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WO2020107131A1 - Accumulateurs rechargeables à l'énergie solaire, basés sur des polymères nanostructurés - Google Patents

Accumulateurs rechargeables à l'énergie solaire, basés sur des polymères nanostructurés Download PDF

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WO2020107131A1
WO2020107131A1 PCT/CL2018/050117 CL2018050117W WO2020107131A1 WO 2020107131 A1 WO2020107131 A1 WO 2020107131A1 CL 2018050117 W CL2018050117 W CL 2018050117W WO 2020107131 A1 WO2020107131 A1 WO 2020107131A1
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pedot
battery according
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María Angélica DEL VALLE DE LA CORTINA
Andrés Mauricio RAMÍREZ RAMÍREZ
Loreto Andrea HERNÁNDEZ DÍAZ
Manuel Alejandro GACITÚA SANTALICES
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Pontificia Universidad Catolica de Chile
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D64/00—Electrodes of devices having potential barriers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D64/00—Electrodes of devices having potential barriers
    • H10D64/60—Electrodes characterised by their materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • 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
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention is framed in the technical field of nanomaterial synthesis, specifically in the development of rechargeable batteries with solar energy based on nanomaterials.
  • inorganic cells are currently over 20% efficient, while organic photovoltaic cells (OPVs) have only reached between 5 and 10%.
  • OOVs organic photovoltaic cells
  • organic compounds have acquired great strength, due to two quite important advantages that, additionally, go hand in hand with the environment: i) a significant decrease in manufacturing costs, since for the Construction of inorganic devices requires the use of clean rooms, with air flow, humidity, controlled temperatures, among others, while OPVs do not have such restrictions; ⁇ I) Its elimination at the end of its useful life generates less contamination of the environment, thinking that the most efficient inorganic cells have compounds such as cadmium or silicon derivatives, which are highly harmful to human health, during their manufacture.
  • the photovoltaic cells based on organic compounds (OPVs) present a mechanism of generation of "electron-hole” torque very different from that of silicon cells, massively used, since in the latter it occurs spontaneously at room temperature and at potentials close to 0 , 1 V, subsequently generating the rapid promotion in opposite directions, to exit the system.
  • OCVs organic compounds
  • the exciton after the absorption of light, the formation of a species in the excited state occurs, called the exciton, which after its formation diffuses to the interface of the donor / acceptor junction, where the formation of the “electron” pair occurs.
  • the operation of the device described in the present invention is similar to that presented by lithium-ion batteries, but in this case the doping / undoping, absorption and desorption process of ions is used, which have polymers such as polythiophene (Pth), poly (3,4-ethylenedioxythiophene) (PEDOT) or polypyrrole (PPy).
  • Pth polythiophene
  • PEDOT poly (3,4-ethylenedioxythiophene)
  • Py polypyrrole
  • the theoretical foundation of recharging this type of battery consists of the use of a photo-anode, whose mission is to absorb photons from a light source, generating two key processes: i) oxidation of the polymer present in said photo-anode and ii) that the photocurrent is used in the reduction of the polymer present in the cathode. While the discharge of the battery consists of the oxidation of the polymer present in the cathode and the reduction of the superficial part of the photo-anode, generated by a potential difference between both electrodes.
  • the photo-anode For the preparation of solar rechargeable batteries, the photo-anode must meet the same expectations as those of inorganic cells, based on two fairly important processes: i) photo-generation of electric charge and ii) the transport of this through of a pn junction, very similar to that of cells of inorganic origin.
  • the cathode must have properties similar to those presented in lithium-ion batteries: i) the discharge reaction must have a very negative DQ value, to generate a high discharge voltage; ii) the structure must be of low mass and capable of exchanging a large quantity of ions, generating a high load capacity; iii) high ion diffusion coefficient, producing a high charge density; ⁇ V) the structure of the cathode must be modified as little as possible during ion exchange, in charging and discharging the battery, allowing a greater number of charge / discharge cycles; v) it must be chemically stable, non-toxic and inexpensive and vi) a material that is easy to handle.
  • Morphology and porosity have been shown to play a fundamental role for photovoltaic devices and rechargeable batteries. These properties can be modified depending on the electrolytic solution (salts, solvent, concentrations) used during the electropolymerization.
  • the photo-anode provides the possibility of recharging through the photocurrent produced at the interface of the hetero-junction nT ⁇ 0 2
  • the electrolytic solution used in batteries plays an important role in contributing to efficiency.
  • these electrolytic salts used it is worth noting three, which are the ones that have been tested the most until now: UCIO 4 , LiPF 6 and LiBF 4 , mainly because they are stable under high voltages. Flan has been used in different solvents, such as acetonitrile, dimethyl sulfoxide, among others, looking for three essential conditions: i) conductivity of the order of 10 2 S-cnr 1 ; ⁇ I) good ionic conductivity and iii) low viscosity.
  • the absence of water in the electrolytic solution does not need to be as strict when no lithium cathode is used (in this case, it is established as a critical limit, 20 ppm of water).
  • the absence of metallic lithium in the charge / discharge mechanism makes it possible to use water, which meets the three essential conditions described above, as the main solvent.
  • EP3202716A1 describes a method of producing titanium oxide particles, by mixing a solution of a titanium alkoxide with a salt of a titanium metal and a compound having a nitrogen-containing 5-membered ring, also comprising a step of generating fine titanium oxide particles by heat and pressurization of said solutions. It is indicated that the preferred temperature used was 150-350 ° C. Also I know indicates that the titanium oxide particles obtained are contacted with a probe sensitive to sunlight, and it is described that the probe used was DYESOL.
  • US5525440A describes a method of producing a photoelectrochemical cell comprising porous titanium dioxide in an electrode layer, an electrolyte, a layer having a chromophore, situated between said electrode and said electrolyte and a conductive transparent layer that delimits the layer of the electrode and said electrolyte.
  • the invention comprises a method that considers the step of forming an electrode layer through a colloidal dispersion of titanium dioxide particles in a solvent.
  • the invention contemplates a post-treatment step, where a temperature of 500 ° C is applied, to evaporate the titanium (IV) chloride that was used to synthesize the titanium dioxide.
  • CN102675877A describes a polypyrrole nanowire, a preparation method and uses.
  • the claimed method describes obtaining a porous aluminum "mold" obtained by secondary anodic oxidation, where one of the sides of the mold is covered with a layer of gold.
  • the mold is then washed with a solution of 2-guanitidine benzimidazole in ethanol, for at least 2 hours, and then said compound is washed with ethanol, thus obtaining one of the sides covered with gold, and the other side has covered pores with said compound.
  • the mold is placed in a pyrrole solution with ethanol.
  • the polymer is electroplated for 2 to 8 hours, using direct current voltage.
  • the gold layer and the mold are removed sequentially by physical and chemical methods.
  • the chemical agent used to remove the "template” was a 5% m / v phosphoric acid solution.
  • the nanowire can be widely used for the detection of traces of Fe 3+ in an organism in the environment.
  • W02009050168A1 describes an arrangement of nanowires to electrically control the controlled release of a therapeutic composition, comprising a set of mannoscope cables, which are tied to a solid, electrically conductive support.
  • the invention also relates to a method of preparing a nanowire array and an electrode. Said method comprises, in a first stage, depositing a polymer matrix on an electrode, forming a first layer.
  • the polymer used can be selected from carbonic acid polyesters, such as bisphenol A polycarbonate, saturated polyesters, etc. This polymer matrix can be used as a container for drug release, but also for the synthesis of nano-structured electrodes.
  • the second stage of the method involves the generation of pores in the polymer matrix, through bombardment of the polymer with heavy ions such as Ar, Kr or Xe.
  • the last stage of the method would consist of dissolving the porous matrix.
  • the "mold” dissolving agent It was dichloromethane, and sodium hydroxide was used to remove the rest of the polymer not bound to the system.
  • US2006021879A1 describes a method of producing a set of oriented nanofibers, by electro synthesis.
  • the method consists of a first step in contacting the electrode with a solution containing 0.5M aniline monomer and 1.0M perchloric acid. Then, current is applied to the electrode with the solution, following the following protocol: 0.08 mA / cm 2 for 0.5 hours, followed by 0.04 mA / cm 2 for 3 hours, and continued for another 3 hours at 0.02 mA / cm 2 .
  • one of the polymers that can be used is polypyrrole. It is also indicated that the use of a mold is not necessary for the nanowires to polymerize.
  • US2013177820A1 describes silica-containing compositions, methods of preparing these compositions, and methods of electrodepositing amorphous silicone originating from these compositions on substrates.
  • a solar rechargeable battery based on polymeric charge storage electrodes Liu P, et al.
  • a rechargeable solar battery comprises a photo anode made up of a PO2 coated electrode and a counter electrode made of polypyrrole nanowires.
  • the electrode was covered by T ⁇ C> 2 and coated with a 2,2'-bis (3,4-ethylenedioxytiphene acetonitrile solution as a photosensitive probe.
  • the polypyrrole electrode was electrochemically deposited with a pyrrole monomer solution 0, 01 M and a 0.1 M electrolyte solution was used.
  • FIG. 1 Construction diagram of the PV cell. JV graphs of the electrodes modified with Ti0 2 a: (B) 180. (C) 300. (D) 600 s.
  • FIG. 1 Construction diagram of the PV cell with PEDOT.
  • Figure 10 Energy diagram: (A) Ti02
  • FIG. 1 J-V graphs of the modified ITO
  • B Dye-1. Modified ITO
  • D Dye-1.
  • Figure 12 Schematic of the loading / unloading process between PEDOT and PPy from the p-doping / p-undoping process in 0.100 mol-L-1 LiCI solution.
  • FIG. 13 Graphical representation of the different energy storage systems tested: (A) A-1. (B) A-2. (C) A-3. (D) A-4.
  • Figure 14 Graphical representation of the loading / unloading sequence.
  • FIG. 15 (A) Transients V / t of charge / discharge obtained at ⁇ 5 mA of charge for the systems: (A) A-1. (B) A-2. Transient V / t of the download process for the systems: (C) A- 1. (D) A-2, at different currents.
  • FIG. 16 V / t transients obtained at ⁇ 5 DA charge / discharge current for (A) A-1 systems. (B) A-2. (C) A-3. (D) A-4. Figure 17. Graphical representation of energy density vs. number of cycles of: (A) load. (B) Discharge, obtained at ⁇ 5 DA, for the different systems studied.
  • FIG. 18 (A) Load / discharge transients V / t obtained at ⁇ 5 mA load current for the systems: (A) A-1. (B) A-2. Transient V / t of the download process for the systems: (C) A-1. (D) A-2, at different currents.
  • Figure 20 Graphical representation of energy density vs. number of cycles of: (A) load. (B) Discharge, obtained at ⁇ 5 mA for the different systems studied.
  • FIG. 21 (A) V / t load / discharge transients obtained at a current of ⁇ 2.3 DA for the A-2 system. (B) Energy density vs. number of cycles obtained from Fig. 21 A.
  • FIG. 22 (A) Representation of photo-recharge / discharge measurements. (B) V / t transients of an A-2 system in the presence and absence of light, for the photo-loading / unloading process.
  • FIG. 23 Schematic representation of the A-2 system in ionic liquid for the process of: (A) Photo-loading. (B) Download.
  • the present invention corresponds to a battery that can be charged with solar energy, consisting of an anode and a cathode with conductive polymers in the form of nanowires deposited on its surface.
  • the present invention corresponds to a battery that can be charged with solar energy, consisting of an anode and a cathode with conductive polymers in the form of nanowires deposited on its surface.
  • the anode consists of an indium doped tin oxide base, on which titanium dioxide (ITO) / TiC> 2 is deposited, in addition to a dye layer and a surface layer of polymer nanowires .
  • the cathode consists of an ITO base and a nanowire surface layer of a second polymer.
  • the anode nanowire surface layer is made with Poly- (3,4-ethylenedioxythiophene) nanowires (PEDOT).
  • PEDOT Poly- (3,4-ethylenedioxythiophene) nanowires
  • the cathode nanowire surface layer is made with polypyrrole (PPy) nanowires.
  • the nanowires are deposited on the surface of the respective base, following the steps of the following process: a) Generate a polymeric layer on an electrode.
  • the mesoporous "mold” is made from silicon oxide or anodized aluminum oxide.
  • the generation of a polymeric layer on an electrode is carried out using a solution of a monomer, with a supporting electrolyte and a solvent.
  • the monomer is selected from EDOT, Py, thiophene, substituted thiophenes, o-phenylenediamine, among others, where its concentration in the solution is between 0.001 mol L 1 and 0.010 mol-L 1
  • the support electrolyte is selected from quaternary ammonium salts, such as tetramethylammonium hexofluorophosphate, tetraethylammonium hexofluorophosphate, tetrabutylammonium hexofluorophosphate, tetramethylammonium tetrafluoroborate, tetraethylammonium tetrachiolamonate, tetrabutylammonium tetrachloride, tetrabutylammonium tetrach
  • tetraethylammonium p-toluenesulfonate tetrabutylammonium p-toluenesulfonate, among others, and its concentration in the solution is between 0.1 mol-L 1 and 1.0 mol-L 1 and the solvent is selected from acetonitrile, dichloromethane, dimethylsulfoxide, dimethylformamide, among others.
  • a potential range is used for VC electrosynthesis between - 2.50 and + 2.50 V, where the disturbance is performed at a potential sweep rate between 50 and 150 mV-s 1 , for a number of cycles, n, between 1 and 10.
  • the mesoporous silicon oxide mesoporous "template” is obtained by mixing between 0.0025 and 0.0045 mol-L 1 of tetraethyl orthosilicate and between 0.1 and 0.2 mol - L 1 of surfactant, which is selected from cetyltrimethylammonium, dodecyltrimethylammonium or dimethyldioctadecylammonium bromides, in ethanolic solution in a concentration between 30 and 70% v / v (ethanol: milli-Q water).
  • surfactant which is selected from cetyltrimethylammonium, dodecyltrimethylammonium or dimethyldioctadecylammonium bromides
  • the modified electrode is introduced with the thin polymer layer obtained in step a), and it is potentiostatically disturbed for a time between 2 and 10 s.
  • the potential to be applied is optimized to synthesize each base polymer. For example, a potential between 1,000 and 1,500 V vs ECS for poly (3,4-ethylenedioxythiophene) (PEDOT) or applying a potential between 0,800 and 1,200 V vs ECS for polypyrrole (PPy)
  • the product from step b is contacted with an acid solution at pH ca. 1 prepared in ethanolic solution in a concentration between 30 and 70% v / v (ethanol: milli-Q water), and subsequently, the electrodes are removed from the solution and allowed to dry.
  • an acid solution at pH ca. 1 prepared in ethanolic solution in a concentration between 30 and 70% v / v (ethanol: milli-Q water)
  • the growth of the nanostructured CPs is performed by applying a potentiodynamic disturbance to the system consisting of the same solution used in step a) and under the same conditions previously described.
  • the electrode is washed by first spraying strong base solution of pH ca. 13, adding it in small doses in the form of a spray on the modified electrode and, later, in the same way, with sodium bicarbonate solution of concentration between 1.0 and 10% m / v. Finally, always spraying, wash with plenty of milliQ grade water.
  • All electrodes are modified using a three compartment anchor cell, using a Pt wire with an area 20 times greater than that of the respective working electrodes.
  • AgCI wire immersed in an aqueous solution of tetramethylammonium chloride is used, in an assembly whose potential is adjusted to that of the saturated calomel electrode (ECS), bringing its potential difference to 0.000 V, therefore that all reported potentials are referred to the ECS.
  • the working electrodes used are Pt disc-shaped and thin-plate "conductive glass”: glass coated with indium doped tin oxide (ITO) and have a geometric area of 0.07 and 0.21 cm 2 , respectively.
  • both working electrodes must be treated: Pt is polished with 0.3 pm alumina suspension, on suede cloth, while ITO is washed with propanol in an ultrasound bath for 5 min, then 5 minutes with acetone and finally, 5 minutes with milli-Q water.
  • the solutions used for the electro-polymerization consist of 0.010 mol-L- 1 of the monomers, 3,4-ethylenedioxythiophene, EDOT, Sigma-Aldrich or pyrrole, Py, Sigma-Aldrich (the latter being doubly distilled before use ), in addition to the following 0.100 mol-L 1 salts: lithium perchlorate (UCIO4), tetrabutylammonium perchlorate (TBACIO4), tetrabutylammonium hexafluorophosphate (TBAPF 6 ), tetraethylammonium hexafluorophosphate (TEAPF 6 ), lithium trifluoromethylsulfonate () 99.9% tetrabutylammonium trifluoromethylsulfonate (TBATFMS), purchased from Sigma-Aldrich, always in acetonitrile, CH 3 CN 99.9%, Merck.
  • UCIO4 tetrabut
  • Mesoporous silica oxide used as a template is prepared from a solution consisting of 0.1 mol-L -1 of sodium nitrate (NaNC> 3 99.0% m / m, Merck) as the supporting electrolyte, 0.0034 mol L -1 of tetraethylorthosilicate (PMD ⁇ ⁇ Si, 99.999% m / m, Aldrich) as a precursor of silicon oxide and 15 mol- 0.1 L -1 hexadecyltrimethylammonium bromide as the surfactant (CIGF BrN ⁇ , 95% m / m, Aldrich), in a 50% v / v ethanolic solution (ethanohagua milli-Q 1: 1), kept under constant stirring for 2.5 h.
  • EXAMPLE 1 Construction of PV cells of ITOIT ⁇ O2IPEDOT and ITO
  • PEDOT tetraethylorthosilicate
  • the modified ITOIT ⁇ O2 electrode is prepared under the conditions indicated previously, after depositing PEDOT in its solid and nanostructured forms.
  • the variant of this type of PV cell is performed with the addition of an intermediate step to the polymer tank, adding a dye, by immersing the ITO
  • the evaluation of the PV cells is carried out in the presence and absence of light.
  • an artificial sun is used, with a power of 100 mW-cnr 2 , while, in the absence of this, a closed metal box is used.
  • the evaluation of the energy storage devices is carried out in the absence and presence of light.
  • an anode made up of only the polymer of interest, PEDOT or PEDOT-nw is used, while PPy is used in the cathode in its solid and nanostructured form. While, in the presence of this, an artificial sun is used, with a power of 100 mW-cnr 2 .
  • the anode is modified, for which, before depositing PEDOT, a film of Ti0 2 and a dye are deposited, turning it into a photo-anode.
  • the removal of the surfactant is carried out with a solution consisting of a hydrochloric acid solution of pH 1 in a 50% v / v ethanolic solution (ethanohagua mili-Q 1: 1).
  • a solution consisting of 0.100 mol-L -1 of TBAPF 6 is used as the supporting electrolyte and 0.010 mol-L -1 of ferrocene (CioHioFe, 98% m / m, Aldrich), as an electroactive species, in acetonitrile.
  • the photovoltaic characterization of the solar cells has been carried out in an anautomated lV under darkness and lighting, using a global solar simulator AM1.5 (Oriel 300W), with an intensity of 100 mW-cnr 2 , which is adjusted with a photovoltaic cell of reference (PV of 0.5 cm2 CIGS, calibrated in NREL, USA). All these measurements are also carried out under environmental conditions.
  • the tests of the different batteries are carried out in an OrigaLys model OGF500 potentiostat / galvanostat, in a charge / discharge module controlled by the OrigaMaster software.
  • EXAMPLE 2 Construction of solar cells based on T1O 2 and nanowires from PEDOT Construction of PV cells from ITO
  • the photovoltaic characterization of the electrochemically prepared ITOIT1O 2 photo-anodes is carried out through the construction of a cell, in which the behavior of T1O 2 as a cathode in this photo-cell is evaluated. For this, it is necessary to deposit, in a first stage, T1O 2 on a “conductive glass” previously stripped at the bottom (remove the ITO from the surface), to subsequently deposit different compounds on the semi-conductor, in the following order: fullerene (40nm), SubPc (20nm), M0O 3 (10nm), as a "gap extractor” and finally, Al (100nm), which is used as a contact (Fig. 1A). Then, the cells are measured potentiodynamically, to record their current density under darkness and lighting, the latter being generated with a 100 mW-cnr 2 solar simulator lamp.
  • Fig . 1 B shows the corresponding JV response to the modified electrode ITO
  • Table 1 shows the summary of the results obtained from the JV graphs, where it is observed that the cell built from the modified electrode at 300 s, has a much higher current density than the other electrodes . Additionally, it is important to note that this cell has also presented the best% FF results.
  • the electrodes modified with PEDOT in its solid and nano-structured form are performed in the presence and absence of light, using for the latter a power of 100 mW-cnr 2 .
  • the Polymer modified working electrode is used as anode.
  • PEDOT / PEDOT-nw is presented in Fig. 2, to which SubPc (18 nm), fullerene (40 nm) is deposited. , Alq3 (9 nm) and Al (100 nm).
  • Fig. 3 shows JV transients corresponding to electrodes modified with PEDOT in its two structural forms, where it is possible to observe that both have similar profiles, although the electrode modified with nanostructures presents a higher current density, which is consistent with a greater effective area.
  • Table 2 summarizes data calculated from the photovoltaic responses of the PEDOT-modified electrodes. Both PEDOT and PEDOT-nw have low efficiency with respect to cells reported in the literature.
  • the PEDOT-nw modified electrodes have a greater efficiency than the PEDOT modified electrodes in solid form, highlighting the increase of an order of magnitude.
  • the% FF, as well as the current density have a value 2 times higher than that recorded for photovoltaic cells built from ITO
  • a positive slope is presented, which is an indication of the presence of a n-type semiconductor, while for PEDOT in its two forms - solid and nano-structured -, there are negative slopes, accounting for a p-type semi-conductor. From these slopes, it is possible to calculate the apparent density of carriers, for the different semi-conductors, SC, being ND the number of donors for SC type-n and NA the number of acceptors for SC type-p, using Ecs. 1 and 2.
  • PMS is the value of the slope
  • e is the charge of an electron
  • eq and e are the dielectric constant in vacuum and the dielectric constant of the semiconductor (considering a value of 100 and 600,000 for T1O2 and PEDOT, respectively), obtaining values of 6,057-1019; 8,246-1017 and 1, 107-1017 enr 3 for T ⁇ 0 2 , PEDOT and PEDOT-nw, respectively.
  • the band gap values are obtained for the different modified electrodes, which present values of 3.86; 2.31 and 2.56 eV, respectively (Fig. 5D-F).
  • the slight increase in the band gap that the PEDOT nano-strands present compared to their solid shape, is attributed to the quantum confinement of the nano-structured materials.
  • Fig. 7 shows SEM micrographs of modified electrodes before and after growth of PEDOT-nw. It can be seen that in both electrodes, when the thin layer of PEDOT is previously electrodeposited, to increase the adherence of the nanostructures, the objective is fulfilled, since these cross sections allow to verify how the polymer grows precisely between the T1O structures 2 of the electrode, showing an excellent cohesion of the hetero-junction, as well as the formation of nano-wires totally adhered to the "support polymer", constituting the conformation that was sought. Thus, in Fig. 7B the presence of nanowires with an approximate diameter of 30 nm is verified, a dimension that is consistent with the size of the nanochannels of the template.
  • the growth of PEDOT occurs between the bar-like structures that T1O 2 presents, until they are completely covered, which would lead to, in some areas of the cell, the polymer to have direct contact with the ITO surface, which acts as a working electrode, causing the system to short-circuit.
  • the first is a commercial dye, called cis- ⁇ > / s (isothiocyanate) bis (2,2'-bipyridil-4, Ruthenium (II) 4'-dicarboxylate), abbreviated as N3.
  • This dye has a Ru metal center and its main characteristics include sensitizing a wide band of the spectrum, which includes semiconductors such as T1O2, even up to wavelengths of 700 nm.
  • the second is a dye that has been recently synthesized in our laboratory and is based on a compound with a donor-pi-acceptor structure, where the acceptor group, cyano acetic acid, is linked to the donor group, aniline, by a conjugated chain. .
  • the addition of the dye is carried out by adsorption on the T1O2-modified ITO electrode, which is immersed for 24 h and then washed with acetone.
  • the subsequent electrosynthesis of the PEDOT nanowires on the surface is carried out under the optimal conditions established above, to prepare the new modified electrodes to be used as a cell, as shown in Fig. 9.
  • the constructed energy diagrams (Fig. 6A-B), are modified including the bands corresponding to the dyes used in this work N3 (Fig. 10A-B) and C-1 (Fig. 10C-D).
  • N3 and C-1 there is a FIOMO of -5.89 and -5.22 eV, respectively, while their LUMO is -3.53 and -2.76 eV, respectively.
  • this one is built inversely, that is, the semiconductor type- / i on the surface of the conductive glass, while the semiconductor type -p (PEDOT or PEDOT-nw) it is exposed to the surface.
  • This conformation is adopted due to the fact that the final device to be built is a rechargeable battery, where the latter would be determined between the doping / undoping process of both polymers, requiring their direct confrontation.
  • the mechanism of electron movement is not altered within the system.
  • the dye is excited forming an electron-hole pair, which travels in the opposite direction, so that the exciton formed travels to the LUMO level of the dye , with promotion to the T1O2 conduction band, which later travels outside the system. Meanwhile, the electronic deficiency generated by this promotion (the gap) travels to the FIOMO of the -p type semiconductor, partially oxidizing the polymer chain.
  • Fig. 1 1 shows JV responses of the ITO
  • Table 3 summarizes the values obtained from the photovoltaic characterization of the cells modified with both dyes.
  • PPy electrodes in their solid and nano-structured forms are evaluated as a charge accumulator device, through their p-doping / p-undoping process (Fig. 12). From this, and initially, the device is charged, which is fully discharged, that is, the anode (PEDOT) is in its reduced state, while the cathode (PPy) is in its oxidized state - doped with anion A- The charging process is carried out by applying current to the system, which generates oxidation of the anode and reduction of the cathode, as shown in Fig. 12A. In reverse, the discharge is performed (Fig. 12B).
  • Fig. 15 shows the V / t transients corresponding to the A-1 and A-2 system charge / discharge process, obtained from a current of ⁇ 5 mA. It is possible to observe three phenomena: i) for system A-1, which contemplates both electrodes in their solid form, a phenomenon of multi-process charging is observed (Fig. 15A), very different from that observed in system A-2 (Fig. 15B), where both electrodes are in their nanostructured form. This behavior can be attributed to different chain lengths obtained during electropolymerization, since a template is used to obtain nano-threads of both polymers, which would generate a more uniform chain length.
  • Fig. 16A-D shows the V / t transients corresponding to the charge / discharge cycles of the different systems studied, applying a disturbance of ⁇ 5 mA. It can be seen that the A-2 system (PEDOT-nw
  • an energy storage device is built, capable of generating a recharge from sunlight, providing its electrical independence.
  • PPy, PPy-nw is constructed, assembling both under the conditions already described.
  • the measurements of these devices consist of two steps; i) photo-recharge and ⁇ i) discharge, independent of each other (Fig. 22A). In Fig.
  • the discharge (Fig. 23B) is carried out by exchanging the photo-anode connector, modifying the Ti0 2
  • the reactions of reduction of PEDOT-nw and oxidation of PPy-nw are thermodynamically favored by the difference in potential between both modified electrodes, which would be ca. 30 mV, value obtained from the CV described in item 3.2. This potential difference is observed in the photo-recharge and discharge (insert Fig. 22B).
  • Table 4 shows the data of the cells and batteries currently marketed, where the different values for each of the devices are observed, including at the end the values obtained in this study. It should be noted that this comparison is only a reference, since it must be kept in mind that the working conditions, characterization and manufacturing are quite different from each other. In this way, the energy density obtained is below the values reported for commercial devices. However, the first energy accumulators present a greater toxicity and need of being treated to protect the environment. On the other hand, lithium-based devices, which would have a higher energy density, have similar toxicity to the device studied, making them quite attractive.
  • the battery based on nanostructured CPs has a rather important advantage, which lies mainly in the total mass of the device and its size, which does not exceed an area of 0.21 cm 2 and a volume of 0.3 cm 3 , therefore it is projected as an excellent candidate for its optimization and commercial development.
  • the recharging protocol of the different devices makes the device designed and characterized here even more interesting, since it would have total independence from electricity, making its free use possible, even in places where electricity is not easily accessible.
  • the set of characteristics exhibited by this solar-based rechargeable battery based on nano-structured CPs make it an excellent candidate for its manufacture, although it is important to consider the prior optimization of the manufacturing parameters, since it has been carried out here. carried out only manually, on a laboratory scale.
  • the present invention has application in the nanopolymer industry, in particular in the use of nanopolymers in the manufacture of rechargeable batteries with solar energy.

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Abstract

La présente invention se situe dans le domaine technique de la synthèse de nanomatériaux, spécifiquement dans l'élaboration d'accumulateurs rechargeables avec l'énergie solaire basés sur des nanomatériaux, lequel accumulateur qui peut être chargé par l'énergie solaire est constitué d'une anode et d'une cathode avec des polymères conducteurs en forme de nanofils déposés sur sa surface.
PCT/CL2018/050117 2018-11-28 2018-11-28 Accumulateurs rechargeables à l'énergie solaire, basés sur des polymères nanostructurés Ceased WO2020107131A1 (fr)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110220188A1 (en) * 2008-11-18 2011-09-15 Konarka Technologies, Inc. Dye Sensitized Photovoltaic Cell

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110220188A1 (en) * 2008-11-18 2011-09-15 Konarka Technologies, Inc. Dye Sensitized Photovoltaic Cell

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Title
DEL VALLE, M.A. ET AL.: "Electrosynthesis and Characterization of Poly(3,4- ethylenedioxythiophene) Nanowires", INT. J. ELECTROCHEM. SCI., vol. 10, 2015, pages 5152 - 5163, XP055711783, Retrieved from the Internet <URL:http://www.electrochemsci.org/papers/vol10/100605152.pdf> [retrieved on 20191106] *
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PEÑA, L.: "Células solares transparentes: desarrollo actual y aplicaciones", TRABAJO DE TITULACION PARA POSTULAR AL TITULO DE MASTER DE ENERGIAS RENOVABLES, 30 September 2011 (2011-09-30), XP055711833, Retrieved from the Internet <URL:http://repositorio.upct.es/bitstream/handle/10317/1869/pfm271,pdf?sequence=1&isAllowed=y> [retrieved on 20190624] *
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