WO2006111079A1 - Dispositif de stockage d'energie aqueux hybride - Google Patents

Dispositif de stockage d'energie aqueux hybride Download PDF

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Publication number
WO2006111079A1
WO2006111079A1 PCT/CN2006/000711 CN2006000711W WO2006111079A1 WO 2006111079 A1 WO2006111079 A1 WO 2006111079A1 CN 2006000711 W CN2006000711 W CN 2006000711W WO 2006111079 A1 WO2006111079 A1 WO 2006111079A1
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Prior art keywords
ion
storage device
energy storage
hybrid
lithium
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PCT/CN2006/000711
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English (en)
Inventor
Yongyao Xia
Yonggang Wang
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Fudan University
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Publication of WO2006111079A1 publication Critical patent/WO2006111079A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01G11/26—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, 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
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • 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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • 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
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • 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
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/145—Liquid electrolytic capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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

  • the present invention relates to a hybrid aqueous energy storage device (battery/supercapacitor).
  • Ni-MH battery used Ni-MH battery as an assistant power source
  • Nissan with a lithium-ion battery a lithium-ion battery.
  • Ni-MH and lithium-ion battery have a high energy density but with a drawback of undesirable cycling life and specific capability, the output specific power is limited to 600 W/kg.
  • the electrochemical double layer capacitor has a long life over than 10,000 cycles, and a high specific power as high as 1500 W/kg, but with a low energy-density ( ⁇ 5 Wh/kg).
  • Li-ion battery using two Li-ion intercalated compounds typically a transition metal oxide positive electrode and a carbon negative material
  • the nonaqueous lithium-ion batteries have been widely used for the portable electric devices, such as note-sized PC, and cell phone etc.
  • the drawbacks of low safety and high fabrication cost due to the use of highly toxic and/or flammable organic solvents limit the application as large-scale batteries, especially for electric vehicle (EV) application.
  • EV electric vehicle
  • the hybrid system of the present invention also consists of capacitor electrode and a Li-ion battery electrode in a Li-ion containing aqueous electrolyte solution in which typically an activated carbon is used as negative electrode, and a Li-ion intercalated compound as the positive electrode.
  • the negative electrode stores charge through a reversible non-faradic reaction of Li-ion on the surface of an activated carbon.
  • the positive electrode utilizes a reversible faradic reaction of Li-ion insertion/extraction in LiMn 2 O 4 .
  • the charge/discharge process is associated with the transfer of Li-ion between two electrodes, which we defined as "hybrid aqueous lithium-ion cell".
  • the electrode reactions of the hybrid system described in the present invention are different from any hybrid electrochemical surpercapacitors and electrochemical double layer supercapacitors in which the salts in electrolyte will be consumed during the charge process.
  • the ion concentration in the electrolyte will affect the energy density of the hybrid electrochemical surpercapacitors, especially in the organic electrolyte based hybrid system.
  • the hybrid system of the present invention has provided a real green energy storage device with a long cycling life, an appreciate energy density, high power, low cost, low toxicity and high safety, especially for the electric vehicle (EV) application.
  • the purpose of the present invention is to provide a real green energy storage device with a long cycling life, an appreciate energy density, high power, low cost, low toxicity and high safety.
  • a hybrid aqueous energy storage device comprises in contiguity a positive electrode membrane, a negative electrode membrane, a separator membrane interposed therebetween, and an aqueous electrolyte containing cation and anion of an ion species of a dissociable salt.
  • the material used for positive electrode is lithium-ion intercalated compounds which can be selected from the group consisting of transition metal oxides, sulfides, phosphates, and fluorides.
  • the negative material of the hybrid system can be selected from material with double layer capacitance behavior, such as activated carbon, mesoporous carbon and carbon nanotubes etc.
  • the negative electrode material can also be of composites based on carbon material with high surface area and pseudocapacitive electrode material.
  • the pseudocapacitive electrode can be selected from transition metal oxides, lithium-ion intercalated compounds, conductive polymer and organic polyiadical.
  • the electrolyte containing at least one ion is lithium-ion in aqueous solution.
  • a lithium-ion contained aqueous is used.
  • the oxygen evolution occurs on the positive electrode when charged to a definite potential.
  • 4 V lithium-ion intercalated compounds are used, which can be selected from the group consisting of oxides, sulfides, phosphates, and fluorides of transition metal including Mn, Ni, Co, Fe, V.
  • the compound can be LiMn 2 O 4 , LiCo ⁇ 2 , LiCo 1Z3 Ni 1Z3 Mn 1Z3 O 2 , LiNiO 2 , LiFePO 4 , and can be doped by other element M which is at least one selected from the group consisting of Li, Mg, Cr, Al, Co, Ni, Mn, Al, Zn, Cu, La. Typically the doped amount of M is less 50% by molar of total amount of the metal. In view of the cost and safety, LiMn 2 O 4 and the other metal element modified LiM x Mn 2- XO 4 are most preferred. As the above electrode materials are normally the semiconductor, it is preferred to add electronic conductors which can be carbon black, acetylene black, and graphite.
  • the composite positive membrane also contains at least one binder selected from the group consisting of PTFE, water-solubility rob, and CMC.
  • the weight content of the binder in the composite electrode membrane is less than 20%.
  • the negative electrode stores charges through a reversible nonfaradic reaction of cation on the surface of porous carbon material (double layer capacitance). The surface area for these porous carbons over than 1000 m 2 /g is preferred.
  • the electronic conductor can be added, and can be carbon black, acetylene black, and graphite.
  • the composite negative membrane also contains at least one binder selected from the group consisting of PTFE, water-solubility rubber, and cellulose.
  • some pseudocapacitance electrode materials which can be selected from the group consisting of LiMn 2 O 4 , VO 2, LiV 3 O 8 , FeOOH, and polyaniline can also be added.
  • the intercalation potential for these pseudocapacitance material is typically at 2.5-3 V vs. Li/Li + "
  • the electrolyte used for this hybrid system can be in liquid or gel state.
  • the electrolyte salts can be the one or the mixed lithium salts, the anion of which is selected from the group consisting of SO 4 2" , NO 3 2" , PO 4 3" , CH 3 COO " , Cl “1 and OH " .
  • the supporting electrolyte salt consisting of the above anion and the other metal cation is preferred to add.
  • the metal cations can be selected from the group consisting of alkaline, alkaline earths, lanthanides, aluminum and zinc ions, such as KCl, K 2 SO 4 , and KNO 3 .
  • the concentration of the electrolyte solution is 0.1 M to 10 M.
  • Some porous materials can also be added to form the gel electrolyte. Such materials can be of porous SiO 2 , polyvedin (PVA), and polyvinylidene fluoride (PVDF).
  • the electrolyte with a pH value over 7 is preferred to assure the utilization of the positive electrode without the evolution of oxygen.
  • a simplified schematic hybrid cell of the present invention is given in Figure 1.
  • the assembled cell is at first charged. In the charge process, lithium-ion is extracted from the positive electrode into the electrolyte, and then adsorbed to the surface of negative electrode. The opposite electrode reaction occurs in the discharge process.
  • the charge/discharge process is associated with the transfer of Li-ion between two electrodes, which we defined as "hybrid aqueous lithium-ion cell".
  • the electrode reactions of the hybrid system described in the present invention are different from any hybrid electrochemical surpercapacitors or electrochemical double layer supercapacitors in which the salts in electrolyte will be consumed during the charge process, such as, AC/AC, AC/Ni(0H) 2 , Li 4 Ti 5 0 12 /AC system.
  • the ion concentration in the electrolyte will affect the energy density of the hybrid electrochemical surpercapacitors, especially for the organic electrolyte based hybrid system.
  • the negative electrode utilizes mainly a reversible non-faradic reaction of Li-ion sorption and de-sorption on the surface of the porous carbon. It is possible to control the charge/discharge potential only by adjusting simply the mass loading ratio of the positive to the negative so as to avoid the oxygen and hydrogen evolution. On other hand, the Li-ion adsorption/de-sorption shows excellent reversibility.
  • the hybrid cell described in the present invention shows a typical average working voltage of about 1.3 V, and exhibits excellent cycling ability.
  • the hybrid system of the present invention has provided a real green energy storage device with a long cycling life, an appreciate energy density, high power, low cost, low toxicity and high safety, especially for the electric vehicle (EV) application.
  • EV electric vehicle
  • the separator membrane used in the hybrid cell of the present invention can be the porous membrane used for the aqueous secondary batteries such as glass fiber membrane used for lead-acid battery, polyethylene membrane in nickel-hydrogen metal battery, and other type of inert electron-insulating, ion-transmissive medium capable of adsorbing electrolyte solution.
  • the case used for the hybrid cell of the present invention can be plastics, metal, or a composite material of metal and polymer.
  • the shape of the hybrid cell of the present invention can be the cylindrical, prismatic, and button type.
  • the technologies for the hybrid cell of the present invention integrates both the secondary battery including lithium-ion, nickel-metal hydrogen, and the lead-acid batteries, and the electrochemical supercapacitors. Therefore, all fabrication process can be also applied in the hybrid cell of the present invention.
  • Figure 1 is a diagrammatic representation of the hybrid cell structure of the present invention
  • Figure 2 is the graphical representation of the structure of a cylindrin hybrid cell
  • Figure 3 is a graphical representation of the charge/discharge characteristics of the hybrid cell of the present invention.
  • a representative embodiment of the present invention may be more particularly fabricated and employed as shown in the following example.
  • a commercial spinel LiMn 2 O 4 was used as positive electrode and a commercial activated carbon was used as negative electrode.
  • Composite electrodes were prepared by mixing the active material with acetylene black and PTFE at the following rate: 80/10/10 for LiMn 2 O 4 electrode and 85/10/5 for AC electrode. The mixtures thus prepared were cold rolled into films. Then the films were pressed onto a nickel grid (1.2 X 10 7 Pa) that served as a current collector to form composite electrodes. The composite electrodes were dried at 100 0 C for several hours.
  • the capacities of positive electrode material (LiMn 2 O 4 ) and negative electrode material (AC) are 80mAh/g and 40mAh/g respectively and the loads of electrodes are 5 mg/cm 2 for positive electrode and 10 mg/cm 2 for negative electrode. Both positive composite electrode and negative composite electrode have the same area.
  • a polyethylene membrane used for the commercial Ni-MH battery was used as a separator.
  • the positive composite electrode, negative composite electrode and the separator membrane were stacked together to form a sandwich structure (positive composite electrode/ separator membrane / negative composite electrode).
  • the sandwich structure including positive composite electrode/ separator membrane / negative composite electrode was rolled to form the 2# battery (14 mm in diameter, and 50 mm in length).
  • the typical structure of this hybrid battery was shown in Figure 2.
  • the charge-discharge curve of this hybrid aqueous cell was shown in Figure 3. As shown in Figure 3, the cut-off voltage of this hybrid cell was controlled between 0 ⁇ 1.8 V with an average work voltage of 1.3 V. The specific capacity of the this hybrid cell was 200 mAh at current density of 1 C and decreased to 190 mAh at current density of 10 C. After 10000 charge-discharge cycles, the retention of capacity of the hybrid cell is 90%.
  • a commercial spinel LiCoO 2 was used as positive electrode.
  • the else parts of this hybrid cell are same as in Example 1.
  • the preparation of composite electrode and fabrication of hybrid cell is same as the process mentioned in Example 1.
  • the capacities of positive electrode material (LiCoO 2 ) and negative electrode material (AC) are 100 mAh/g and 40 mAh/g respectively and the loads of electrodes are 3.4 mg/cm 2 for positive electrode and 10 mg/cm for negative electrode.
  • the cut-off voltage of this hybrid cell was controlled between 0 ⁇ 1.8 V with an average work voltage of 1.0 V.
  • the specific capacity of the this hybrid cell was 190 mAh at current density of 1 C and decreased to 185 mAh at current density of 10 C. After 10000 charge-discharge cycles, the retention of capacity of the hybrid cell is 91%.
  • a commercial spinel LiCo 1Z3 Ni 1Z3 Mn 1Z3 O 2 was used as positive electrode.
  • the else parts of this hybrid cell are same as in Example 1.
  • the preparation of composite electrode and fabrication of hybrid cell is same as the process mentioned in Example 1.
  • the capacities of positive electrode material (LiCo 1Z3 Ni 1Z3 Mn 1Z3 O 2 ) and negative electrode material (AC) are 100 mAh/g and 40 mAh/g respectively and the loads of electrodes are 4 mg/cm 2 for positive electrode and 10 mg/cm 2 for negative electrode.
  • the cut-off voltage of this hybrid cell was controlled between 0 ⁇ 1.8 V with an average work voltage of 1.0 V.
  • the specific capacity of the this hybrid cell was 230 mAh at current density of 1 C and decreased to 210 mAh at current density of 10 C. After 10000 charge-discharge cycles, the retention of capacity of the hybrid cell is 92%.
  • a commercial spinel LiMg 02 Mn 1 , 8 O 4 was used as positive electrode.
  • the else parts of this hybrid cell are same as in Example 1.
  • the preparation of composite electrode and fabrication of hybrid cell is same as the process mentioned in Example 1.
  • the capacities of positive electrode material (LiMg C2 Mn L8 O 4 ) and negative electrode material (AC) are 78 mAh/g and 40mAh/g respectively and the loads of and electrodes are 5.5 mg/cm 2 for positive electrode and 10 mg/cm 2 for negative electrode.
  • the cut-off voltage of this hybrid cell was controlled between 0 ⁇ 1.8 V with an average work voltage of 1.3 V.
  • the specific capacity of the this hybrid cell was 190 mAh at current density of 1 C and decreased to 185 mAh at current density of 10 C. After 10000 charge-discharge cycles, the retention of capacity of the hybrid cell is 91%.
  • a commercial spinel LiMn 2 O 4 was used as positive electrode.
  • a mixture of commercial AC and LiV 3 O 8 (the mass ration of AC/LiV 3 Os is 2/1) was used as negative electrode.
  • the else parts of this hybrid cell are same as in Example 1.
  • the preparation of composite electrode and fabrication of hybrid cell is same as the process mentioned in Example 1.
  • the capacities of positive electrode material (LiMn 2 O 4 ) and negative electrode material (AC/LiV 3 Os) are all 80 mAh/g and the loads of both electrodes are 10 mg/cm 2 .
  • the cut-off voltage of this hybrid cell was controlled between 0 ⁇ 1.8 V with an average work voltage of 1.2 V.
  • the specific capacity of the this hybrid cell was 300 mAh at current density of 2 C and decreased to 250 mAh at current density of 10 C. After 10000 charge-discharge cycles, the retention of capacity of the hybrid cell is 80%.
  • a commercial AC was used as positive electrode.
  • the else parts of this hybrid cell are same as in Example 1.
  • the preparation of composite electrode and fabrication of hybrid cell is same as the process mentioned in Example 1.
  • the capacities of positive electrode material and negative electrode material are all 40 mAh/g and the loads of both electrodes are lOmg/cm 2 .
  • the cut-off voltage of this hybrid cell was controlled between 0 - 1.0V with an average work voltage of 0.5 V.
  • the specific capacity of this hybrid cell was 100 mAh at current density of 1 C and kept at 100 mAh when the current density increases to 10 C. After 10000 charge-discharge cycles, the retention of capacity of the hybrid cell is 95%.

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Abstract

L'invention concerne un dispositif de stockage électrique aqueux hybride à supercondensateur/batterie, selon lequel un condensateur double couche est joint à un mécanisme intercalé pour former un système hybride. Les composés au lithium ionique intercalés sont utilisés en tant que matériau d'électrode positive. Du charbon actif, du carbone mésoporeux, du carbone, des nanotubes de carbone, etc. sont utilisés en tant que matériau d'électrode négative. Une solution aqueuse contenant du lithium ionique est utilisée en tant qu'électrolyte.
PCT/CN2006/000711 2005-04-21 2006-04-18 Dispositif de stockage d'energie aqueux hybride WO2006111079A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN200510025269.6 2005-04-21
CNB2005100252696A CN1328818C (zh) 2005-04-21 2005-04-21 混合型水系锂离子电池

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WO2006111079A1 true WO2006111079A1 (fr) 2006-10-26

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009040521A1 (fr) * 2007-09-25 2009-04-02 Anthony John Maxwell Système de stockage d'énergie dans lequel l'électrolyte comprend un drainage minier acide
WO2009126525A2 (fr) 2008-04-07 2009-10-15 Carnegie Mellon University Dispositif de stockage d'énergie secondaire électrochimique sous forme d'électrolyte aqueux basé sur des ions de sodium
EP2323146A1 (fr) * 2009-11-11 2011-05-18 Taiwan Textile Research Institute Électrolyte aqueux pour condensateur électrolytique à double couche et condensateur électrolytique à double couche doté de celui-ci
US8137830B2 (en) 2011-07-19 2012-03-20 Aquion Energy, Inc. High voltage battery composed of anode limited electrochemical cells
WO2012126499A1 (fr) * 2011-03-18 2012-09-27 Cnrs Condensateur électrochimique
US8298701B2 (en) 2011-03-09 2012-10-30 Aquion Energy Inc. Aqueous electrolyte energy storage device
WO2013012830A3 (fr) * 2011-07-19 2013-04-11 Aquion Energy Inc. Batterie haute tension composée de cellules électrochimiques limitées à l'anode
US8652672B2 (en) 2012-03-15 2014-02-18 Aquion Energy, Inc. Large format electrochemical energy storage device housing and module
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CN104362393A (zh) * 2014-10-10 2015-02-18 恩力能源科技（南通）有限公司 一种可充放水系离子电池
CN106532891A (zh) * 2017-01-11 2017-03-22 云南昆船智能装备有限公司 一种超级电容与蓄电池混合储能及供电充电方法
CN106532891B (zh) * 2017-01-11 2023-11-14 云南昆船智能装备有限公司 一种超级电容与蓄电池混合储能及供电充电方法
WO2018166667A1 (fr) 2017-03-14 2018-09-20 Robert Bosch Gmbh Supercondensateur hybride, procédé de fabrication d'un supercondensateur hybride et véhicule
DE102017204207A1 (de) 2017-03-14 2018-09-20 Robert Bosch Gmbh Hybrid-Superkondensator, Verfahren zur Herstellung eines Hybrid-Superkondensators und Fahrzeug

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