EP2586048A1 - An energy storage device and method thereof - Google Patents

An energy storage device and method thereof

Info

Publication number
EP2586048A1
EP2586048A1 EP20100853575 EP10853575A EP2586048A1 EP 2586048 A1 EP2586048 A1 EP 2586048A1 EP 20100853575 EP20100853575 EP 20100853575 EP 10853575 A EP10853575 A EP 10853575A EP 2586048 A1 EP2586048 A1 EP 2586048A1
Authority
EP
European Patent Office
Prior art keywords
lead
substrate
storage device
integrated
dioxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20100853575
Other languages
German (de)
French (fr)
Other versions
EP2586048A4 (en
Inventor
Ashok Kumar Shukla
Musuwathi Krishnamoorthy Ravikumar
Shaik Abdul Gaffoor
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Indian Institute of Science IISC
Original Assignee
Indian Institute of Science IISC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Indian Institute of Science IISC filed Critical Indian Institute of Science IISC
Priority claimed from PCT/IN2010/000439 external-priority patent/WO2011161686A1/en
Publication of EP2586048A1 publication Critical patent/EP2586048A1/en
Publication of EP2586048A4 publication Critical patent/EP2586048A4/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • H01G11/04—Hybrid capacitors
    • 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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • 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
    • H01G11/32—Carbon-based
    • 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
    • H01G11/46—Metal oxides
    • 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
    • H01G11/66—Current collectors
    • H01G11/68—Current collectors characterised by their material
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • 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
    • H01G11/52—Separators
    • 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
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • 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 disclosure is related to hybrid capacitors specifically to Pb0 2 /Activated Carbon hybrid ultracapacitors.
  • the hybrid ultracapacitor of the present disclosure is simple to assemble, bereft of impurities and can be fast charged/discharged with high faradiac efficiency.
  • Supercapacitors are being projected as potential devices that could enable major advances in energy storage.
  • Supercapacitors are governed by the same physics as conventional capacitors but utilize high-surface-area electrodes and thinner dielectrics to achieve greater capacitances allowing energy densities greater than those of conventional capacitors and power densities greater than those of batteries.
  • Supercapacitors can be divided into three general classes, namely electrical-double-layer capacitors, pseudocapacitors and hybrid capacitors. Each class is characterized by its unique mechanism for charge storage, namely faradaic, non-faradaic and the combination of the two.
  • Faradaic processes such as oxidation-reduction reactions, involve the transfer of charge between electrode and electrolyte as in a battery electrode while a non-faradaic mechanism does not use a chemical mechanism and rather charges are distributed on surfaces by physical processes that do not involve the making or braking of chemical bonds "similar to electrical "double-layer.
  • a hybrid supercapacitor combines a battery electrode where the energy is stored in chemical form and an electrical-double-layer electrode where the energy is stored in physical form.
  • a Pb0 2 /Activated Carbon supercapacitor comprises a positive plate akin to a lead acid cell and a high surface-area activated carbon electrode as negative plate. The charge- discharge reactions at the positive and negative plates of such a hybrid supercapacitors are as follows.
  • the (+) plate is realized by electrochemical plating and cycling in sulpuric acid/ perchloric acid while the (-) plate is prepared by pasting activated carbon onto a lead sheet.
  • the said hybrid supercapacitor stores energy both in chemical and physical forms.
  • the hybrid capacitors known in the prior art employ conventional Pb0 2 plates that require sizing and mixing of the active materials of - appropriate compositions, pasting, drying, curing and formation. Such electrodes are not fully amenable to fast charge/discharge processes desirous of a capacitor.
  • an energy-storage device (1) comprising: a substrate- integrated-lead-dioxide electrode (2), an activated-carbon electrode (3), and a separator (4) soaked in an electrolyte (5) and placed in-between the substrate-integrated- lead-dioxide electrode and the carbon electrode in a container (6); an energy storage device (7) comprising plurality of energy storage device (1) of claim 1 connected in series; a method of preparing substrate-integrated lead dioxide comprising acts of, a) etching pre- polished lead sheets; b) washing the etched lead sheets with deionized water; c) immersing the washed lead sheets in mixture of sulphuric acid and perchloric acid to obtain a layer of lead sulphate; and d) oxidizing the lead sulphate to lead dioxide to obtain substrate- integrated lead dioxide; a method of manufacturing an energy storage device (1), comprising acts of: a) preparing substrate-integrated-lead-dioxide electrode (2),
  • Figure 1 Schematic diagram of substrate-integrated Pb0 2 /activated-carbon ultracapacitor.
  • Figure 2 Schematic diagram of substrate-integrated Pb0 2 /activated-carbon ultra capacitors connected in series.
  • Figure 3 Schematic diagram of electrochemical cell employed for preparing substrate- integrated Pb0 2 electrodes.
  • Figure 4 XRD patterns for the positive electrodes.
  • Figure 5 Cyclic voltammograms for a Pb0 2 / Activated Carbon Hybrid Ultracapacitor.
  • Figure 7 Life-cycle test.
  • Figure 8 Constant current charge/discharge characteristics.
  • Figure 9 Constant-potential charge and constant-current discharge characteristics.
  • the present disclosure is in relation to an energy storage device (1) comprising:
  • the energy storage device (1) is a hybrid capacitor.
  • the separator (4) is made of material selected from a group comprising porous glass and porous polymers, preferably porous glass.
  • the electrolyte is selected from a group comprising sulphuric acid, methanesulfonic acid, perflurosulphonic acid, and preferably sulphuric acid.
  • the sulphuric acid is concentrated in range from about 4M to about 7M, preferably about 6M.
  • the energy storage device (1) is of faradiac efficiency ranging from about 94% to about 96%, preferably 95%.
  • the present disclosure is also in relation to an energy-storage device (7) comprising plurality of energy-storage device (1) connected in series.
  • the present disclosure is also in relation to a method of preparing substrate-integrated lead dioxide comprising acts of,
  • the etching is carried out using Nitric acid.
  • the Nitric acid is of concentration ranging from about 0.5M to about 1.5M, preferably about 1M.
  • the sulphuric acid is concentrated in the range from about 4M to about 7M, preferably about 6M.
  • the perchloric acid is concentrated in the range from about 0.05M to about 0.2M, preferably about 0.1M.
  • the oxidation of lead sulphate to lead dioxide is by using the lead sulphate as an anode in an electrochemical cell.
  • the present disclosure is also in relation to a method of manufacturing an energy-storage device (1), comprising acts of:
  • the container (6) is made of material selected from a group comprising porous glass and porous polymer, preferably porous glass.
  • the present disclosure is also in relation to a method of using energy-storage device (1 or 7), said method comprising act of conjugating said energy-storage device with electrical device for generating electrical energy to devices in need thereof for working.
  • the present disclosure is related to realizing substrate-integrated Pb0 2 / Activated-carbon hybrid ultracapacitor bereft of impurities.
  • the hybrid ultra capacitors of the present disclosure are simple to assemble, bereft of impurities, and can be fast charged / discharged with faradaic efficiencies as high as 95%.
  • the positive electrodes, substrate-integrated Pb0 2 are made by electrochemical formation of pre-polished and etched lead metal sheets. Specifically, the substrate-integrated Pb0 2 is obtained by oxidizing PbS0 4 which is formed when lead sheets come in contact with sulfuric acid. Subsequent to their formation, the electrodes are washed copiously with de-ionized water to wash off all the impurities. The XRD patterns for the formed electrodes were recorded and found to be free of impurities. The XRD patterns provided in the figure 4 clearly suggest the formation of lead dioxide.
  • the negative electrode is an activated carbon electrode.
  • Pb0 2 electrode is a battery-type electrode and activated carbon is a double-layer-capacitor electrode.
  • Figure 5 is a cyclic voltammogram for Pb0 2 /activated carbon hybrid ultracapacitor at a scan rate of 10 mV/s showing a peak for the oxidation of PbS0 4 to Pb0 2 at 2 V during the anodic scan and the corresponding reduction of Pb0 2 to PbS0 4 at 1.5V during the cathodic scan.
  • the oxidation and reduction peaks reflect the Pb0 2 / Activated carbon to be a hybrid device.
  • the battery electrodes are charged at C/10 rate (lOh duration) and discharged at C/5 rate (5h duration). If the battery electrodes are charged/discharged at C rate or at higher rates their cycle-life is affected. Faradaic efficiency of the battery electrodes depends on the particle size of the active materials, porosity of the electrode, internal resistance of the electrode, etc. The battery electrodes have low faradaic efficiency.
  • the present disclosure provides, electrochemically formed and substrate-integrated Pb0 2 as battery-type electrode that can be charged and discharged at higher rates with faradiac efficiencies as high as 95%.
  • the same has been illustrated in Figure 8.
  • the figure 8 shows current charge and discharge curve at 50 mA for the substrate-integrated Pb0 2 / Activated hybrid ultracapacitor exhibiting faradiac efficiency as high as 95%.
  • Figure 6 shows the charge and discharge polarization curves at 25 mA, 50 mA and 100 mA for a substrate-integrated Pb0 2 / Activated carbon hybrid ultracapacitor prepared by using Teflon as binder in the carbon electrodes.
  • the capacitance is calculated from the discharge curve using the equation:
  • V 2 is the voltage at the beginning of discharge and V ⁇ is the voltage at the end of discharge. It is found that the hybrid ultracapacitor has a capacitance of 10.79F at 25mA, 10.05F at 50 mA and 9.738F at 100 mA.
  • the figure 7 shows the cycle-life data for the substrate-integrated Pb0 2 / / Activated carbon hybrid ultracapacitor at 0.1 A suggesting the hybrid ultracapacitors to have high cycle-life.
  • the cycle-life test involves the following four steps.
  • Step 1 Charging the ultracapacitor at 2.3V for 10 min.
  • Step 2 Open-circuit voltage measurement for 5s.
  • Step 3 Discharge the ultracapacitor at constant current at 0.2A.
  • Step 4 Open-circuit voltage measurement for 30s.
  • Figure 10 shows the cycle-life data for the substrate-integrated Pb0 2 /Activated-carbon hybrid ultracapacitor.
  • Figure 9 illustrates the discharge curves at varying currents for the substrate-integrated Pb0 2 / Activated-carbon hybrid ultracapacitor followed by their charging at 2.3V for lOmin.
  • the hybrid capacitor of the present disclosure is connected in series to obtain capacitors wherein the cell voltage gets added up while their effective capacitance decreases akin to conventional capacitor.
  • Figure 11 shows the discharge curves at 0.2A current for substrate- integrated Pb0 2 / Activated-carbon hybrid ultracapacitor cell comprising two and three cells connected in series. The figure indicates that the cell voltage is added up when two or more cells are connected in series while their effective capacitances decrease akin to conventional capacitors.
  • the method of manufacturing substrate-integrated Pb0 2 /activated-carbon hybrid ultracapacitor (1) essentially comprises: preparing substrate integrated lead dioxide electrode (2), preparing activated-carbon electrode (3), and mounting the substrate- integrated-lead-dioxide electrode (2), the activated-carbon electrode (3) in a container (6) with separator(4) soaked in an electrolyte (5) in-between the substrate-integrated lead dioxide and the carbon electrode to manufacture the energy-storage device.
  • the devices of the present disclosure can be easily conjugated with electrical devices for generating electrical energy to devices in need thereof for working.
  • Substrate-integrated- Pb0 2 electrodes are prepared by etching pre-polished lead sheets (thickness 300 ⁇ ) in 1M HNO3 for 60s and subsequently washed copiously with deionized water. The sheets were then immersed in 6 M aqueous H 2 S0 4 with 0.1 M HC10 4 as additive at room temperature. On immersing in aqueous sulfuric acid, a thin layer of lead sulfate is formed on the surface of the lead sheet which is oxidized to Pb0 2 by using it as anode in an electrochemical cell fitted with a counter electrode. The process is repeated for about five times to prepare the fully-formed substrate-integrated Pb0 2 electrodes. The electrochemical cell employed for this purpose is connected to a constant current dc supply as shown schematically in figure3. B. Preparation of PVDF bonded activated carbon electrodes.
  • Activated-carbon electrodes are prepared by pasting activated carbon ink containing polyvinylidene difluoride as a binder.
  • a carbon paste was obtained by mixing 85% of high-surface-area carbon (BET surface area is about 2000 m 2 /g and particle size ⁇ 10 nm) with 10 wt. % of carbon black (particle size is about 1 ⁇ ) and 5 wt. % of binder like PVDF dissolved in an appropriate quantity of dimethylformamide solvent or teflon.
  • 0.1 g of PVDF is dissolved in 10 ml of DMF and 1.7 g of high surface area carbon (Meadwestvaco 090177) and 0.2 g of carbon black was added.
  • the mixture was mixed well in an ultrasonicator for 5 min.
  • the resulting carbon ink was brush coated onto two graphite electrodes of area 3.5 cm x 6.0 cm with that had a tag area of 1cm width and 3 cm length.
  • the carbon paste was applied on both sides of the carbon electrodes so that each side of the electrode in order to get a 0.5 g of active material.
  • the electrodes were dried in air oven for overnight (about 10 h) at 80°C.
  • 6V substrate-integrated Pb0 2 -AC HUCs were assembled by connecting three 2V HUCs in series.
  • 2V/100F substrate-integrated Pb0 2 /PVDF-bonded AC HUCs comprising a substrate-integrated Pb0 2 electrode of size 3.5cm x 6 cm with a tag of 1cm width and 3 cm length formed by aforementioned method and a PVDF-bonded carbon electrode prepared as described above were assembled using a 3 mm thick AGM (adsorbed glass mat) soaked with 6 M H 2 S0 4 acid as the separator and electrolyte.
  • the complete assembly, Pb0 2 - (AGM+H 2 S0 4 ) - AC was then assembled into a plexiglass container. The cell was then tested for its electrochemical characteristics.
  • 12V substrate-integrated Pb0 2 -AC hybrid ultracapacitor was then assembled into a plexiglass container.
  • Pb0 2 /PVDF-bonded AC HUCs comprising a substrate- integrated Pb0 2 electrode of size 3.5cm x 6 cm with tags (6a, 6b) of 1cm width and 3 cm length formed by aforementioned method and a PVDF-bonded carbon electrode prepared as described above were assembled using a 3 mm thick AGM (adsorbed glass mat) soaked with 6 M H 2 S0 4 acid as the separator and electrolyte. The complete assembly, Pb0 2 - (AGM+H 2 S0 4 ) - AC, was then assembled into a plexiglass container. The cell was then tested for its electrochemical characteristics.
  • a 12V substrate-integrated Pb0 2 -AC hybrid ultracapacitor was realized by connecting six single cells in series in a commercial lead-acid battery container. Each cell of this 12V hybrid ultracapacitor comprises 9 positive and 8 negative plates of size 4.5cm x 7 cm with the tag (6b) area of 0.5cm x 0.5 cm and 0.3mm thickness for the positive plate and 0.8mm thickness for negative plates (6a); 1mm thick AGM sheets were used as separator. A unique method was used to interconnect the graphite electrodes.
  • the tag portion of the negative electrodes (6a) is electroplated with Tin followed by electroplating with lead which facilitates the graphite electrode tags (6b) to solder with each other.
  • the graphite electrodes in each cell were soldered with lead by torch-melt method using an appropriately designed group-burning fixture. Subsequently, the cells were interconnected in series.

Abstract

The present disclosure is related to hybrid capacitors specifically to PbO2/Activated Carbon hybrid capacitors. The hybrid super capacitor of the present disclosure is simple to assemble, bereft of impurities and can be fast charged/discharged with high faradiac-efficiency.

Description

AN ENERGY STORAGE DEVICE AND METHOD THEREOF
TECHNICAL FIELD
The present disclosure is related to hybrid capacitors specifically to Pb02/Activated Carbon hybrid ultracapacitors. The hybrid ultracapacitor of the present disclosure is simple to assemble, bereft of impurities and can be fast charged/discharged with high faradiac efficiency.
BACKGROUND
Supercapacitors (also termed as ultracapacitors) are being projected as potential devices that could enable major advances in energy storage. Supercapacitors are governed by the same physics as conventional capacitors but utilize high-surface-area electrodes and thinner dielectrics to achieve greater capacitances allowing energy densities greater than those of conventional capacitors and power densities greater than those of batteries. Supercapacitors can be divided into three general classes, namely electrical-double-layer capacitors, pseudocapacitors and hybrid capacitors. Each class is characterized by its unique mechanism for charge storage, namely faradaic, non-faradaic and the combination of the two. Faradaic processes, such as oxidation-reduction reactions, involve the transfer of charge between electrode and electrolyte as in a battery electrode while a non-faradaic mechanism does not use a chemical mechanism and rather charges are distributed on surfaces by physical processes that do not involve the making or braking of chemical bonds "similar to electrical "double-layer. A hybrid supercapacitor combines a battery electrode where the energy is stored in chemical form and an electrical-double-layer electrode where the energy is stored in physical form. A Pb02/Activated Carbon supercapacitor comprises a positive plate akin to a lead acid cell and a high surface-area activated carbon electrode as negative plate. The charge- discharge reactions at the positive and negative plates of such a hybrid supercapacitors are as follows.
(+) plate: PbS04+2H20<→Pb02 + H2S04+ 21^ + 2e" (-) plate: 2C + 2H++2e"<→2(C"Hads +)di
Accordingly, the net charge-discharge reactions for the hybrid supercapacitor can be written as follows.
PbS04+2H20+2C<→Pb02+ H2S04+2(C-Hads +)di The (+) plate is realized by electrochemical plating and cycling in sulpuric acid/ perchloric acid while the (-) plate is prepared by pasting activated carbon onto a lead sheet. The said hybrid supercapacitor stores energy both in chemical and physical forms.
The hybrid capacitors known in the prior art employ conventional Pb02 plates that require sizing and mixing of the active materials of - appropriate compositions, pasting, drying, curing and formation. Such electrodes are not fully amenable to fast charge/discharge processes desirous of a capacitor.
STATEMENT OF DISCLOSURE
The present disclosure is in relation to an energy-storage device (1) comprising: a substrate- integrated-lead-dioxide electrode (2), an activated-carbon electrode (3), and a separator (4) soaked in an electrolyte (5) and placed in-between the substrate-integrated- lead-dioxide electrode and the carbon electrode in a container (6); an energy storage device (7) comprising plurality of energy storage device (1) of claim 1 connected in series; a method of preparing substrate-integrated lead dioxide comprising acts of, a) etching pre- polished lead sheets; b) washing the etched lead sheets with deionized water; c) immersing the washed lead sheets in mixture of sulphuric acid and perchloric acid to obtain a layer of lead sulphate; and d) oxidizing the lead sulphate to lead dioxide to obtain substrate- integrated lead dioxide; a method of manufacturing an energy storage device (1), comprising acts of: a) preparing substrate-integrated-lead-dioxide electrode (2), b) preparing activated-carbon electrode (3), and c) mounting the substrate-integrated-lead- dioxide electrode (2), the activated-carbon electrode (3) in a container (6) with separator (4) soaked in an electrolyte (5) in-between the substrate-integrated-lead-dioxide and the carbon electrodes to manufacture the energy-storage device; a method of using energy- storage device (1 or 7), said method comprising act of conjugating said energy-storage device with electrical device for generating electrical energy to devices in need thereof for working.
BRIEF DESCRIPTION OF ACCOMPANYING FIGURES
Figure 1 : Schematic diagram of substrate-integrated Pb02/activated-carbon ultracapacitor.
Figure 2: Schematic diagram of substrate-integrated Pb02/activated-carbon ultra capacitors connected in series.
Figure 3: Schematic diagram of electrochemical cell employed for preparing substrate- integrated Pb02 electrodes. Figure 4: XRD patterns for the positive electrodes.
Figure 5: Cyclic voltammograms for a Pb02/ Activated Carbon Hybrid Ultracapacitor.
Figure 6: Constant current charge/discharge cycles.
Figure 7: Life-cycle test.
Figure 8: Constant current charge/discharge characteristics. Figure 9: Constant-potential charge and constant-current discharge characteristics.
Figure 10: Cycle-life test for Pb02/PVDF-bonded Activated-Carbon Hybrid
Ultracapacitor.
Figure 11 : Constant-current discharge characteristics for 6V/40F Pb02/ Activated Carbon Hybrid Ultracapacitor. DESCRIPTION OF DISCLOSURE
The present disclosure is in relation to an energy storage device (1) comprising:
a) a substrate-integrated-lead-dioxide electrode (2),
b) an activated-carbon electrode (3), and c) a separator (4) soaked in an electrolyte (5) and placed in-between the substrate- integrated-lead-dioxide electrode and the carbon electrode in a container (6).
In an embodiment of the present disclosure, the energy storage device (1) is a hybrid capacitor.
In still another embodiment of the present disclosure, the separator (4) is made of material selected from a group comprising porous glass and porous polymers, preferably porous glass.
In yet another embodiment of the present disclosure, the electrolyte is selected from a group comprising sulphuric acid, methanesulfonic acid, perflurosulphonic acid, and preferably sulphuric acid.
In yet another embodiment of the present disclosure, the sulphuric acid is concentrated in range from about 4M to about 7M, preferably about 6M.
In yet another embodiment of the present disclosure, the energy storage device (1) is of faradiac efficiency ranging from about 94% to about 96%, preferably 95%.
The present disclosure is also in relation to an energy-storage device (7) comprising plurality of energy-storage device (1) connected in series.
The present disclosure is also in relation to a method of preparing substrate-integrated lead dioxide comprising acts of,
a) etching pre-polished lead sheets;
b) washing the etched lead sheets with deionized water;
c) immersing the washed lead sheets in mixture of sulphuric acid and perchloric acid to obtain a layer of lead sulphate; and
d) oxidizing the lead sulphate to lead dioxide to obtain substrate integrated lead dioxide.
In still another embodiment of the present disclosure, the etching is carried out using Nitric acid.
In yet another embodiment of the present disclosure, the Nitric acid is of concentration ranging from about 0.5M to about 1.5M, preferably about 1M.
In yet another embodiment of the present disclosure, the sulphuric acid is concentrated in the range from about 4M to about 7M, preferably about 6M. In yet another embodiment of the present disclosure, the perchloric acid is concentrated in the range from about 0.05M to about 0.2M, preferably about 0.1M.
In yet another embodiment of the present disclosure, the oxidation of lead sulphate to lead dioxide is by using the lead sulphate as an anode in an electrochemical cell.
The present disclosure is also in relation to a method of manufacturing an energy-storage device (1), comprising acts of:
a) preparing substrate-integrated-lead-dioxide electrode (2),
b) preparing activated carbon electrode (3), and
c) mounting the substrate-integrated-lead-dioxide electrode (2), the activated carbon electrode (3) in a container (6) with separator(4) soaked in an electrolyte (5) in-between the substrate-integrated lead dioxide and the carbon electrode to manufacture the energy storage device.
In yet another embodiment of the present disclosure, the container (6) is made of material selected from a group comprising porous glass and porous polymer, preferably porous glass.
The present disclosure is also in relation to a method of using energy-storage device (1 or 7), said method comprising act of conjugating said energy-storage device with electrical device for generating electrical energy to devices in need thereof for working.
The present disclosure is related to realizing substrate-integrated Pb02/ Activated-carbon hybrid ultracapacitor bereft of impurities. The hybrid ultra capacitors of the present disclosure are simple to assemble, bereft of impurities, and can be fast charged / discharged with faradaic efficiencies as high as 95%.
In the current disclosure, the positive electrodes, substrate-integrated Pb02 are made by electrochemical formation of pre-polished and etched lead metal sheets. Specifically, the substrate-integrated Pb02 is obtained by oxidizing PbS04 which is formed when lead sheets come in contact with sulfuric acid. Subsequent to their formation, the electrodes are washed copiously with de-ionized water to wash off all the impurities. The XRD patterns for the formed electrodes were recorded and found to be free of impurities. The XRD patterns provided in the figure 4 clearly suggest the formation of lead dioxide. The negative electrode is an activated carbon electrode.
In the current disclosure of Pb02/ Activated carbon hybrid ultracapacitor, Pb02 electrode is a battery-type electrode and activated carbon is a double-layer-capacitor electrode. Figure 5 is a cyclic voltammogram for Pb02/activated carbon hybrid ultracapacitor at a scan rate of 10 mV/s showing a peak for the oxidation of PbS04 to Pb02 at 2 V during the anodic scan and the corresponding reduction of Pb02 to PbS04 at 1.5V during the cathodic scan. The oxidation and reduction peaks reflect the Pb02/ Activated carbon to be a hybrid device.
Generally, the battery electrodes are charged at C/10 rate (lOh duration) and discharged at C/5 rate (5h duration). If the battery electrodes are charged/discharged at C rate or at higher rates their cycle-life is affected. Faradaic efficiency of the battery electrodes depends on the particle size of the active materials, porosity of the electrode, internal resistance of the electrode, etc. The battery electrodes have low faradaic efficiency.
The present disclosure provides, electrochemically formed and substrate-integrated Pb02 as battery-type electrode that can be charged and discharged at higher rates with faradiac efficiencies as high as 95%. The same has been illustrated in Figure 8. The figure 8 shows current charge and discharge curve at 50 mA for the substrate-integrated Pb02/ Activated hybrid ultracapacitor exhibiting faradiac efficiency as high as 95%.
Figure 6 shows the charge and discharge polarization curves at 25 mA, 50 mA and 100 mA for a substrate-integrated Pb02/ Activated carbon hybrid ultracapacitor prepared by using Teflon as binder in the carbon electrodes. The capacitance is calculated from the discharge curve using the equation:
C(F) = I(A) x t(s)/(V2-V
where V2 is the voltage at the beginning of discharge and V\ is the voltage at the end of discharge. It is found that the hybrid ultracapacitor has a capacitance of 10.79F at 25mA, 10.05F at 50 mA and 9.738F at 100 mA. The figure 7 shows the cycle-life data for the substrate-integrated Pb02//Activated carbon hybrid ultracapacitor at 0.1 A suggesting the hybrid ultracapacitors to have high cycle-life. The cycle-life test involves the following four steps.
Step 1. Charging the ultracapacitor at 2.3V for 10 min.
Step 2. Open-circuit voltage measurement for 5s.
Step 3. Discharge the ultracapacitor at constant current at 0.2A.
Step 4. Open-circuit voltage measurement for 30s.
Figure 10 shows the cycle-life data for the substrate-integrated Pb02/Activated-carbon hybrid ultracapacitor.
Figure 9 illustrates the discharge curves at varying currents for the substrate-integrated Pb02/ Activated-carbon hybrid ultracapacitor followed by their charging at 2.3V for lOmin.
The hybrid capacitor of the present disclosure is connected in series to obtain capacitors wherein the cell voltage gets added up while their effective capacitance decreases akin to conventional capacitor. Figure 11 shows the discharge curves at 0.2A current for substrate- integrated Pb02/ Activated-carbon hybrid ultracapacitor cell comprising two and three cells connected in series. The figure indicates that the cell voltage is added up when two or more cells are connected in series while their effective capacitances decrease akin to conventional capacitors.
The method of manufacturing substrate-integrated Pb02/activated-carbon hybrid ultracapacitor (1) essentially comprises: preparing substrate integrated lead dioxide electrode (2), preparing activated-carbon electrode (3), and mounting the substrate- integrated-lead-dioxide electrode (2), the activated-carbon electrode (3) in a container (6) with separator(4) soaked in an electrolyte (5) in-between the substrate-integrated lead dioxide and the carbon electrode to manufacture the energy-storage device. The devices of the present disclosure can be easily conjugated with electrical devices for generating electrical energy to devices in need thereof for working.
The technology of the instant application is elaborated in detail with the help of following examples. However, the examples should not be construed to limit the scope of the disclosure.
Example:
Preparation of substrate-integrated Pb02/Activated Carbon Hybrid Ultracapacitors A. Preparation of Substrate-Integrated Pb02 Electrodes.
Substrate-integrated- Pb02 electrodes are prepared by etching pre-polished lead sheets (thickness 300 μηι) in 1M HNO3 for 60s and subsequently washed copiously with deionized water. The sheets were then immersed in 6 M aqueous H2S04 with 0.1 M HC104 as additive at room temperature. On immersing in aqueous sulfuric acid, a thin layer of lead sulfate is formed on the surface of the lead sheet which is oxidized to Pb02 by using it as anode in an electrochemical cell fitted with a counter electrode. The process is repeated for about five times to prepare the fully-formed substrate-integrated Pb02 electrodes. The electrochemical cell employed for this purpose is connected to a constant current dc supply as shown schematically in figure3. B. Preparation of PVDF bonded activated carbon electrodes.
Activated-carbon electrodes are prepared by pasting activated carbon ink containing polyvinylidene difluoride as a binder. In brief, a carbon paste was obtained by mixing 85% of high-surface-area carbon (BET surface area is about 2000 m2/g and particle size < 10 nm) with 10 wt. % of carbon black (particle size is about 1 μπι) and 5 wt. % of binder like PVDF dissolved in an appropriate quantity of dimethylformamide solvent or teflon. Typically, 0.1 g of PVDF is dissolved in 10 ml of DMF and 1.7 g of high surface area carbon (Meadwestvaco 090177) and 0.2 g of carbon black was added. The mixture was mixed well in an ultrasonicator for 5 min. The resulting carbon ink was brush coated onto two graphite electrodes of area 3.5 cm x 6.0 cm with that had a tag area of 1cm width and 3 cm length. The carbon paste was applied on both sides of the carbon electrodes so that each side of the electrode in order to get a 0.5 g of active material. Then the electrodes were dried in air oven for overnight (about 10 h) at 80°C.
C. Assembly of Substrate-Integrated Pb02-AC Hybrid Ultracapacitors (HUCs) a) 6V substrate-integrated Pb02-AC hybrid ultracapacitor.
6V substrate-integrated Pb02-AC HUCs were assembled by connecting three 2V HUCs in series. 2V/100F substrate-integrated Pb02/PVDF-bonded AC HUCs comprising a substrate-integrated Pb02 electrode of size 3.5cm x 6 cm with a tag of 1cm width and 3 cm length formed by aforementioned method and a PVDF-bonded carbon electrode prepared as described above were assembled using a 3 mm thick AGM (adsorbed glass mat) soaked with 6 M H2S04 acid as the separator and electrolyte. The complete assembly, Pb02 - (AGM+H2S04) - AC, was then assembled into a plexiglass container. The cell was then tested for its electrochemical characteristics. b) 12V substrate-integrated Pb02-AC hybrid ultracapacitor.
12V Pb02-AC HUCs were assembled by connecting six HUCs in series. The details for assembling the HUCs are given as under.
2V/100F substrate-integrated Pb02/PVDF-bonded AC HUCs comprising a substrate- integrated Pb02 electrode of size 3.5cm x 6 cm with tags (6a, 6b) of 1cm width and 3 cm length formed by aforementioned method and a PVDF-bonded carbon electrode prepared as described above were assembled using a 3 mm thick AGM (adsorbed glass mat) soaked with 6 M H2S04 acid as the separator and electrolyte. The complete assembly, Pb02 - (AGM+H2S04) - AC, was then assembled into a plexiglass container. The cell was then tested for its electrochemical characteristics. c) 12V substrate-integrated Pb02-AC hybrid ultracapacitor. A 12V substrate-integrated Pb02/ Activated carbon hybrid ultracapacitor was realized by connecting six single cells in series in a commercial lead-acid battery container. Each cell of this 12V hybrid ultracapacitor comprises 9 positive and 8 negative plates of size 4.5cm x 7 cm with the tag (6b) area of 0.5cm x 0.5 cm and 0.3mm thickness for the positive plate and 0.8mm thickness for negative plates (6a); 1mm thick AGM sheets were used as separator. A unique method was used to interconnect the graphite electrodes. The tag portion of the negative electrodes (6a) is electroplated with Tin followed by electroplating with lead which facilitates the graphite electrode tags (6b) to solder with each other. The graphite electrodes in each cell were soldered with lead by torch-melt method using an appropriately designed group-burning fixture. Subsequently, the cells were interconnected in series.
It is found that these hybrid ultracapacitors yield a capacitance value of 120F at 5C rate of discharge. While various aspects and embodiments have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the following claims.

Claims

WE CLAIM:
1. An energy storage device (1) comprising:
a) a substrate-integrated-lead-dioxide electrode (2),
b) an activated carbon electrode (3), and
c) a separator (4) soaked in an electrolyte (5) and is fixed in-between the substrate- integrated-lead-dioxide electrode and the carbon electrode in a container (6).
2. The energy-storage device as claimed in claim 1, wherein the energy storage device (1) is a hybrid capacitor.
3. The energy-storage device as claimed in claim 1, wherein the separator (4) is made of material selected from a group comprising porous glass and porous polymers, preferably porous glass.
4. The energy-storage device as claimed in claim 1, wherein the electrolyte is selected from a group comprising sulphuric acid, methanesulfonic acid, perflourosulphonic acid, preferably sulphuric acid.
5. The energy storage device as claimed in claim 4, wherein the sulphuric acid is concentrated in range from about 4M to about 7M, preferably about 6M.
6. The energy storage device as claimed in claim 1, wherein the energy storage device (1) is of faradiac efficiency ranging from about 94% to about 96%, preferably 95%.
7. An energy storage device (7) comprising plurality of energy storage device (1) of claim 1 connected in series.
8. A method of preparing substrate-integrated-lead-dioxide comprising acts of, etching pre-polished lead sheets;
a) washing the etched lead sheets with deionized water;
b) immersing the washed lead sheets in mixture of sulphuric acid and perchloric acid to obtain a layer of lead sulphate; and
c) oxidizing the lead sulphate to lead dioxide to obtain substrate-integrated lead dioxide.
9. The method of preparation of substrate-integrated lead dioxide as claimed in claim 8, wherein the etching is carried out using nitric acid.
10. The method of substrate-integrated lead dioxide as claimed in claim 9, wherein the nitric acid is of concentration from about 0.5M to about 1.5M, preferably about 1M.
11. The method of preparation of substrate integrated lead dioxide as claimed in claim 8, the sulphuric acid is concentrated in the range from about 4M to about 7M, preferably about 6M.
12. The method of preparation of substrate integrated lead dioxide as claimed in claim 8, wherein the perchloric acid is concentrated in the range from about 0.05M to about 0.2M, preferably about 0.1M.
13. The method of preparation of substrate-integrated lead dioxide as claimed in claim 8, wherein the oxidation of lead sulphate to lead dioxide is by using the lead sulphate as an anode in an electrochemical cell.
14. A method of manufacturing an energy storage device (1), comprising acts of:
a) preparing substrate-integrated lead dioxide electrode (2),
b) preparing activated carbon electrode (3), and
c) mounting the substrate-integrated lead dioxide electrode (2), the activated carbon electrode (3) in a container (6) with separator(4) soaked in an electrolyte (5) in- between the substrate-integrated lead dioxide and the carbon electrode to manufacture the energy storage device.
15. The method as claimed in claim 14, wherein the container (6) is made of material selected from a group comprising porous glass and porous polymer, preferably porous glass.
16. A method of using energy-storage device (1 or 7), said method comprising act of conjugating said energy-storage device with electrical device for generating electrical energy to devices in need thereof for working.
EP10853575.8A 2010-06-22 2010-06-28 An energy storage device and method thereof Withdrawn EP2586048A4 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN1744MU2010 2010-06-22
PCT/IN2010/000439 WO2011161686A1 (en) 2010-06-22 2010-06-28 An energy storage device and method thereof

Publications (2)

Publication Number Publication Date
EP2586048A1 true EP2586048A1 (en) 2013-05-01
EP2586048A4 EP2586048A4 (en) 2016-01-20

Family

ID=47996921

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10853575.8A Withdrawn EP2586048A4 (en) 2010-06-22 2010-06-28 An energy storage device and method thereof

Country Status (1)

Country Link
EP (1) EP2586048A4 (en)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6628504B2 (en) * 2001-05-03 2003-09-30 C And T Company, Inc. Electric double layer capacitor
US20080113268A1 (en) * 2006-10-23 2008-05-15 Buiel Edward R Recombinant Hybrid Energy Storage Device
US8911893B2 (en) * 2008-10-31 2014-12-16 Galen J. Suppes Convection battery configuration for connective carbon matrix electrode

Also Published As

Publication number Publication date
EP2586048A4 (en) 2016-01-20

Similar Documents

Publication Publication Date Title
CN110176591B (en) Aqueous zinc ion secondary battery and preparation method of anode based on organic electrode material
Prasad et al. Electrochemically synthesized MnO2-based mixed oxides for high performance redox supercapacitors
KR100534845B1 (en) Method for Manufacturing Nano-structured Electrode of Metal Oxide
JP2019516236A (en) Device and method for high voltage and solar cells
CN113257582A (en) Porous interconnected corrugated carbon-based network (ICCN) composite
CN102938331A (en) Foam nickel-base MnO2/C composite electrode material and preparation method thereof
JP2007180431A (en) Lithium ion capacitor
CN103426640A (en) Method for manufacturing thin film composite material
Shendkar et al. Hybrid composite polyaniline-nickel hydroxide electrode materials for supercapacitor applications
Peng et al. Hierarchically nitrogen-doped mesoporous carbon nanospheres with dual ion adsorption capability for superior rate and ultra-stable zinc ion hybrid supercapacitors
Brousse et al. Asymmetric and hybrid devices in aqueous electrolytes
US9147529B2 (en) Energy storage device and method thereof
CN112952212A (en) Aqueous manganese dioxide-metal secondary battery
US9036332B2 (en) Energy storage device, an inorganic gelled electrolyte and methods thereof
AU2012285404A1 (en) An energy storage device, an inorganic gelled electrolyte and methods thereof
CN103500665B (en) The ultracapacitor of tool core-shell type electrode
JP2014521231A5 (en)
KR100745193B1 (en) Manufacturing method of cnf/daaq composite electrode for supercapacitor
EP2586048A1 (en) An energy storage device and method thereof
CN110745871A (en) Electrode material CuCo of bimetal sulfide super capacitor2S4Preparation method of (1)
CN112053852A (en) Water-based capacitor battery and preparation method thereof
CN218215015U (en) Film electrode super capacitor battery
KR101837556B1 (en) Electrode material for supercapacitor utilizing cobalt oxide-nanocarbon composite consolidated active-conducting materials structured core-shell quantum dots type and fabrication process thereof
KR20030051078A (en) Supercapacitor and methods for manufacturing Ruthenium Oxide and Electrode used in the Supercapacitor
Shendkar et al. Hybrid composite polyaniline-nickel hydroxide electrode materials for

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20121203

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RA4 Supplementary search report drawn up and despatched (corrected)

Effective date: 20151222

RIC1 Information provided on ipc code assigned before grant

Ipc: H01G 9/00 20060101AFI20151223BHEP

Ipc: H01M 10/12 20060101ALI20151223BHEP

Ipc: H01M 4/14 20060101ALI20151223BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20160722