAQ-TFP film via electropolymerization of PEDOT.
  • A Electrochemical QCM data showing separate polymerization cycles (1 st , 2 nd , 3rd. 4th anc j ⁇ th ⁇ s h owm g a consistent mass increase of 30 ⁇ g cm" 2 per cycle except for the first cycle (15 ⁇ g cm "2 ).
  • B Cyclic voltammograms at 20 mV s "1 during EDOT
  • Each cycle is corresponds with panel (A) (1 st , 2 nd , 3 rd , 4 th , and 5 th ).
  • C FTIR spectra of an example of an as-synthesized DAAQ-TFP film, the film after two electropolymerization cycles, a film after nine electropolymerization cycles, and PEDOT.
  • D XPS depth profile (Ar ion beam etch) of the Ni s and S 2p regions (1 st , 2 nd , 3 rd , 4 th , and 5 th ). The Nis profiles are scaled three-fold in intensity for visual clarity.
  • Figure 7 shows electrochemical performance of examples of PEDOT-modified and as-synthesized DAAQ-TFP COF films.
  • A CV response at 20 mV sec "1 in 0.5 M H 2 S0 4 of a PEDOT-modified DAAQ-TFP film, 1 ⁇ -thick and the same as-synthesized DAAQ- TFP film before EDOT polymerization.
  • the inset presents the cyclic voltammetric response for the unmodified film using an expanded current scale.
  • B The integrated charge associated with the oxidative wave of a PEDOT-modified DAAQ-TFP COF film and unmodified
  • DAAQ-TFP COF film recorded over various scan rates indicate that the PEDOT-modified films store more charge and tolerate faster scan rates than the unmodified films.
  • Figure 8 shows charge storage performance and device integration of an example of a PEDOT-modified DAAQ-TFP film.
  • A Average capacitances calculated from 10 cycles of galvanostatic charge-discharge experiments at various C rates (error bars show ⁇ 1 standard deviation).
  • B Extended cycling of a PEDOT-modified DAAQ-TFP film showing stability over 10,000 cycles. First three cycles are at a rate of IOC, then over 10,000 cycles at a rate of lOOC, followed by another three cycles at IOC showing no loss in capacitance over the cycles.
  • C CV in a two-electrode device configuration, in which the counter is a high-surface area carbon electrode.
  • Figure 9 shows an example of a making a conducting-polymer modified covalent organic framework (COF) of the present disclosure.
  • Figure 10 shows representative AFMs of examples of crystalline DAAQ-TFP COF films (A) before EDOT polymerization and (B) after EDOT polymerization.
  • Figure 11 shows representative AFMs of examples of crystalline DAAQ-TFP
  • Figure 12 shows representative AFM of PEDOT-modified Au AFMs for a polymerization to yield approximately 805 nm thick film for control experiments.
  • Figure 13 shows representative AFMs of an example of a PEDOT-modified
  • Figure 14 shows representative SEMs of examples of post-polymerization
  • Figure 15 shows cross sectional SEM of examples of post-polymerization
  • Figure 16 shows representative GIXD of examples of DAAQ-TFP films on
  • the top row corresponds to a DAAQ-TFP COF film prior to
  • Figure 17 shows representative GIXD of examples of DAB-TFP films on Au substrates.
  • Figure 18 shows GIXD of examples of PEDOT polymerized on Au substrate.
  • Figure 19 shows mass (left axis and left-most line) and resistance (right axis and right-most line) change for EQCM polymerization of EDOT within an example of DAAQ-TFP on QCM chip.
  • Figure 20 shows recorded mass (left axis and left-most line) and resistance
  • Figure 21 shows (A) Kr gas adsorption isotherm for a DAAQ-TFP COF without PEDOT (1), 2 cycle polymerization a PEDOT / DAAQ-TFP COF (2), and a 9 cycle polymerization PEDOT / DAAQ-TFP COF (3).
  • Figure 22 shows examples of CVs used to approximate the number of anthraquinones accessed in an example of a PEDOT-modified DAAQ-TFP COF films.
  • the left CV shows an unmodified DAAQ-TFP COF film and the right shows a PEDOT-modified DAAQ-TFP COF film
  • Figure 23 shows the effect of number of cycles in a EDOT polymerization on
  • Figure 24 shows the effect of electropolymerization scan rate.
  • A Cyclic voltammograms for unmodified DAAQ-TFP COF (1) and PEDOT / DAAQ-TFP COF (2) where the PEDOT was polymerized at 2 mV s "1 for 5 cycles. CVs taken at 20 mV s "1 in 0.5 M H2SO4.
  • B Scan rate dependence of film prepared in Figure 19 at 20 mV s "1 (1), 50 mV s "1 (2), and 100 mV s "1 (3).
  • Figure 25 shows an overlay of cyclic voltammograms (20 mV s "1 , 0.5 M
  • Figure 26 shows equivalent circuit modeling for PEDOT / DAAQ-TFP systems.
  • Figure 27 shows impedance spectra comparing a PEDOT / DAAQ-TFP (1) and a DAAQ-TFP COF (2).
  • Figure 28 shows galvanostatic charge discharge profiles over 10 cycles for a
  • Figure 29 shows (A) Volumetric capacitances obtained from a PEDOT on gold control experiment. (B) CV of an example of PEDOT which has been
  • Figure 30 shows potential / Capacity profiles for a DAAQ-TFP COF (1)
  • Figure 31 shows (A) Capacitance over various C rates (x-axis) for a PEDOT /
  • DAAQ-TFP COF (1) over the entire voltage window (-0.4 to 0.6 V vs Ag/AgCl) and for a PEDOT / DAAQ-TFP COF (2) in the non-faradaic window (0.35 - 0.6 V V vs Ag/AgCl).
  • Figure 32 shows (A) Reaction scheme to synthesize an example of DAB-TFP COF film (B) CV of a PEDOT / DAB-TFP COF (1) and an unmodified DAB-TFP COF (2).
  • Figure 33 shows galvanostatic charge / discharge experiment for an example of a PEDOT-modified DAAQ/TFP COF film at 50 C.
  • One trace is cycle 1
  • the other trace is cycle 10.
  • (A) displays the CV response for an example of a PEDOT-modified DAAQ-TFP film at 0.5, 1, 5, and 10 mV s "1 and (B) for 20, 50, 100, 300, and 500 mV s "1 .
  • (C) displays the integrated charge for the oxidative and reductive anthraquinone waves along with the coulombic efficiency (CE, right y-axis) over all scan rates probed in (A) and (B).
  • (D) is a zoom-in of the slowest scan rates shown in part (C).
  • Figure 36 shows capacitance responses over a variety of C-rates for a three- electrode and a two-electrode set up.
  • Figure 37 shows assembly of an example of a cell. Starting from the cathode, (A) Ti current collector, (B) a PEDOT / DAAQ-TFP COF, (C) separator and activated carbon, (D) Ti current collector, (E) stainless steel piece and spring, and (F) shows two cell connected in series using Arbin channels connected by wires with the LED attached to the setup.
  • A Ti current collector
  • B PEDOT / DAAQ-TFP COF
  • C separator and activated carbon
  • D Ti current collector
  • E stainless steel piece and spring
  • F shows two cell connected in series using Arbin channels connected by wires with the LED attached to the setup.
  • Figure 38 shows powder XRD of an example of a PEDOT modified DAAQ- TFP powder, showing diffraction pattern maintained.
  • Figure 39 shows overlay of IR spectra of a DAAQ-TFP COF powder, an example of a chemically polymerized PEDOT-modified DAAQ-TFP COF powder, an example of an electropolymerized PEDOT-modified DAAQ-TFP COF film and a
  • Figure 40 shows CV response for a coin cell fabricated from an example of a
  • PEDOT-modified DAAQ-TFP COF powder where the PEDOT to COF mass ratio is 1 : 1 (1) and similarly fabricated coin cells with only activated carbon (2) or with PEDOT only as the active material (3).
  • the mass used in the normalization is the combined active electrode and counter electrode mass.
  • Figure 41 shows GCDC potential profiles for an example of a coin cell fabricated from an example of a PEDOT-modified DAAQ-TFP COF powder where the PEDOT to COF mass ration is 1 : 1 and an activated carbon counter electrode.
  • Capacitance over a variety of C rates where the left axis is the capacitance accounting for the mass of the active electrode only and the right is the capacitance when the whole device is considered.
  • B IOC
  • C 20C
  • D lOOC
  • E 200C.
  • Figure 42 shows GCDC potential profiles for an example of a coin cell fabricated from an example of a PEDOT-only coin cell with activated carbon as counter electrode.
  • A Capacitance over a variety of C rates where the left axis is the capacitance accounting for the mass of the active electrode only and the right is the capacitance when the whole device is considered.
  • B IOC (C) 20C
  • D 50C
  • E lOOC
  • F 200C.
  • Figure 43 shows physical mixture (grinding) of a 1-to-l PEDOT / COF mixture where the PEDOT was chemically polymerized separately from the DAAQ-TFP COF powder.
  • Ranges of values are disclosed herein. The ranges set out a lower limit value and an upper limit value. Unless otherwise stated, the ranges include all values to the magnitude of the smallest value (either lower limit value or upper limit value) and ranges between the values of the stated range.
  • the present disclosure provides conducting-polymer modified covalent organic frameworks (COFs), methods of making conducting-polymer modified covalent organic frameworks, and uses thereof.
  • COFs conducting-polymer modified covalent organic frameworks
  • the present disclosure also provides materials and devices comprising conducting-polymer modified covalent organic frameworks.
  • Such frameworks provide materials which have properties that make them useful for applications such as, for example, incorporation in electronic devices.
  • Conducting-polymer modified covalent organic frameworks offer a new strategy for assembling organic semiconductors into robust networks with atomic precision and long-range order.
  • COFs incorporate organic subunits into periodic two- and three- dimensional porous crystalline structures held together by covalent bonds rather than noncovalent interactions. These linkages provide robust materials with precise and predictable control over composition, topology, and porosity. The relative geometries of the reactive groups in the starting materials determine the COF's topology, which does not change significantly as other functional groups are varied.
  • Two-dimensional COFs can assemble functional aromatic systems into cofacially-stacked morphologies ideal for transporting excitons or charge carriers through the material.
  • the term "moiety" refers to a chemical entity that has two or more termini that can be covalently bonded to other chemical species. Examples of moieties include, but are not limited to:
  • alkyl group refers to branched or unbranched hydrocarbons.
  • alkyl groups include substituted or unsubsituted methyl groups (-CH3), ethyl groups, propyl groups, butyl groups, isopropyl groups, tert-butyl groups, and the like.
  • the alkyl group can be a C1-C20 alkyl group including all integer numbers of carbons and ranges of numbers of carbons there between.
  • the alkyl group can be unsubstituted or substituted with one or more substituent.
  • substituents include, but are not limited to, various substituents such as, for example, halogens (-F, -CI, -Br, and -I), aliphatic groups (e.g., alkenes, alkynes), aryl groups, alkoxides, carboxylates, carboxylic acids, ether groups, and the like, and combinations thereof.
  • aryl group refers to a C5 to
  • the aryl group can comprise polyaryl moieties (such as, e.g. fused rings and/or biaryl moieties).
  • the aryl group can be
  • substituents include, but are not limited to, various substituents such as, for example, halogens (-F, -CI, -Br, and - I), aliphatic groups (e.g., alkenes, alkynes), aryl groups, alkoxides, carboxylates, carboxylic acids, ether groups, and the like, and combinations thereof.
  • suitable aryl groups include phenyl groups and biphenyl groups.
  • the present disclosure provides conducting-polymer modified covalent organic frameworks.
  • the conducting-polymer modified COFs comprise one or more COF layers and one or more conducting polymers.
  • the conducting polymers at least partially fill a portion of or all of the COF pores and/or at least partially coat the exposed surfaces of the COFs (e.g., COF layers or COF films).
  • the COFs are redox active COFs.
  • the COFs are, for example, beta- ketoenamine linked COFs, imine linked COFs, hydrazone linked COFs, imide linked COFs, or boronate ester linked COFs. It is desirable that the COFs exhibit reversible redox processes. Examples of COFs and methods of making the COFs are described in Examples 1 and 2. In an embodiment, the COFs comprise co-facially stacked aromatic moieties.
  • Examples of suitable COFs are known in the art. Examples of suitable COFs can be made by methods known in the art.
  • COFs include, but are not limited to, COFs comprising redox- active 2,6-diaminoanthraquinone (DAAQ) moieties (e.g., a 2D COF linked by ⁇ - ketoenamines, imines, or enamines).
  • DAAQ redox- active 2,6-diaminoanthraquinone
  • the DAAQ moieties can be reduced to
  • the COF is DAAQ-TFP COF.
  • the COFs can be layered sheets of 2D COFs that typically adopt nearly eclipsed stacked structures, providing continuous nanometer-scale channels normal to the stacking direction, as well as significant ⁇ -orbital overlap between monomers in adjacent layers. These features can provide an accessible high surface area interface for double-layer formation and pathways for charge transfer to/from, for example, redox-active groups that comprise the walls.
  • the COFs are crystalline.
  • the COFs can form crystallites (i.e., discrete structures) where the longest dimension of the crystallites can be from 50 nm to 10 microns, including all values to the nanometer and ranges of nanometers therebetween.
  • the COF comprise at least 2 unit cells, at least 5 unit cells, and at least 10 unit cells.
  • the COFs may be present as a thin film (e.g., a film having a thickness of 10 nm to 10 microns, including all values to 10 nm and ranges therebetween).
  • the COF have a porous (e.g., microporous (pores with a longest dimension of less than 2 nm) or mesoporous structure (pores with a longest dimension of 2 nm to 50 nm).
  • the porous structure forms a repeating pattern (i.e., not a random distribution of pores).
  • the framework has pores, where the pores run parallel to the stacked aromatic moieties.
  • the pores have a longest dimension (e.g., a diameter) of from 2 nm to 6 nm, including all values to the 0.05 nm and ranges to the 0.1 nm therebetween. In one example, the pores are 2.3 nm in diameter.
  • the COFs can have high surface area.
  • the COFs can have a surface area 500 m 2 /g to 2500 m 2 /g, including all values to the m 2 /g and ranges of surface area therebetween.
  • the surface area of the COFs can be determined by methods known in the art, for example, by BET analysis of gas (e.g., nitrogen) adsorption isotherms.
  • one or more of the COFs have one or more redox active compounds covalently attached to the one or more of the COFs.
  • a COF comprises one or more redox active compounds or one or more moieties derived from one or more redox active compounds covalently attached to one or more moieties of the COF (e.g., one or more redox active moieties of the COF).
  • a COF comprises one or more moieties (e.g., one or more redox active moieties of the COF) that have one or more redox active compounds or one or more moieties derived from one or more redox active compounds.
  • the one or more redox active compounds or one or more moieties derived from one or more redox active compounds can form the sides of hexagonal repeat units of the COF.
  • redox active compounds examples include:
  • n is (e.g., is independently at each occurrence in the composition) 1 to 12
  • alkyl is (e.g., is independently at each occurrence in the composition) a Ci to C20 alkyl group as described herein
  • aryl is (e.g., is independently at each occurrence in the composition) a C5 to C20 aryl group as described herein
  • halogen is (e.g., is independently at each occurrence in the composition) -F, -CI, -Br, or -I.
  • one or more conducting-polymer modified COF layers are disposed on a substrate.
  • the substrate is a conducting substrate (e.g., a metal or metal coated substrate such as a gold or gold-coated substrate).
  • compositions comprising one or more conducting polymer modified COFs of the present disclosure.
  • a thin film comprises one or more conducting polymer modified COFs (e.g., one or more conducting polymer modified COF layers).
  • a composition can comprise one or more conducting polymer modified COFs and a carbon-containing material (e.g. a conducting carbon-containing material).
  • a carbon-containing material e.g. a conducting carbon-containing material
  • Examples of carbon-containing materials include activated carbons, carbon black, graphitic carbon, graphene, carbon nanotubes, and the like.
  • the composition can also comprise one or more binders.
  • the present disclosure provides a method for making conducting- polymer modified COFs as described herein.
  • the method comprises electropolymerizing a conducting-polymer in the presence of a COF (e.g., COF layer or COF layers) such that a conducting-polymer modified COF layer or layers are formed.
  • a COF e.g., COF layer or COF layers
  • the method comprises multiple electropolymerization steps (e.g., two to 20 electropolymerization steps, including all integer number of electropolymerization steps and ranges therebetween).
  • An example of a method of making conducting polymer modified COFs is shown in Figure 9.
  • the method comprises electropolymerizing a conducting- polymer onto a COF-modified substrate.
  • the substrate can serve as a working electrode that can be used, for example, in an electropolymerization using cyclic voltammetry.
  • An example of a suitable conducting polymer of the present disclosure is PEDOT.
  • Other examples of conducting polymers include poly(3,4-ethylenedioxythiophene),
  • poly(vinylferrocene) poly(triphenylene), poly(azulene), poly(furan), poly(3- phenylthiophene), poly(3-[4fluorophenyl]thiophene), poly([fluoro-3-alkyl]thiophene), poly(isobenzo[c]thiophene), poly(benzothienoindole), poly(l,4-di[2-thienyl]-l,2-butadiene), poly(naphthalene), poly(anthracene), polyacene, poly(heteroacene).
  • the conducting polymer may be amorphous.
  • the conducting polymers can be formed by polymerizing conducting monomers.
  • the conducting monomers (a portion or all of the monomers) may have one or more redox active compounds covalently bonded to them.
  • a method consists essentially of a combination of the steps of the methods disclosed herein. In another embodiment, a method consists of such steps.
  • the present disclosure provides devices comprising at least one conducting polymer modified COF of the present disclosure.
  • the conducting polymer modified COFs can be incorporated in electrical devices such as, for example, electrical energy storage systems (e.g., in an electrical energy storage device such as a super capacitor).
  • an electrochemical supercapacitor comprises a conducting polymer modified COF of the present disclosure.
  • a composition comprising one or more covalent organic framework layers (COFs) of the present disclosure with conducting polymer, at least partially, disposed in the pores and/or surface of the covalent organic framework layers.
  • COFs covalent organic framework layers
  • a composition according to Statement 1 wherein one or more of the COF layers and/or the conducting polymer comprises one or more redox active compounds and/or one or more moieties derived from redox active compounds (e.g., one or more of the COF layers (e.g., one or more of the COFs of the one or more COF layers) have one or more redox active compounds and/or one or more moieties derived from one or more redox active compound(s) covalently attached to one or more of the COF layers (e.g., one or more of the COFs of the one or more COF layers) and/or one or more of the COF layers (e.g., one or more of the COFs of the one or more COF layers) comprises one or more moieties (e.g., one or more redox active moieties of the COF(s) that comprise one or more redox active compounds and/or one or more moieties derived from one or more redox active compounds and/or the conducting
  • DAAQ 2,6-diaminobenzene
  • TFP 1,3,5-triformylphluroglucinol
  • Statement 11 A composition according to Statement 10, where the thin film is disposed on at least a portion of a substrate.
  • Statement 12 A composition according to Statements 10 or 11, where the substrate is a metal substrate or metal-coated substrate.
  • a conducting polymer modified COF comprising a COF with conducting polymer, at least partially, disposed in the pores and/or surface of the covalent organic framework.
  • Statement 14 A conducting polymer modified COF according to Statement 13, where the COF and/or conducting polymer comprises redox active moieties or one or more moieties derived from one or more redox active compounds (e.g., a COF has one or more redox active compounds and/or one or more moieties derived from one or more redox active compounds covalently attached to the COF and/or a COF comprises one or more moieties (e.g., one or more redox active moieties of the COF) that comprise one or more redox active compounds and/or one or more moieties derived from one or more redox active compounds and/or the conducting polymer has one or more redox active compounds and/or one or more moieties derived from one or more redox active compounds).
  • the COF and/or conducting polymer comprises redox active
  • Statement 16 A conducting polymer modified COF according to any one of Statements 13 to 15, where the conducting polymer is poly(3,4-ethylenedioxythiophene) PEDOT.
  • DAAQ 2,6- diaminobenzene
  • TFP 1,3,5-triformylphluroglucinol
  • Statement 18 A conducting polymer modified COF according to any one of Statements 13 to 17, where one or more of the covalent organic framework layers comprises DAAQ moieties.
  • Statement 20. A conducting polymer modified COF according to any one of Statements 13 to 19, wherein the pores of one or more of the COF have a dimension of 2 mm to 50 nm.
  • Statement 21. A conducting polymer modified COF according to any one of Statements 13 to 20, wherein the surface area of the COF is 500 m 2 /g to 2500 m 2 /g.
  • Statement 22 A conducting polymer modified COF according to any one of Statements 13 to 21, wherein the composition is in the form of a thin film.
  • Statement 23 A conducting polymer modified COF according to Statement 22, wherein the thin film is disposed on at least a portion of a substrate.
  • Statement 24 A conducting polymer modified COF according to Statements 22 or 23, wherein the substrate is a metal substrate or metal-coated substrate.
  • Statement 25 A method for making one or more covalent organic framework layers with conducting polymers, at least partially, disposed in the pores and/or surface of the covalent organic framework layers: electropolymerizing a conducting-monomer in the presence of one or more COF layers, wherein the one or more conducting-polymer modified COF layers are formed.
  • An electronic device comprising one or more covalent organic framework layers with conducting polymers, at least partially, disposed in the pores and/or surface of the covalent organic framework layers.
  • Statement 27 An electronic device according to Statement 26, wherein the device is selected from the group consisting of batteries and capacitors.
  • Statement 28 An electronic device according to Statements 26 or 27, wherein the capacitor is a super capacitor.
  • the DAAQ-TFP COF / PEDOT composite films may also be charged and discharged much more quickly than unmodified DAAQ-TFP COF while maintaining a larger percentage of their capacity.
  • DAAQ-TFP COF / PEDOT exhibits a capacitance of 159 F cm "3 when charged at 1600 C (2.25 s).
  • an unmodified DAAQ-TFP COF of the same thickness exhibits a capacitance of only 6.3 F cm "3 .
  • the DAAQ-TFP COF / PEDOT composite films show outstanding stability to repeated charge/discharge cycles, with no loss of capacitance observed after at least 2250 cycles.
  • DAAQ-TFP thin films were prepared using previously described conditions, in which a solution of TFP in DMF was added dropwise over 1 h to a solution of DAAQ in DMF containing a Au substrate. Varying the initial monomer concentration provided control of the resulting film thickness.
  • an initial DAAQ concentration ([DAAQJo) of 22 mM provided DAAQ-TFP thin films with thicknesses of 810 ⁇ 224 nm thick as determined by AFM. The chemical composition and crystallinity of these films were very similar to those described previously.
  • PEDOT was electropolymerized within a DAAQ-TFP thin film working electrode by performing cyclic voltammetry in a CFbCN solution of EDOT (100 mM, 100 mM BU4CIO4 supporting electrolyte).
  • the voltammetric response of the system was characteristic of the electropolymerization of a conductive polymer, showing a continuous increase in current with each subsequent scan.
  • the voltage at which these redox processes occur (-0.8 V vs Ag/AgC10 4 ) is also consistent with that expected for EDOT
  • Synchrotron Source indicated that the as-synthesized DAAQ-TFP films are crystalline, with the expected peak at 0.23 A "1 that corresponds to the (100) reflection of the hexagonal lattice. This peak is also observed in films that were subjected to two electropolymerization cycles, indicating that the periodicity of the DAAQ-TFP thin film is retained under the
  • XPS performed on a DAAQ-TFP COF film subjected to nine PEDOT electropolymerization cycles was also consistent with the formation of PEDOT in and / or on the COF host.
  • the peaks for the Nis electrons were used as a marker for the DAAQ-TFP COF, and the S 2p peak was used to indicate the presence of PEDOT.
  • XPS spectra were recorded after a series of exposures to an Ar ion beam that etches both materials, providing a quantitative measure of the amounts of each material as a function of film depth. Prior to etching, an intense S 2p signal is observed, along with no signal above baseline in the Nis region. Upon increased etching, the Nis peak is observed and the S 2p decreases in intensity but does not disappear (Figure 2D).
  • the PEDOT / DAAQ-TFP COF composite film demonstrated an enhanced current response using cyclic voltammetry, as compared to an unmodified DAAQ-TFP COF film (0.5 M H2SO4, 20 mV s "1 scan rate, Figure 3 A). In both CVs, we see highly reversible electrochemistry consistent with the rapid electron transfer to / from anthraquinones.
  • the PEDOT / DAAQ-TFP COF exhibits more than an order of magnitude increased current. These responses correspond to the storage of only 0.230 mC of charge for the as-synthesized DAAQ-TFP thin films and 9.3 mC for the PEDOT modified COF sample. Furthermore, the PEDOT-modified film retains its higher charge storage capacity at faster scan rates up to at least 500 mV s "1 . In contrast, the as-synthesized DAAQ-TFP thin film shows ca. 70% lower capacitance at scan rates greater than 100 mV s "1 ( Figure 3B). These experiments indicate that the electropolymerization of PEDOT in a redox-active COF film provides dramatically enhanced charge storage, capacity, and rate, most likely by improving the film's conductivity.
  • PEDOT / DAAQ-TFP electrodes consistently show higher capacitances than the unmodified DAAQ-TFP COF, and maintain more than 80% of their capacitance when charged or discharged at 10 - 100 C, corresponding to charge times of 360 - 36 seconds, respectively.
  • DAAQ-TFP film even retains up to 50% of its maximum capacity (350 F cm “3 ) at the extremely high charging rate of 1600 C, corresponding to a charging time of 2.25 s ( Figure 4A).
  • the unmodified COF films show only moderate capacitances at 10 C (20 F cm “3 ), which decrease even further at higher charge / discharge rates.
  • the PEDOT-modified DAAQ-TFP COF films also show promising stability over the course of many charge-discharge cycles. For example, the capacitance of the film was recorded at 10 C for three cycles, then 100 C for 2250 cycles, and then three more cycles at 10 C. No decrease in capacitance is observed under these conditions, which is consistent with the long-term stability of the unmodified DAAQ-TFP COF film to at least 5000 cycles that we previously reported (Figure 4B).
  • the resulting composite film shows both enhanced charge capacity and more rapid charging and discharging processes, making these systems of interest for electrical energy storage devices.
  • PEDOT-infiltrated COF films exhibit improved electrochemical responses, including quantitative access to their redox-active groups, even for 1 ⁇ -thick COF films that otherwise provide poor electrochemical performance.
  • PEDOT- modified COF films can accommodate high charging rates (10-1600C) without
  • the resulting PEDOT-modified COF films exhibit quantitative electrochemical accessibility of their redox-active groups and enable the use of at least 1 ⁇ thick films that can sustain fast charging rates (up to 1600C) without compromising performance.
  • This improved performance relative to as-synthesized COF films corresponds to a thirty-fold increase in volumetric energy density and a twelve-fold increase in volumetric power density.
  • gravimetric capacitances are less meaningful than volumetric capacitance because the mass of the active material is often only a small fraction of the weight of the device, negligible and capacitances based on active material mass can be artificially high.
  • the electropolymerization of PEDOT within a nanoporous COF template represents a means to organize the conductive polymer at the nanometer length scale, which is an increasingly important capability for electrochromic, drug delivery, electrocatalytic, and EES devices, among other applications.
  • Templated electropolymerizations form conducting polymers, such as polypyrrole, polythiophene, or polyaniline, as nanowire arrays, which respond rapidly in electrochemical devices largely because of short counter ion diffusion lengths.
  • the porous templates are removed.
  • the pore-confined PEDOT effectively wires the redox-active groups of the COF to the electrode, enabling the use of thicker films and faster charging rates.
  • PEDOT was electropolymerized within a DAAQ-
  • DAAQ-TFP thin films were prepared by adding a DMF solution of 2,4,6- triformylphloroglucinol (TFP) over 1 h to a DMF solution of DAAQ containing a gold substrate.
  • TFP 2,4,6- triformylphloroglucinol
  • DAAQ-TFP thin films were prepared by adding a DMF solution of 2,4,6- triformylphloroglucinol (TFP) over 1 h to a DMF solution of DAAQ containing a gold substrate.
  • TFP 2,4,6- triformylphloroglucinol
  • An X-ray photoelectron spectroscopy (XPS) depth profile of the elemental composition of a PEDOT-modified DAAQ-TFP film subjected to nine electropolymerization cycles further indicates the presence of PEDOT throughout the 2D COF film. XPS spectra were recorded after a series of exposures to an Ar ion beam that etches both the PEDOT and the COF.
  • the PEDOT-modified DAAQ-TFP composite films exhibited dramatically enhanced current responses in cyclic voltammetry experiments when compared to an unmodified DAAQ-TFP film (0.5 M H 2 S0 4 , 20 mV s _1 scan rate, Figure 7A). While both CVs exhibit reversible electrochemistry consistent with electron transfer between the anthraquinones and the working electrode, the PEDOT-modified DAAQ-TFP films exhibited more than an order of magnitude increased current.
  • the PEDOT-modified DAAQ-TFP film even retains 50% of its maximum capacitance (350 F cm “3 ) at the extremely high charging rate of 1600C, corresponding to a charging time of only 2.25 s (Figure 8 A).
  • the unmodified DAAQ-TFP films show only moderate capacitances at IOC (20 F cm "3 ), which decreased further at higher charge/discharge rates.
  • the PEDOT-modified DAAQ-TFP films also showed desirable stability over 10,000 charge-discharge cycles (Figure 8B). The capacitance of the film was measured at IOC for three cycles, then at lOOC for 10,000 cycles, and finally three more cycles at IOC. No decrease in capacitance was observed under these conditions.
  • PEDOT-modified DAAQ-TFP COF powder (1 : 1 PEDOT/COF by mass as active electrode and activated carbon counter electrode) was integrated into coin cells. When two of these cells were connected in series, they successfully powered a green LED for 30 s. Electrochemical performance testing of the cells show that they exhibit well- defined redox waves associated with the reduction and oxidation of the anthraquinone moieties in both the CV and GCDC responses ( Figures 41 and 42) with a capacitance of 197 F g "1 based on the active composite electrode or 30 F g "1 when the mass of the active and counter electrodes are considered.
  • these cells are not optimized and the gravimetric capacitances are expected to increase by identification of the minimal mass of counter electrode and PEDOT to elicit the same electrochemical performance.
  • they demonstrate a means to fabricate working charge storage devices from conducting polymer- modified COFs, even as methods to access thicker films continue to emerge.
  • composites show significant improvements in volumetric energy and power densities relative to unmodified COF films, as well as desirable stability to cycling.
  • N,N-dimethylformamide was added to a glass vial.
  • a gold electrode 2.5 cm x 1.3 cm was submerged in the solution, and a septum was used to seal the vial.
  • the solution was placed on a hotplate preheated to 90 °C.
  • TFP 10 mg, 0.048 mmol was added over the course of one hour via syringe from a 10 mg mL "1 solution in DMF. During the course of the addition, the reaction mixture was gently swirled. After the addition, the reaction was allowed to proceed at 90 °C for an additional 3 h. The total reaction time was 4 h (including TFP addition), and the final volume was 4.2 mL after TFP addition.
  • the film which covered electrode was removed, rinsed three times with DMF and twice with acetone then dried in air.
  • Electropolymerization was carried out in a standard three electrode set up under an argon atmosphere with a DAAQ-TFP COF film on gold (prepared as described above) as the working electrode, a Ag/AgC10 4 reference electrode, and either a coiled Pt wire or high surface area carbon counter electrode.
  • a controlled area (0.64 cm 2 ) surface cell was used for electrochemistry experiments.
  • a 0.1 M solution of EDOT was prepared in 0.1 M TBAP, and nine electropolymerization cycles between -0.5 and 1.1 V vs Ag/AgC10 4 at 20 mV s "1 were carried out.
  • the PEDOT-modified DAAQ-TFP on gold was rinsed 3x with acetonitrile and 2x with acetone before electrochemical testing.
  • Electrochemical testing of PEDOT-modified DAAQ-TFP films After electropolymerization, the prepared films were rinsed as described above and submerged in 0.5 M H2SO4. For initial testing, cyclic voltammetry with scan rate dependence, or galvanostatic charge/discharge experiments were performed in a three electrode
  • Capacitances were obtained from the discharge curves by multiplying the applied current by the time of discharge and normalizing by the examined voltage window and geometric film volume. Film volumes were obtained from the electrochemical cell area and the experimentally determined film thicknesses as described above. Sample calculations can be found below. Thin films were also tested in a two-electrode thin film set-up where films were countered to a high surface area carbon after shorting the reference and counter electrode together. Sample calculations for volumetric capacitance and electrochemically accessible anthraquinones can be found below.
  • GXD Grazing incidence X-ray diffraction
  • CRISS Cornell High Energy Synchrotron Source
  • Motorized slits were used to define a 0.2 ⁇ 3 (VxH) mm 2 beam.
  • the data were collected using a 640- element ID diode-array, of which each element incorporates its own pulse counting electronics capable of count rates of -105 photons s "1 .
  • a set of 0.1° Soller slits were used on the detector arm to define the in-plane resolution. The scattering geometry is described in detail elsewhere.
  • Atomic force micrographs were taken on an Asylum MFP-3D-BIO operating in tapping mode and equipped with a Tap300DLC diamond-like carbon or Tapl50Al-G Si tip with aluminum reflex coating (tip composition was not seen to affect image quality).
  • Electrochemical-Quartz Crystal Microbalance (EQCM) experiments were performed using a Stanford Research Systems QCM 200 interfaced to a Princeton Applied Research Versastat3 potentiostat.
  • DAAQ-TFP COF was grown on O100RX3 quartz resonators (Au with Ti adhesion layer) using the slow addition method described below.
  • a water-jacketed beaker was used to maintain a constant temperature of 25 °C during the EQCM experiment. The changes in mass and resistance were monitored over the
  • TFP 1,3,5-triformylphloroglucinol
  • DAAQ-TFP Films Crystalline film growth: To a glass vial, a DAAQ (17 mg, 0.071 mmol) in N,N-dimethylformamide was added. A gold electrode (2.5 cm x 1.3 cm) was submerged in the solution and a septum cap placed on the top of the vial.
  • Electropolymerization of 3,4-ethylenedioxythiophene (EDOT) The electropolymerization was performed in a standard three-electrode configuration under an Ar atmosphere. The cell consisted of a DAAQ-TFP COF film on gold (prepared as described above) as the working electrode, a Ag/AgC10 4 reference electrode, and either a coiled Pt wire or high surface area carbon counter electrode. A controlled area (0.64 cm 2 ) surface cell was used for electrochemistry experiments. A 0.1 M solution of EDOT was prepared in 0.1 M TBAP, and nine electropolymerization cycles between -0.5 and 1.1 V vs Ag/AgC10 4 at 20 mV s "1 were performed.
  • EDOT 3,4-ethylenedioxythiophene
  • a nine-cycle polymerization passes the oxidative potential 10 times, because the initial cycle starts from open circuit, which is approximately 0.2 V vs Ag/AgC10 4 .
  • the counter electrode was placed in the same location relative to the working electrode during electropolymerization (c.a. 2 cm separation). After electropolymerization, the working electrode was rinsed three times with acetonitrile and two times with acetone prior to its electrochemical testing.
  • AFM Atomic Force Microscopy
  • the Sauerbrey mass of the electrodeposited PEDOT was calculated using the Sauerbrey equation Af is the frequency change, fo is the resonant
  • Electropolymerization was optimized at nine cycles (20 mV s "1 , 0.1 M EDOT / 0.1 M TBAP / MeCN, Figures 23 and 24). When the electropolymerization was carried out for two or five cycles, the amount of charged stored in the films was less than the theoretical (assessed through integration of the anthraquinone oxidation peak). When an 18 cycle polymerization was tested, the amount of charge stored in the film diminished with increased scan rate indicating poor access to the anthraquinones. This is consistent with densely polymerizing and overloading the COF with PEDOT such that electrolyte and counter ions cannot "keep up" with the redox-processes at the higher scan rates.
  • Each unit cell provides one anthraquinone, so 8.3 X 10 12 quinones are exposed providing 1.6 X 10 13 electrons or 2.7 X 10 -11 moles of electrons
  • the onset potential for PEDOT doping depends on a number of variables including solvent and polymer chain length. However, it is generally negative of 0.0 V vs Ag/AgCl as is evident in Figure 7. However, the formal potential for oxidation of the DAAQ groups is only slightly positive of the onset of PEDOT doping. Thus, the PEDOT is not fully doped at potentials where DAAQ begins to be oxidized. This means that there can be some extent of "operationally" self- discharge especially at very slow sweep rates since the electrode would be effectively "spending more time” in the potential region where these processes would be operative.
  • Figure 43 demonstrates that DAAQ-TFP COF is physically mixed via grinding with PEDOT to prepare a slurry modified electrode similar to our previous preparation, 3 the conducting polymer does not infiltrate the pores and is not intimately mixed with the COF.
  • This CV response provides further support that both the chemical and electrochemical polymerization of EDOT is filling the pores of the DAAQ-TFP COF.
  • PEDOT modified DAAQ-TFP COF powder or coin cell preparation The 10: 1 and 1 : 1 PEDOT/COF composites were synthesized via chemical oxidation of EDOT in the presence of DAAQ-TFP COF powder. A 43 mg portion of EDOT was added into a mixture COF powder (30 mg) in methanol (MeOH) at 0 °C. After 15 minutes of mixing, Fe(C10 4 )3 (0.214 g) was dissolved in MeOH and slowly added to the mixture of COF and EDOT. After stirring for 6 hours, dark blue powder was obtained. The polymer was extensively washed using MeOH to remove traces of Fe(C10 4 )3 and dried at 90 °C overnight.
  • MeOH methanol
  • Coin-shaped electrodes of both cathode (PEDOT/COF) and anode (activated carbon, AC) were prepared by adding 90 mg of material (for cathode, 80 mg of PEDOT/COF + 10 mg Super P carbon, for anode 90 mg of activated carbon) to a scintilation vial that is equipped with a stir bar and 10 mg of polytetrafluoroethylene (PTFE) as a binder. Less than 1 mL of ethanol was added and the mixture was allowed to vigorously mix at 60 °C until the mixture is almost dry. The gels were rolled into a thin film and was allowed to dry at 60 °C overnight.
  • material for cathode, 80 mg of PEDOT/COF + 10 mg Super P carbon, for anode 90 mg of activated carbon
  • PTFE polytetrafluoroethylene
  • a lithium-ion battery CR2032 cell was used as the device chamber, and was assembled, by stacking a Ti-foil, PEDOT/COF (cathode), separator, activated carbon, Ti-foil, stainless steel, spring and a cap (Figure 32).
  • the diameters of the components may be found in Table 3.
  • CV characterization of single coin cell device was tested by contact using Cu tape. After individual cells were confirmed to be working, two cells were connected in series using Arbin channels connect by wires ( Figure 23F). In order to charge a 2.2 V LED, the setup was charged to 2.2 V for 10 s, then was allowed to relax until the LED dimmed completely (about 30 s).

Abstract

L'invention concerne des couches d'une structure organique covalente (COF) comportant un polymère conducteur, lequel est au moins partiellement placé dans les pores et/ou la surface des couches de la structure organique covalente. Les couches de la structure organique covalente comportant un polymère conducteur peuvent être fabriquées par l'électropolymérisation d'un ou de plusieurs monomères conducteurs en présence d'un ou de plusieurs couches de COF. Un dispositif électronique tel que, par exemple, un accumulateur ou un condensateur, peut comprendre une ou plusieurs couches de cette structure organique covalente comportant un polymère conducteur.
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