WO2015174043A1 - Supercondensateur à anode au cyanométallate métallique et cathode carbonée - Google Patents

Supercondensateur à anode au cyanométallate métallique et cathode carbonée Download PDF

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Publication number
WO2015174043A1
WO2015174043A1 PCT/JP2015/002300 JP2015002300W WO2015174043A1 WO 2015174043 A1 WO2015174043 A1 WO 2015174043A1 JP 2015002300 W JP2015002300 W JP 2015002300W WO 2015174043 A1 WO2015174043 A1 WO 2015174043A1
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WIPO (PCT)
Prior art keywords
group
supercapacitor
anode
cathode
metals
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PCT/JP2015/002300
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English (en)
Inventor
Yuhao Lu
Long Wang
Jong-Jan Lee
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Sharp Kabushiki Kaisha
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Publication date
Priority claimed from US14/274,686 external-priority patent/US9443664B2/en
Application filed by Sharp Kabushiki Kaisha filed Critical Sharp Kabushiki Kaisha
Publication of WO2015174043A1 publication Critical patent/WO2015174043A1/fr

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    • 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
    • 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

Definitions

  • This invention generally relates to electrochemical capacitors and, more particularly, to a supercapacitor made from a hexacyanometallate cathode and activated carbon anode.
  • a supercapacitor, or electrochemical capacitor (EC), constitutes one type of device for electrochemical energy storage and conversion.
  • the electrochemical capacitor consists of two electrodes separated by an electrolyte-soaked separator by which the two electrodes are electrically isolated.Based upon the electrode type and the energy storage mechanism, the supercapacitor may be classified into one of the two following categories: (1) an electric double layer capacitor (EDLC), in which the energy is stored at the interface between the electrode and electrolyte through electrostatic charge accumulation, or (2) a pseudo-capacitor (or ultra-capacitor), whereby one electrode undergoes faradic reactions while the other electrode maintains the electrostatic charge accumulation.
  • EDLC electric double layer capacitor
  • pseudo-capacitor or ultra-capacitor
  • the state-of-the-art commercial activated carbon materials have surface areas of 1000-3500 m 2 /g and capacitances of ⁇ 200 F/g [NPL 1]. Physical adsorption of the electrostatic charge restricts the capacitance from further increases. Therefore, the introduction of faradic reactions to supercapacitors results in the so-called pseudo-/ultra-capacitors.
  • pseudo-capacitors demonstrate much larger capacitances than EDLC because Faradic reactions can store charges both on the surface and in the bulk of the electrode materials.
  • Ruthenium oxide (RuO 2 ) for example, exhibits a high capacitance of 720 F/g based upon the faradic reaction of where the redox couple, Ru 3+/4+ , is reversible during the dis/charge process[NPL 2].
  • a robust material for the pseudo-capacitor electrode must demonstrate fast transport of charges and electrons in its structure(s), in order to ensure a high power density.
  • Fig. 1 depicts the crystal structure of a metal hexacyanometallate (prior art).
  • Prussian blue analogues belong to a class of mixed valence compounds called transition metal hexacyanometallates.
  • the hexacyanometallates have a general formula A m M1 X M2 Y (CN) 6 , where M1 and M2 are transition metals.
  • the crystal structure of metal hexacyanometallates has an open framework which can facilitate fast and reversible intercalation processes for alkali and alkaline ions (A m ).
  • Dr. Goodenough ⁇ s group investigated a series of Prussian blue analogues in a sodium battery with organic electrolyte, and found that KFe(II)Fe(III)(CN) 6 demonstrated the highest capacity of ca. 95 mAh/g, while KMnFe(CN) 6 , KNiFe(CN) 6 , KCuFe(CN) 6 , and KCoFe(CN) 6 demonstrated a capacity of 50 ⁇ 70 mAh/g[NPL5]. In the first 30 cycles, the capacity retention of KFeFe(CN) 6 was higher than 97%.
  • Patent application 13/603,322 Supercapacitor with Hexacyanometallate Cathode, Activated Carbon Anode, and Aqueous Electrolyte, incorporated herein by reference, describes a method for fabricating a supercapacitor with a hexacyanometallate (positive electrode), an activate carbon (negative electrode), and an aqueous electrolyte containing metal salt. Alkali ion or alkaline earth ions are inserted in, and extracted from the hexacyanometallate lattice during the charge/discharge of the supercapacitor.
  • a supercapacitor is described herein that has a metal cyanometallate (MCM) electrode that functions as the negative electrode (anode), and carbonaceous materials that perform as positive electrode (cathode).
  • MCM metal cyanometallate
  • MCM material can be described using the chemical formula of A X M1 Y M2 Z (CN) N . MH 2 O.
  • M1 and M2 may be the same or different metal ions, such as titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), calcium (Ca), magnesium (Mg), strontium (Sr), and barium (Ba).
  • A may be selected from a broad group of cations including alkali and alkaline earth metals.
  • the electrolyte may be an aqueous, non-aqueous, polymer, gel, or solid electrolyte.
  • the electrolyte contains salts, DB, to realize the energy storage and conversion.
  • the cations, D can be hydrogen (H + ), lithium (Li + ), sodium (Na + ), potassium (K + ), ammonium (NH 4 + ), rubidium (Rb + ), cesium (Cs + ), magnesium (Mg 2+ ), calcium (Ca 2+ ), strontium (Sr 2+ ), barium (Ba 2+ ), cobalt (Co 2+ ), iron (Fe 2+ ), (Fe 3+ ), copper (Cu 2+ ), tetramethylammonium, tetraethylammonium, or complex cations.
  • the anions, B can be selected from fluorine (F), chlorine (Cl), bromine (Br), iodine (I), carbon trioxide (CO 3 ), sulfur trioxide (SO 3 ), sulfate (SO 4 ), phosphate (PO 4 ), aluminate anion (AlO 2 ), nitrate (NO 3 ), hydroxide (OH - ), perchlorate (ClO 4 ), tetrafluoroborate anion (BF 4 - ), hexafluorophosphate (PF 6 ), hexafluoroarsenate ion (AsS 6 ), trifluoromethanesulfonic (CF 3 SO 3 ), N-fluoromethanesulfony (N(SO 2 CF 3 ) 2 ), N-fluoroethanesulfony imide (N(SO 2 CF 2 CF 3 ) 2 ), complex anions, or combinations thereof.
  • the supercapacitor
  • a method for charging a supercapacitor initially provides a supercapacitor with a MCM particle anode, an electrolyte including a salt (DB) made up of cations (D + ) and anions (B - ), and a cathode including carbonaceous materials .
  • the method connects an external charging device between the anode and cathode, and the charging device supplies electrons to the anode and accepts electrons from the cathode.
  • cations are inserted into the anode while anions are absorbed on the surface of the cathode.
  • anions are absorbed at the cathode as follows: where "d” and "b” are quantities.
  • Fig. 1 depicts the crystal structure of a metal hexacyanometallate (prior art).
  • Fig. 2 is a partial cross-sectional view of a supercapacitor.
  • Fig. 3A demonstrates the behavior of a supercapacitor with an activated carbon positive electrode and a Berlin Green negative electrode.
  • Fig 3B demonstrates the behavior of a supercapacitor with an activated carbon positive electrode and a Berlin Green negative electrode.
  • Fig. 4 is a flowchart illustrating a method for charging a supercapacitor.
  • Fig. 2 is a partial cross-sectional view of a supercapacitor.
  • the supercapacitor 200 comprises an anode 202 including metal cyanometallate (MCM) particles 204 overlying a current collector 206.
  • MCM particles 204 have the chemical formula A X M1 Y M2 Z (CN) N . MH 2 O;
  • A is selected from a first group of metals
  • M1 and M2 are transition metals
  • N is less than or equal to 6;
  • An electrolyte 208 includes cations 210 selected from a second group of materials and anions 212 selected from a third group of materials.
  • a cathode 214 including carbonaceous materials 216 overlies a current collector 218.
  • the first group of metals includes alkali metals, alkaline earth metals, and combinations thereof. More explicitly, the first group of metals includes lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), calcium (Ca), strontium (Sr), barium (Ba), silver (Ag), aluminum (Al), and magnesium (Mg).
  • M1 is a metal with 2 + or 3 + valance positions.
  • M2 is a metal with 2 + or 3 + valance positions. M1 and M2 are each independently derived, meaning they may be the same metal or different metals.
  • M1 and M2 metals include titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), calcium (Ca), magnesium (Mg), strontium (Sr), and barium (Ba).
  • the second group of materials that make up the cations 210 include hydrogen (H), lithium (Li), sodium (Na), potassium (K), ammonium (NH 4 ), rubidium (Rb), cesium (Cs), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), cobalt (Co), iron (Fe), copper (Cu), tetramethylammonium, tetraethylammonium, and combinations thereof.
  • the third group of materials that make up the anions 212 include fluorine (F), chlorine (Cl), bromine (Br), iodine (I), carbon trioxide (CO 3 ), sulfur trioxide (SO 3 ), sulfate (SO 4 ), phosphate (PO 4 ), aluminate anion (AlO 2 ), nitrate (NO 3 ), hydroxide (OH - ), perchlorate (ClO 4 ), tetrafluoroborate anion (BF 4 - ), hexafluorophosphate (PF 6 ), hexafluoroarsenate ion (AsS 6 ), trifluoromethanesulfonic (CF 3 SO 3 ), N-fluoromethanesulfony (N(SO 2 CF 3 ) 2 ), N-fluoroethanesulfony imide (N(SO 2 CF 2 CF 3 ) 2 ), and combinations thereof.
  • the electrolyte 208 may be an aqueous, non-aqueous, polymer, gel, or solid electrolyte.
  • an ion permeable membrane 220 is used to separate the anode 202 from the cathode 214.
  • Both the MCM particles 204 and carbonaceous materials 216 are porous materials that enable electrolyte to fill their pores.
  • the carbonaceous materials 216 of the cathode 214 may be activated carbon, carbon black, carbon paper, or carbon cloth.
  • the MCM particles A X M1 Y M2 Z (CN) N . MH 2 O demonstrate frameworks that consist of M1-N-C-M2 skeletons and large interstitial space as shown in Fig. 1 that "A" cations can occupy.
  • the cations can be quickly and reversibly inserted / extracted into/out their interstitial spaces, making MCM a good electrode material for supercapacitors.
  • Carbonaceous materials e.g. activated carbon
  • aqueous, non-aqueous, gel, polymer, or solid electrolytes can be used between them.
  • Positive electrode Negative electrode: The reaction on the positive electrolyte occurs quickly because the anions are just absorbed on the electrode surface. As to the anodic reaction, sodium-ions have to diffuse into the interstitial space of Berlin Green material. This step has been evaluated in an electrochemical cell consisting of Berlin Green electrode and sodium metal electrode. Berlin Green showed an excellent rate capability.
  • Figs. 3A and 3B demonstrate the behavior of a supercapacitor with an activated carbon positive electrode and a Berlin Green negative electrode.
  • the Berlin Green supercapacitor delivered a capacity of ⁇ 110 milliamp hours per gram (mAh/g).
  • the supercapacitor worked at a high power density with a considerable energy density.
  • Fig. 3A depicts the voltage vs. capacity of the Berlin Green supercapacitor in the first charge/discharge cycle.
  • Fig. 3B depicts the capacity retention of the Berlin Green supercapacitor.
  • Fig. 4 is a flowchart illustrating a method for charging a supercapacitor. Although the method is depicted as a sequence of numbered steps for clarity, the numbering does not necessarily dictate the order of the steps. It should be understood that some of these steps may be skipped, performed in parallel, or performed without the requirement of maintaining a strict order of sequence. Generally however, the method follows the numeric order of the depicted steps. The method starts at Step 400.
  • Step 402 provides supercapacitor comprising a metal cyanometallate (MCM) particle anode, an electrolyte including a salt (DB) comprising cations (D + ) and anions (B - ), and a cathode including carbonaceous materials , see Fig. 2.
  • Step 404 connects an external charging device (current source) between the anode and cathode.
  • the charging device supplies electrons to the anode and accepts electrons from the cathode.
  • Step 408 inserts cations into the anode, and absorbs anions on a surface of the cathode.
  • Providing the anode in Step 402 includes the MCM particles having the chemical formula A X M1 Y M2 Z (CN) N . MH 2 O;
  • A is selected from a first group of metals
  • M1 and M2 are transition metals
  • N is less than or equal to 6;
  • Step 408 performs the following reaction at the cathode: where "d” and "b" are quantities;
  • Step 406 performs the following reaction at the anode:
  • the first group of metals includes alkali metals, alkaline earth metals, and combinations thereof. Specific examples from the first group of metals include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), calcium (Ca), strontium (Sr), barium (Ba), silver (Ag), aluminum (Al), and magnesium (Mg).
  • M1 and M2 are each independently derived, and are typically selected from the following group: titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), calcium (Ca), magnesium (Mg), strontium (Sr), and barium (Ba).
  • the cations may be hydrogen (H), lithium (Li), sodium (Na), potassium (K), ammonium (NH 4 ), rubidium (Rb), cesium (Cs), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), cobalt (Co), iron (Fe), copper (Cu), tetramethylammonium, tetraethylammonium, or combinations thereof.
  • the anions may be fluorine (F), chlorine (Cl), bromine (Br), iodine (I), carbon trioxide (CO 3 ), sulfur trioxide (SO 3 ), sulfate (SO 4 ), phosphate (PO 4 ), aluminate anion (AlO 2 ), nitrate (NO 3 ), hydroxide (OH - ), perchlorate (ClO 4 ), tetrafluoroborate anion (BF 4 - ), hexafluorophosphate (PF 6 ), hexafluoroarsenate ion (AsS 6 ), trifluoromethanesulfonic (CF 3 SO 3 ), N-fluoromethanesulfony (N(SO 2 CF 3 ) 2 ), N-fluoroethanesulfony imide (N(SO 2 CF 2 CF 3 ) 2 ), or combinations thereof.
  • the electrolyte may be an aqueous, non-aqueous, polymer, gel, or solid electrolytes.
  • the carbonaceous materials of the cathode may be activated carbon, carbon black, carbon paper, or carbon cloth.
  • the process of discharging the supercapacitor is essentially the reverse of the charging process, with the anode and cathode being connected to a load instead of a current source.
  • the reactions at the anode and cathode during discharge are presented below.
  • Positive electrode Negative electrode: Examples of particular materials and process steps have been presented to illustrate the invention. However, the invention is not limited to merely these examples. Other variations and embodiments of the invention will occur to those skilled in the art.
  • a supercapacitor with a metal cyanometallate anode and carbon cathode has been provided with an associated charging method.

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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 procédé de charge d'un supercondensateur. Le procédé consiste à utiliser initialement un supercondensateur ayant une anode à particules de cyanométallate métallique (MCM), un électrolyte comprenant un sel (DB) constitué de cations (D+) et d'anions (B-) et une cathode comprenant des matériaux carbonés. Le procédé consiste à connecter un dispositif de charge externe entre l'anode et la cathode, et le dispositif de charge fournit des électrons à l'anode et accepte des électrons provenant de la cathode. En réponse au dispositif de charge, des cations sont introduits dans l'anode tandis que des anions sont absorbés sur la surface de la cathode. L'invention concerne également un dispositif à supercondensateur.
PCT/JP2015/002300 2014-05-10 2015-04-30 Supercondensateur à anode au cyanométallate métallique et cathode carbonée WO2015174043A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14/274,686 2014-05-10
US14/274,686 US9443664B2 (en) 2012-03-28 2014-05-10 Supercapacitor with metal cyanometallate anode and carbonaceous cathode

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WO2015174043A1 true WO2015174043A1 (fr) 2015-11-19

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016202979A1 (de) * 2016-02-25 2017-08-31 Robert Bosch Gmbh Hybridsuperkondensator
US10122049B2 (en) 2014-02-06 2018-11-06 Gelion Technologies Pty Ltd Gelated ionic liquid film-coated surfaces and uses thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101546650A (zh) * 2009-04-10 2009-09-30 中南大学 一种超级电容器电极材料及其制备
JP2011180469A (ja) * 2010-03-03 2011-09-15 National Institute Of Advanced Industrial Science & Technology プルシアンブルー型金属錯体ナノ粒子を具備する電気化学素子、これを用いたエレクトロクロミック素子及び二次電池
WO2012177932A2 (fr) * 2011-06-22 2012-12-27 The Board Of Trustees Of The Leland Stanford Junior University Matériaux d'électrode de batterie à longue durée de vie de cycles à haute charge présentant une structure d'ossature ouverte
US20130257378A1 (en) * 2012-03-28 2013-10-03 Yuhao Lu Transition Metal Hexacyanoferrate Battery Cathode with Single Plateau Charge/Discharge Curve

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101546650A (zh) * 2009-04-10 2009-09-30 中南大学 一种超级电容器电极材料及其制备
JP2011180469A (ja) * 2010-03-03 2011-09-15 National Institute Of Advanced Industrial Science & Technology プルシアンブルー型金属錯体ナノ粒子を具備する電気化学素子、これを用いたエレクトロクロミック素子及び二次電池
WO2012177932A2 (fr) * 2011-06-22 2012-12-27 The Board Of Trustees Of The Leland Stanford Junior University Matériaux d'électrode de batterie à longue durée de vie de cycles à haute charge présentant une structure d'ossature ouverte
US20130257378A1 (en) * 2012-03-28 2013-10-03 Yuhao Lu Transition Metal Hexacyanoferrate Battery Cathode with Single Plateau Charge/Discharge Curve

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10122049B2 (en) 2014-02-06 2018-11-06 Gelion Technologies Pty Ltd Gelated ionic liquid film-coated surfaces and uses thereof
DE102016202979A1 (de) * 2016-02-25 2017-08-31 Robert Bosch Gmbh Hybridsuperkondensator

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