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WO1992017910A1 - Cathode en bioxyde de maganese pour piles alcalines rechargeables en bioxyde de manganese a caracteristiques de surcharge ameliorees - Google Patents

Cathode en bioxyde de maganese pour piles alcalines rechargeables en bioxyde de manganese a caracteristiques de surcharge ameliorees Download PDF

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Publication number
WO1992017910A1
WO1992017910A1 PCT/CA1992/000143 CA9200143W WO9217910A1 WO 1992017910 A1 WO1992017910 A1 WO 1992017910A1 CA 9200143 W CA9200143 W CA 9200143W WO 9217910 A1 WO9217910 A1 WO 9217910A1
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WO
WIPO (PCT)
Prior art keywords
manganese dioxide
nio
mass
catalysts
cathode
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.)
Ceased
Application number
PCT/CA1992/000143
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English (en)
Inventor
Karl Kordesch
Leo Binder
Erkal Kahraman
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.)
Battery Technologies Inc
Original Assignee
Battery Technologies Inc
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Filing date
Publication date
Application filed by Battery Technologies Inc filed Critical Battery Technologies Inc
Publication of WO1992017910A1 publication Critical patent/WO1992017910A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
    • 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
    • H01M10/34—Gastight accumulators
    • 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
    • H01M4/04—Processes of manufacture in general
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

Definitions

  • the present invention relates to a manganese dioxide cathode for rechargeable alkaline manganese dioxide cells with improved overcharge properties, more particularly to catalysts added to the conventional manganese dioxide cathode material which substantially improve the overcharge properties of the cell.
  • the oxygen overcharge principle is well know n from the nickel-cadmium batteries.
  • the imbalance of the electrode capacities is essential, in order to assure that the cathode reaches the fully charged state first. This is achieved by there being still CdO left in the anode when the nickel oxide is starting to evolve oxygen gas.
  • the oxygen then travels to the anode and recombines with the metallic cadmium.
  • nickel oxide -- hydrogen cells the liberated ox y g en reacts with the hy drogen gas in a catalytic reaction supported by the surface of the fuel cell type anode and forms water. Due to the fact that this is a closed cycle in a gas-tight sealed cell, the overall electrolyte concentration does not change and the only product of the overcharge reaction is heat.
  • the object of the invention is to provide a manganese dioxide cathode material which has improved overcharge properties, which enables the use of chargers with operational voltage above 1.75 V, in which the formation of manganates is effectively prevented during overcharge, whereby there will be a smaller decrease in capacity durin g cycle life, and in w hich the end of charge state can be monitored more easily.
  • the amount of said catalysts lies between 1 and 5 mass%.
  • nickel oxide in an amount of at most 5 mass% , preferably 1 to 3 mass%, in combination with either one of vanadium pentoxide ( 2O5) or nickel cobaltite (NiO.C ⁇ 2 ⁇ 3 ) is preferable, due to improved potential characteristics in the overcharge region.
  • the substantially improved overcharge properties of manganese dioxide cathodes that are achieved according to this invention can be utilized in all types of rechargeable cells using manganese dioxide as the cathode electrode. It must be understood, however, that in the overcharge mode, oxy gen gas is developed and the cell design should provide a reaction (recombination) for this oxygen gas. This constitutes no problems for a number of cell types, while in other cells specific measures should be introduced for this purpose.
  • the overcharge potential curves will be changed in such a way that a well-detectable voltage increase is obtained in the overcharge period which can be used to trigger an end of charge signal before irreversible cathode reactions could start.
  • This behavior enables the use of conventional or at least less precise charger circuits, since there will be no need to inhibit the increase of the charging voltage above 1.75 V.
  • Figure 1 shows the schematic arrangement of a test cell
  • Figure 2 shows the basic measuring arrangement
  • Figure 3 comprises oxygen evolution verses time diagrams for clifficult catalysts
  • Figure 4 shows potential curves for the catalysts of FIG. 3
  • FIG. 5 shows oxygen evolution curves: the catalyst is V2O5;
  • Figure 6 shows potential curves: the catalyst is 2O5;
  • Figure 7 shows oxygen evolution curves: the catalyst is NiO.Co 2 0 3 ;
  • Figure 9 shows oxygen evolution curves in a charge-discharge cycle: the catalyst is 5% NiO.C ⁇ Og, and current density is 10 mA/cm 2
  • Figure 10 is similar to Figure 9 but with a 7.5 mA/cm 2 current density; and Figure 11 shows potential curves compared to a zinc reference, for the tests of Figs. 9 and 10.
  • the required compounds were prepared by mixing aqueous solutions containing the nitrates of the oxide formin g metals in stoic hio etric ratio, evaporizing the water and heating the residue for at least 3 hours at a temperature of 850 ° C in the presence of air . T he p rod uct were tested b y X -ray inspection.
  • Man ganese dioxide electrodes were prepared be using the following materials: a) electrolytic manganese dioxide, Mitsui, IBA sample No. 18 b) graphite power, Lonza, KS 44, IC-sample No. 1 c) Hostaflon powder, Hoechst, PTFE 2071.
  • the basic mixture was 82 mass% of electrolytic manganese dioxide, 10 mass% of graphite, and 8 mass% of Hostaflon. After dry mixin g these co mponents, the p o w der obtained w as immersed in benzine (boiling range 80-110 ° C) and homogenized for 3-4 hours. Subsequently the excess benzine was separated be filtration and the solid residue was kneaded until the paste had a suitable consistency for the following rolling process . Rolling started with a sheet of about 4mm thickness and was continued step by step until a final thickness of 0.8 to 0.9 mm was achieved. In the last step the foil was rolled on a nickel screen used as a current collector. Finally, the product was dried at 40 ° C for 12 hours. Circular electrodes with a diameter of 50.2 mm were cut out, contacted with a nickel wire and used as working electrodes in the test cell.
  • cathode electrodes were made by adding 1 to 5 mass% amount of the above listed catalysts i) to iv) before the dry mixing step.
  • the test cell was made as illustrated in Fig. 1.
  • a pair of polymetacrylate plates 1, 2 were used which could be fitted by four bolts (not shown). Appropriate recesses were provided on the plates to give space to a circular electrode and to the electrolyte.
  • Plate 2 which received the working electrode 3 (i.e. the manganese dioxide cathode with the catalyst under test), was fitted with a tube system 4 for gas collection.
  • a separator sheet 5 was placed between the two plates 1, 2.
  • a counter electrode 6 made by a nickel screen and a reference electrode 7 formed by a zinc wire were placed in a spaced geometry, and the so obtained compartment was vented to let the produced hydrogen escape. On the other side, the evolved oxygen was collected and its volume was recorded.
  • the compartments were filled with 9 molar KOH, the plates were fitted together, and sealed in an airtight way.
  • the working and counter electrodes 3 and 6 were connected to a galvanostat 10 and a potential recorder 11 was coupled to the working and reference electrodes 6, 7 (Fig. 2).
  • the evolved oxygen volume was measured by meter 12.
  • the working electrodes were applied in 90 to 95 % charged con dition ( as the y w ere prod uced ) , an d this means that the overcharge reactions started nearly as soon as the cell was powered by the galvanostat.
  • the tests were performed with cathode samples from the various catalyst types and amounts; as well as with a conventional manganese dioxide cathode without and catalyst, as standard.
  • the first series of experiments was started to establish the properties of an undoped MnC_2 electrode comparing it with electrodes containing 5 mass% of doping oxide.
  • Fig. 3 shows, the amount of evolved oxygen is significantly different and clearly depending on the nature of the added oxide. The only exception is found in curve 3 (zinc -cobaltite ZnO.C ⁇ 2 ⁇ which is close to curve 1 (undoped Mn ⁇ 2), and shows no advantage of this additive.
  • the overcharge experiments were carried out by applying constant current densities between 3 mA/cm 2 . The straight line shows the theoretic oxygen gas volume.
  • # 7 corresponds to 5% iO.C ⁇ 2 ⁇
  • # 11 corresponds to 1% NiO.C ⁇ 2 ⁇ 3
  • Fig . 7 demonstrates that the extent of the oxygen evolution is nearly not determined by the amount of additive. 1% of nickel cobaltite gives the same result as 5% and it is possible that even contents below 1% will be active.
  • the potential versus time functions sho wn in Fig . 8 point out that there seems to be an optimum at a concentration of 3%, which was the least effective from the point of view of oxygen evolution.
  • # 7 shows a fully charged electrode, 5% iO.C ⁇ 2 0 doped
  • # 13 shows a 1 hour predischarged electrode, 5% NiO.C ⁇ 2 ⁇ 3 doped current density : 10 mA/c ⁇ r_2 Fig. 10:
  • # 12 shows a 2 hours predi ⁇ charged electrode, 5% NiO.C ⁇ 2 ⁇ 3 doped current density: 7.5 mA/cm 2
  • manganese dioxide without any catalyst shows a coulombic efficiency of only 75 to 85%.
  • the difference to 100% is given by the creation of manganese and permanganate which proportionate back to Mn ⁇ 2 and lower MnO-oxides.
  • the Mn0 2 is again able to discharge and to be charged .
  • the lo was oxides are not rechargeable, and constitute irreversible loss.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inert Electrodes (AREA)

Abstract

Cathode en bioxyde de manganèse pour piles alcalines rechargeables en bioxyde de manganèse présentant des caractéristiques améliorées de surcharge. Elle comporte, en plus des constituants traditionnels, au maximum 10 % en masse de catalyseur, ce qui rend st÷chiométriquement équivalent au courant de charge le dégagement d'oxygène pendant la surcharge et cela, sans qu'il ne se produise de réaction secondaire avec le manganate. Les catalyseurs appropriés (seuls ou combinés) font partie du groupe constitué de CoAl2O4 (= CoO.Al2O3), ZnCo2O4 (= ZnO.Co2O3), NiCo2O4 (= NiO.Co2O3), V2O5, NiO, Co3O4, NiO.2CoO.
PCT/CA1992/000143 1991-04-05 1992-04-03 Cathode en bioxyde de maganese pour piles alcalines rechargeables en bioxyde de manganese a caracteristiques de surcharge ameliorees Ceased WO1992017910A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
HU1120/91 1991-04-05
HU911120A HU211445B (en) 1991-04-05 1991-04-05 Manganese dioxide cathode with improved supercharge characteristics for rechargeable alcaline manganese dioxide cells

Publications (1)

Publication Number Publication Date
WO1992017910A1 true WO1992017910A1 (fr) 1992-10-15

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PCT/CA1992/000143 Ceased WO1992017910A1 (fr) 1991-04-05 1992-04-03 Cathode en bioxyde de maganese pour piles alcalines rechargeables en bioxyde de manganese a caracteristiques de surcharge ameliorees

Country Status (3)

Country Link
AU (1) AU1458592A (fr)
HU (1) HU211445B (fr)
WO (1) WO1992017910A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0747982A1 (fr) * 1995-06-07 1996-12-11 Eveready Battery Company Cathodes contenant des additifs pour cellules électrochimiques
WO1998015987A1 (fr) * 1996-10-10 1998-04-16 Merck Patent Gmbh Materiau d'electrode modifie et son utilisation
WO1998034289A1 (fr) * 1997-01-31 1998-08-06 Merck Patent Gmbh Nouvelles electrodes en dioxyde de manganese, leur procede de fabrication et leur utilisation
EP0815604A4 (fr) * 1995-02-13 1999-12-29 Duracell Inc Additifs destines a des piles electrochimiques primaires dotees de cathodes contenant du dioxide de manganese
WO2000079622A1 (fr) * 1999-06-23 2000-12-28 Eveready Battery Company, Inc. Additifs ameliorant les performances pour piles electrochimiques
WO2001082396A3 (fr) * 2000-04-26 2002-07-25 Gillette Co Cathode pour batterie a commande pneumatique
US6524750B1 (en) 2000-06-17 2003-02-25 Eveready Battery Company, Inc. Doped titanium oxide additives
US6749964B2 (en) 2000-03-31 2004-06-15 MERCK Patent Gesellschaft mit beschränkter Haftung Active positive-electrode material in electrochemical cells, and process for the production of these materials
US6756115B2 (en) 2000-11-30 2004-06-29 Em Industries, Inc. 3D structural siliceous color pigments
US6818347B1 (en) 2000-06-21 2004-11-16 University Of California Performance enhancing additives for electrochemical cells
CN109119635A (zh) * 2013-12-20 2019-01-01 苏州宝时得电动工具有限公司 电池

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989004070A1 (fr) * 1987-10-27 1989-05-05 Klaus Tomantschger Recombinaison catalytique d'oxygene emis dans des cellules galvaniques

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989004070A1 (fr) * 1987-10-27 1989-05-05 Klaus Tomantschger Recombinaison catalytique d'oxygene emis dans des cellules galvaniques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF POWER SOURCES. vol. 36, no. 1, October 1991, LAUSANNE CH pages 45 - 56; E. KARAMAN ET AL: 'Overcharge Protection of MnO2 Cathodes' *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0815604A4 (fr) * 1995-02-13 1999-12-29 Duracell Inc Additifs destines a des piles electrochimiques primaires dotees de cathodes contenant du dioxide de manganese
EP0747982A1 (fr) * 1995-06-07 1996-12-11 Eveready Battery Company Cathodes contenant des additifs pour cellules électrochimiques
US6348259B1 (en) 1996-10-10 2002-02-19 Merck Patent Gesellschaft Mit Modified electrode material and its use
WO1998015987A1 (fr) * 1996-10-10 1998-04-16 Merck Patent Gmbh Materiau d'electrode modifie et son utilisation
WO1998034289A1 (fr) * 1997-01-31 1998-08-06 Merck Patent Gmbh Nouvelles electrodes en dioxyde de manganese, leur procede de fabrication et leur utilisation
US6337160B1 (en) 1997-01-31 2002-01-08 Merck Patent Gesellschaft Mit Beschrankter Manganese dioxide electrodes, process for producing the same and their use
WO2000079622A1 (fr) * 1999-06-23 2000-12-28 Eveready Battery Company, Inc. Additifs ameliorant les performances pour piles electrochimiques
US6749964B2 (en) 2000-03-31 2004-06-15 MERCK Patent Gesellschaft mit beschränkter Haftung Active positive-electrode material in electrochemical cells, and process for the production of these materials
WO2001082396A3 (fr) * 2000-04-26 2002-07-25 Gillette Co Cathode pour batterie a commande pneumatique
US7238448B1 (en) 2000-04-26 2007-07-03 The Gillette Company Cathode for air assisted battery
US7615508B2 (en) 2000-04-26 2009-11-10 The Gillette Company Cathode for air assisted battery
US6524750B1 (en) 2000-06-17 2003-02-25 Eveready Battery Company, Inc. Doped titanium oxide additives
US6818347B1 (en) 2000-06-21 2004-11-16 University Of California Performance enhancing additives for electrochemical cells
US6756115B2 (en) 2000-11-30 2004-06-29 Em Industries, Inc. 3D structural siliceous color pigments
CN109119635A (zh) * 2013-12-20 2019-01-01 苏州宝时得电动工具有限公司 电池

Also Published As

Publication number Publication date
AU1458592A (en) 1992-11-02
HU211445B (en) 1995-11-28
HU911120D0 (en) 1991-10-28
HUT63660A (en) 1993-09-28

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