WO2002056325A1 - Condensateur electrochimique avec un materiau d'electrode assurant le stockage de l'energie - Google Patents

Condensateur electrochimique avec un materiau d'electrode assurant le stockage de l'energie Download PDF

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Publication number
WO2002056325A1
WO2002056325A1 PCT/US2001/000756 US0100756W WO02056325A1 WO 2002056325 A1 WO2002056325 A1 WO 2002056325A1 US 0100756 W US0100756 W US 0100756W WO 02056325 A1 WO02056325 A1 WO 02056325A1
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WO
WIPO (PCT)
Prior art keywords
electrochemical capacitor
iron
electrochemical
capacitor
group
Prior art date
Application number
PCT/US2001/000756
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English (en)
Inventor
Lih-Ren Shiue
Nae-Lih Wu
Dien-Shi Wu
Ching-Wen Chao
Yi-Ping Lan
Original Assignee
Lih-Ren Shiue
Nae-Lih Wu
Dien-Shi Wu
Ching-Wen Chao
Yi-Ping Lan
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 Lih-Ren Shiue, Nae-Lih Wu, Dien-Shi Wu, Ching-Wen Chao, Yi-Ping Lan filed Critical Lih-Ren Shiue
Priority to PCT/US2001/000756 priority Critical patent/WO2002056325A1/fr
Priority to US10/204,369 priority patent/US6678147B2/en
Publication of WO2002056325A1 publication Critical patent/WO2002056325A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
    • 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
    • Y02E60/13—Energy storage using capacitors
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to an energy storage device that can enhance the performances of batteries in numerous applications. More specifically, the present invention relates to an iron oxide compound used as the electrode material for supercapacitors.
  • Supercapacitor is also known as ultracapacitor or electric double layer capacitor. In rigid terms, though there is some distinction among them, they all can store a large quantity of charges up to several thousands farad ( F ) in compact sizes. Furthermore, they all have high power density ( > 1 KW/Kg) , high charge-discharge life ( > 10 4 cycles ) , and high discharge efficiency ( > 90% ) .
  • the high power density of supercapacitor derives from its quick-discharge characteristics in conjunction with large capacity of energy-storage. Such high power density imparts supercapacitors and the like a unique role as the peak-current provider in hand-held electronic devices, portable power tools, electrical vehicles ( EVs ) and automatic actuators.
  • All primary and secondary batteries are generally used to deliver small currents for lengthy times. This is due to the energy storage of batteries involves bulk oxidation-reduction which is thermodynamically controlled. Some batteries, such as lead-acid batteries, are capable of discharging quickly, delivering an instant large current greater than 100A in applications like the ignition of automobiles. Nevertheless, the batteries can only provide such large output at very short periods and infrequent repetitions, otherwise the batteries will soon be drained or damaged. In addition to miniaturization of the consumer electronics with inevitable shrinkage of batteries, the ENs are in urgent need for reducing oil consumption and air pollution, batteries should work in parallel with supercapacitors to fulfill the power requirements that batteries alone could not offer. In the parallel connection of batteries and supercapacitors, the latter can virtually provide any peak-current required repeatedly.
  • supercapacitors are a more versatile energy-storage device than battery. Especially in the regenerative braking of ENs, supercapacitors can quickly and safely save the residual kinetic energy of EVs for later use.
  • supercapacitor in the energy-management system of batteries has been validated. However, the present market prices of supercapacitors, as well as their dimensions and specifications, prevent them from general acceptance. Regardless of their merits, supercapacitors must offer an affordable price to be commercially viable. To lower the cost of supercapacitors, an inexpensive and readily made electrode material should be found.
  • the most frequently used electrode materials for supercapacitors include activated carbons and metal oxides. Metal oxides are superior to activated carbons in energy density, conductivity and workability. Oxides of various transition metals including ruthenium, rhodium, iridium, titanium, cobalt, molybdenum, tungsten, vanadium, manganese and nickel are investigated.
  • Ruthenium oxide ( RuO ) either in crystalline or amorphous state, and iridium oxide are determined to have a specific capacitance in the range of 100 - 750 F/g, which is equivalent to or three-time-higher than the value attainable from carbons. Ruthenium is a by-product in the extraction of platinum, hence Ru is rare and expensive. Cost-wise, RuO is unsuitable as the electrode material for making supercapacitors for general use. Other compounds such as sulfides, hydrides and nitrides of the aforementioned metals, iron and lead sulfides, as well as molybdenum and tungsten carbides and borides have been tested as the electrode material for electrochemical capacitor.
  • the primary object of the present invention is to provide supercapacitors comprising iron oxide as the active material of electrodes of the supercapacitors.
  • Iron oxide with a chemical composition of Fe x O y H Z5 where 1.0 ⁇ x ⁇ 3.0, 0.0 ⁇ y ⁇ 4.0, and 0.0 ⁇ z ⁇ 1.0 can be yielded in a thin film on iron, steel, or other substrates.
  • the electrode materials show capacitance of as high as 0.5 F/cm 2 or 320 F/g.
  • Another object of the present invention is to demonstrate that the black iron
  • magnetite ( 10,111 ) oxide or magnetite ( Fe 3 O 4 ) is the major component of Fe x O y H z to be responsible for the high energy-storage capacity of iron oxide.
  • Other form of iron oxide such as FeO, Fe 2 O 3 or FeO(OH) is likely present with the magnetite. Nevertheless , its presence appears to cause no adverse effects.
  • Yet another object of the present invention is to provide a direct growth of iron oxide film on iron, steel or other substrates.
  • Methods of one-step preparation include chemical oxidation, electrochemical oxidation, dip-coating, and electrophoretic deposition. Among them, chemical oxidation appears to be the most convenient way.
  • the film-coated substrates are ready to form supercapacitors.
  • binder nor additional electrode-fabricating equipment is required in the present invention.
  • Supercapacitors of the present invention can be prepared in simple procedures and no binder is needed, the present invention can further reduce the preparation cost of supercapacitors.
  • Still another object of the present invention is to provide iron oxide as the sole or partial ingredient of the electrode materials for supercapacitors.
  • Iron oxide may be used alone, or it may mix with carbons, metal powders or mineral particles to form a composite electrode for supercapacitors.
  • Iron-oxide film may also be formed on a porous support such as Sb-doped SnO .
  • the aforementioned combinations utilize the low-cost iron oxide to prepare affordable supercapacitors.
  • the last object of the present invention is to provide an environment-friendly material, iron oxide, for fabricating supercapacitors. Iron oxides are commonly present in numerous ores on earth. Scraps from the spent iron-oxide-electrodes of supercapacitors will cause no harm to the environments. Furthermore, the iron-oxide-electrodes are easy to regenerate and the substrates may be used repeatedly.
  • FIG.1 is the X-ray diffraction pattern of a Fe 3 O film electrode prepared by chemically oxidizing a carbon steel substrate in a boiling solution containing 1 OOOg NaOH, 12g NaNO 3 and 12g Na 2 Cr 2 O in 1 liter de-ionized water.
  • the arrowed reflection are due to Fe 3 O , while those marked with ⁇ are due to the substrate, Fe.
  • FIG.2 is a cyclic voltammogram of two electrodes of 2cm x 2cm substrate under 50 mN/sec scanning rate in O. ' IM Na 2 SO and 0.5M KOH.
  • FIG.3 is a cyclic voltammogram of two electrodes of 2cm x 2cm Fe 2 O 3 /Fe substrate under 50 mN/sec scanning rate in 0.1M Na 2 SO 4 and 0.5M KOH.
  • FIG.4 is a cyclic voltammogram of Fe 3 O film electrodes in IM Na SO aqueous solution under 20 mV/sec scanning rate.
  • FIG.5 is a cyclic voltammogram of electrodes consisting of a mixture layer of iron oxyhydroxide and oxide deposited on titanium substrates in IM Na 2 SO 4 aqueous solution under 20 mV/sec scanning rate.
  • FIG.6 is a constant-current charge-discharge plot of electrodes consisting of a mixture layer of iron oxyhydroxide and oxide deposited on titanium substrates in IM Na 2 SO aqueous solution under a current density of 5 mA/cm 2 .
  • FIG.7 is a self-discharge curve of a primitive supercapacitor containing two serially connected cells. Each cell consists of two pairs of 8cm x 8cm Fe 3 O /Fe electrodes connected in-parallel.
  • FIG.8 is a group of discharge curves of a primitive supercapacitor using 8cm x 8cm
  • Fe 3 O 4 /Fe electrodes under various constant currents.
  • the prototype device is rated as 2.5 V x 0.1 F, and LED is the abbreviation of the assignee.
  • supercapacitors may utilize two different mechanisms, double layer (DL) or surface reduction-oxidation, to store electric charges and form double layer capacitance or pseudocapacitance.
  • a DL of opposite charges is automatically formed on the solid-liquid interface when a conductor is placed in an electrolyte solution, which blocks the diffusion of ions or species to the conductor for analysis. DL is thus minimized from the interface of solid and liquid in electrochemical analyses.
  • the DL structure is deliberately maximized to store static charges to form DL capacitance in supercapacitors. There is no charge transfer in DL capacitance, yet the psudocapacitance comes from faradaic reactions involving surface or adsorbed species at the electrode-electrolyte interface.
  • the energy stored in capacitors can be determined by the following formula:
  • E 1/2 CV 2 (1)
  • C capacitance in farad (F)
  • V the working voltage of capacitor in volt.
  • CV cyclic voltammetry
  • Iron oxide formed in aqueous solutions is likely in hydrous states and is best described by a chemical composition of Fe x O y H z , where 1.0 ⁇ x ⁇ 3.0, 0.0 ⁇ y ⁇ 4.0, and 0.0 ⁇ z ⁇ 1.0.
  • FIG. 2 shows the 10th CV graph of two free-standing electrodes of black Fe 3 O 4 thin-film on 2 cm x 2 cm iron substrate in an aqueous solution containing 0.1M Na 2 SO and 0.5M KOH under 50 mV/sec scanning rate. No reference electrode is used in the analysis. Except slight tilt at both ends, the CV loop is a nice rectangle, which is a typical capacitor behavior, with rapid change of current at voltage reversal. Furthermore, the voltammogram remains the same shape in many cycles of voltage scanning. This indicates that the iron oxide has good reversibility, conductivity and sorption-desorption characteristics. From FIG. 2 and equation (2), the iron oxide electrodes produced are estimated to have capacitance of 0.03 F/cm 2 .
  • Example 2 the iron oxide electrodes produced are estimated to have capacitance of 0.03 F/cm 2 .
  • Thin Fe 2 O /Fe electrodes were prepared according to example 1 except the cooking time is extended to 20 minutes. At that time, reddish-brown color on the substrates was also observed.
  • Fe 2 O 3 /Fe electrodes were also analyzed by CV as example 1, and one of the result is shown in FIG. 3. It is clearly seen that the CV loop of Fe 2 O 3 is not a normal behavior of capacitors. Thus, the capacitance of the Fe 2 O 3 electrode material can not be estimated precisely. However, there is a significant difference between the capacitance of the two iron oxides, and it may be interpreted from their difference in crystal structure and conductivity.
  • Fe 3 O is an inverse spinel consisting of two oxidation states of iron, Fe(II) and
  • Fe(III) with the less abundant Fe(II) restricted to four-fold tetrahedral sites and the more abundant Fe(III) distributed evenly between the tetrahedral sites and six-fold octahedral sites, which gives Fe 3 O 4 the formula as
  • Fe(II) and Fe(III) which imparts Fe 3 O as a semiconductor with resistivity of 10 "2 ⁇ -cm.
  • Fe 2 O 3 is a rhomohedral oxide consisting of a hexagonal close packed oxygen array with two thirds of the octahedral interstices occupied by Fe(III).
  • Fe 2 O is an insulator with a band gap of 3.1 eN
  • surface area of the electrodes should not be responsible for the great capacitance difference between Fe 3 O 4 and F ⁇ 2 ⁇ 3 . Instead, the difference in the conductivity of the iron oxides should be the cause.
  • Example 3 lcm x 1cm carbon steel substrates were cooked in one liter de-ionized water containing lOOOg NaOH, 12g NaNO 3 and 12g Na 2 Cr 2 O 7 at 135 -145°C for 20 minutes to produce a 3 ⁇ m composite iron-oxide layer predominantly in Fe 3 O .
  • a sandwich-type cell was prepared by disposing a glass-fiber separator soaked with IM Na 2 SO 4 electrolyte between two iron-oxide electrodes. The cell was analyzed by CV using 20 mV/sec scanning rate between -0.8 volt and +0.8 volt.
  • FIG. 4 shows the result of CV graph.
  • C e _ of the electrode material studied is determined to be 0.38 F/cm 2 . Assuming the density of the porous oxide layer is 4.0 g/cm 3 , and using the known layer thickness of 3 ⁇ m, the above capacitance is converted to a specific capacitance of 320 F/g of the electrode material.
  • An electrochemical capacitor was built according to example 3 except that 0.5M Na 3 PO 4 aqueous solution was used as the electrolyte.
  • the capacitance of the electrode material was determined using the same procedures as example 3 and was found to be 0.08 F/cm 2 .
  • An electrochemical capacitor was assembled according to example 3 except that iron plates were used as the substrates. As demonstrated in example 3, the cell was examined using CV and the same electrolyte except higher scanning rate of 50 mV/sec was used. The capacitance of the electrode material was determined to be
  • Example 6 An electrochemical capacitor was made according to example 3 except that an aqueous solution containing IM Na 2 SO 4 and 0.001M KOH was used as the electrolyte. CN measurement was conducted using the same procedures as example 3, and Cei was found to be 0.2 F/cm .
  • Example 7 1cm x 1cm iron substrates were oxidized in one liter water containing lOOOg
  • a sandwich-type cell was prepared by disposing a glass-fiber separator soaked with 0.1M Na 2 SO electrolyte between two anodized electrodes. The cell was analyzed by CN using 20 mN/sec scanning rate between -0.8 volt and +0.8 volt, and C e ⁇ was determined to be 0.05 F/cm 2 .
  • Example 8 lcm x 1cm titanium substrates were first coated with an conductive porous Sb-doped Sn ⁇ 2 layer. The latter was then electroplated in IM aqueous FeSO solution under a constant current of 195 mA for 5 minutes so that iron was deposited within the interstices, as well as on the surface of the porous layer. There are two functions for the Sn ⁇ 2 layer: to provide porous sites for the formation of iron and iron oxide particles, and to provide a highly conductive pathway for the iron oxide. The electroplated substrates were then thermally oxidized in 0.01 torr air at 700°C for 3 minutes. An electrochemical capacitor was assembled according to example 3, CN measurement was conducted as well. C e ⁇ of the electrode material was found to be 0.04 F/cm 2 .
  • Example 9 Two Sn ⁇ 2 -coated titanium substrates prepared according to example 8 were immersed in IM FeSO 4 aqueous solution at pH 8. A stream of oxygen gas was bubbled through the solution for 30 minutes to yield a composite layer of yellowish iron oxyhydroxide [FeO(OH)] and black iron oxide within the interstices, as well as on the surface of the porous SnO 2 layer.
  • an electrochemical capacitor was assembled according to example 3, CN measurement was conducted and shown in FIG.5. It is a quasi-rectangle CN loop indicating that the electrode materials have good kinetic reversibility and conductivity. Cei of the electrode materials was found to be 0.04 F/cm 2 .
  • 8cm x 8 cm Fe 3 O /Fe electrodes were prepared according to example 1, and a unit cell was constructed simply by placing four pieces of electrodes in a regular plastic bag with a Manila paper disposed between every two electrodes. Without using spot or laser welding, the electrodes were clamped in parallel connection. After an aliquot of an aqueous solution containing 0.1M ⁇ a 2 SO and 0.5M KOH was put into the bag, it was sealed using a heat sealer. Neither additional encapsulation, nor compression was applied to the electrodes for intimate contact. Two loose unit-cells were connected in series to form primitive supercapacitors. Then, alligator clips were connected to the anode and cathode of supercapacitor for electrochemical and electrical characterizations.
  • FIG.7 shows a self-discharge curve of the primitive device after being charged to 2.8 volt. Initially the voltage of the device decreases very rapidly then levels off. Such behavior is commonly observed for regular capacitors as well as supercapacitors including commercial products. Nevertheless, the present invention shows a high self-discharge rate that is in accordance with many loose ends in the current cell-design.
  • FIG. 8 contains the discharge curves of the fully charged device under various constant currents. Therefrom, the specifications of the prototype are extracted and listed in the following table:
  • the present invention has demonstrated promising qualities for commercial use.
  • the prototype shows low ESR (equivalent series resistance) which is very important in high frequency and high power applications, and thin cell-thickness (1.7 mm) which is in compliance with the miniaturization of electronic devices.
  • FIG 8 also shows that the prototype is capable of delivering a peak current as high as 10 A, and that is useful in applications requiring pulse powers.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

L'invention concerne un film d'oxyde de fer développé directement sur du fer, de l'acier ou d'autres substrats par oxydation chimique ou électrochimique, et qui constitue un matériau prometteur pour le stockage de l'énergie par adsorption en surface de charges statiques. Comme les matériaux d'électrodes des dispositifs de stockage de l'énergie, l'oxyde de fer présente une composition chimique de FexOyHz, où 1.0≤ x ≤ 3.0, 0.0≤ y ≤ 4.0, et 0.0 ≤ z ≤ 1.0. On utilise une solution aqueuse ou organique d'un sel métallique comprenant des sulfates, sulfites, hydroxydes, chlorures, phosphates et nitrates comme électrolyte pour les dispositifs électrochimiques. La voltamétrie cyclique indique que les électrodes fer-oxyde dans les électrolytes peuvent stocker des charges aussi importantes que 0.5 F/cm2 ou 320 F/g des matériaux d'électrodes. Les condensateurs électrochimiques utilisant de l'oxyde de fer comme matériau d'électrode constituent une source d'énergie économique et viable pour des systèmes électroniques portatifs, les outils à commande mécanique et les véhicules électriques.
PCT/US2001/000756 2001-01-09 2001-01-09 Condensateur electrochimique avec un materiau d'electrode assurant le stockage de l'energie WO2002056325A1 (fr)

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Application Number Priority Date Filing Date Title
PCT/US2001/000756 WO2002056325A1 (fr) 2001-01-09 2001-01-09 Condensateur electrochimique avec un materiau d'electrode assurant le stockage de l'energie
US10/204,369 US6678147B2 (en) 2001-01-09 2001-01-09 Electrochemical capacitor with electrode material for energy storage

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7842178B2 (en) 2005-04-18 2010-11-30 University Of Iowa Research Foundation Magnet incorporated electrically conductive electrodes
EP2816576A1 (fr) 2013-06-19 2014-12-24 Instytut Elektrotechniki Procédé de fabrication d'un matériau d'oxyde d'électrode, matériau d'oxyde d'électrode et applications du matériau d'oxyde d'électrode

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5872698A (en) * 1996-02-01 1999-02-16 Bai; Lijun Composite multilayer electrodes for electrochemical cells
US5963417A (en) * 1995-11-09 1999-10-05 Wisconsin Alumni Research Foundation Electrochemical capacitor
US6094338A (en) * 1997-07-09 2000-07-25 Mitsubishi Chemical Corporation Electric double-layer capacitor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5963417A (en) * 1995-11-09 1999-10-05 Wisconsin Alumni Research Foundation Electrochemical capacitor
US5872698A (en) * 1996-02-01 1999-02-16 Bai; Lijun Composite multilayer electrodes for electrochemical cells
US6094338A (en) * 1997-07-09 2000-07-25 Mitsubishi Chemical Corporation Electric double-layer capacitor

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7842178B2 (en) 2005-04-18 2010-11-30 University Of Iowa Research Foundation Magnet incorporated electrically conductive electrodes
EP2816576A1 (fr) 2013-06-19 2014-12-24 Instytut Elektrotechniki Procédé de fabrication d'un matériau d'oxyde d'électrode, matériau d'oxyde d'électrode et applications du matériau d'oxyde d'électrode

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