WO2010058574A1 - ファイバー電池用ニッケル正極 - Google Patents

ファイバー電池用ニッケル正極 Download PDF

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WO2010058574A1
WO2010058574A1 PCT/JP2009/006205 JP2009006205W WO2010058574A1 WO 2010058574 A1 WO2010058574 A1 WO 2010058574A1 JP 2009006205 W JP2009006205 W JP 2009006205W WO 2010058574 A1 WO2010058574 A1 WO 2010058574A1
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Prior art keywords
nickel
fiber
positive electrode
electrode
active material
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PCT/JP2009/006205
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English (en)
French (fr)
Japanese (ja)
Inventor
高▲さき▼智昭
境哲男
向井孝志
岩城勉
堤香津雄
西村和也
Original Assignee
独立行政法人産業技術総合研究所
川崎重工業株式会社
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Application filed by 独立行政法人産業技術総合研究所, 川崎重工業株式会社 filed Critical 独立行政法人産業技術総合研究所
Priority to EP09827355.0A priority Critical patent/EP2367223B1/en
Priority to CN2009801456150A priority patent/CN102217122A/zh
Priority to KR1020117014015A priority patent/KR101343777B1/ko
Priority to JP2010539146A priority patent/JP5408804B2/ja
Priority to US13/130,000 priority patent/US9620770B2/en
Publication of WO2010058574A1 publication Critical patent/WO2010058574A1/ja

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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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/32—Nickel oxide or hydroxide electrodes
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/26—Processes of manufacture
    • H01M4/28—Precipitating active material on the carrier
    • H01M4/29—Precipitating active material on the carrier by electrochemical methods
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/75—Wires, rods or strips
    • 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
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • 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 nickel positive electrode for a fiber battery provided with a fibrous current collector.
  • the nickel positive electrode of the present invention is intended for nickel positive electrodes for secondary batteries using an aqueous solution as an electrolyte, specifically nickel positive electrodes for nickel-hydrogen batteries and nickel-cadmium batteries, and the like.
  • the present invention can also be applied to a nickel positive electrode for a zinc battery.
  • These batteries are portable, stationary, and mobile power sources.
  • spare and mobile power sources that are used under conditions that do not fully charge and discharge are mainly targeted. Become.
  • a secondary battery using a general-purpose aqueous solution as an electrolyte is composed of a plate-like positive electrode, a separator, and a plate-like negative electrode.
  • an aqueous solution such as caustic potash or caustic soda containing lithium hydroxide is used as an electrolytic solution, and in the lead storage battery, dilute sulfuric acid is used to constitute the battery.
  • a square shape including a plate shape and a cylindrical shape including a coin shape are generally used.
  • positive electrodes and negative electrodes are alternately arranged via separators, and a positive electrode terminal and a negative electrode terminal are taken out collectively.
  • Many alkaline secondary batteries have a cylindrical shape, and an electrode group consisting of a positive electrode, a separator, and a negative electrode is wound and inserted into an electrolytic cell, and a lid and a can are insulated to form a positive electrode terminal and a negative electrode terminal, respectively.
  • Square alkaline secondary batteries are also popular.
  • alkaline secondary batteries such as nickel-cadmium batteries and nickel-hydrogen batteries that are widely used have a relatively thick thickness of about 0.65 to 0.8 mm for high capacity use.
  • electrodes for these alkaline secondary batteries sintered and foamed nickel-type electrodes are well known as positive electrodes, and active materials are included in current collectors having a two-dimensional structure such as punching metal as negative electrodes.
  • Paste-type electrodes that are applied with paste and pressed are mainly used.
  • the sintered type is a sintered body obtained by sintering carbonyl nickel on a punching metal or the like
  • the foamed nickel type is a resin after nickel plating is applied to the foamed resin. Is a porous body obtained by incineration removal. In addition, many porous bodies with irregularities formed by machining have been proposed, but have not reached the practical level.
  • a polyamide nonwoven fabric having a thickness of about 80 to 200 ⁇ m and a polyolefin-based nonwoven fabric subjected to hydrophilic treatment are mainly used.
  • paper, porous polyolefin plates and glass fiber cloth are used, and generally it is necessary to impregnate a large amount of sulfuric acid directly involved in the charge / discharge reaction. A thick porous body is also used.
  • the current collector is a fibrous material (carbon fiber) having an electroconductive surface coated with an active material.
  • a fiber battery is proposed (see Patent Document 1).
  • the first group of fiber electrodes is arranged in the first layer so as to be parallel to each other
  • the second group of fiber electrodes is arranged in the second layer so as to be parallel to each other
  • the second layer is arranged in the first layer.
  • a plurality of fiber anodes, a plurality of fiber cathodes, an electrolyte, a lateral sealing case that laterally surrounds the fiber anode, the fiber cathode, and the electrolyte, and end portions that seal both ends of the lateral sealing case A battery is proposed in which the end of the fiber anode extends from the end plate and the end of the fiber cathode extends from the end plate (see Patent Document 3). ). According to this battery, since a battery having a large electrode surface area is easily manufactured, it is described that the charge capacity per volume of the battery can be increased.
  • either one of the long negative electrode material or the positive electrode material formed by forming an electrode active material on the outer periphery of each electrode is used as a core material, and the other electrode is interposed on the outer periphery via a polymer solid electrolyte.
  • a cord-type battery in which electrode materials are provided coaxially and sealed as a whole by sealing them with an exterior material (see Patent Document 4).
  • the configuration of this battery is basically the same as that of a general-purpose Luclanche type dry battery. That is, in the dry battery, a positive electrode material is provided at the center, a negative electrode material is provided at the peripheral portion, and an electrolyte is provided between them.
  • Patent Document 5 discloses that for the purpose of obtaining a nickel electrode that has a small reaction resistance and positive-polarity polarization and does not lead to a decrease in capacity at an early stage and is sufficiently reliable at high temperatures and has a long life. Filling a porous metal substrate such as a nickel substrate with nickel hydroxide obtained by electrolytic deposition as part of the total amount of active material required, and adding the nickel hydroxide obtained by chemical impregnation method to the total amount of active material required A nickel electrode plate for a battery filled with a majority of is described.
  • JP 2003-317794 A JP-A-8-227726 JP-A-8-264203 Japanese Patent Laid-Open No. 2001-110445 JP-A-9-283136
  • the thickness of the nickel electrode is about 400 ⁇ m even if it is the smallest, and the diffusion of ions and electrons moving through the active material is rate-limiting. Output is difficult.
  • Patent Document 1 describes a fiber battery.
  • Patent Documents 2, 3, and 4 do not describe a nickel positive electrode for an alkaline secondary battery that is a subject of the present invention.
  • Patent Document 5 merely describes an active material filling method for a sintered nickel electrode.
  • the present invention has been made in view of such problems of the prior art, and an object of the present invention is to provide a nickel battery positive electrode for a fiber battery that enables high output and high capacity in addition to long life. There is.
  • the nickel positive electrode for a fiber battery of the present invention is obtained by charging a fiber electrode formed by forming a ⁇ -Ni (OH) 2 active material layer on the surface of a carbon fiber. It is characterized by forming an active material layer of ⁇ -NiOOH on the surface of carbon fiber.
  • the nickel positive electrode for a fiber battery of the present invention further changes the ⁇ -NiOOH in the vicinity of the carbon fiber to ⁇ -NiOOH by further charging the nickel positive electrode for the fiber battery, and the outside of the active material layer of the ⁇ -NiOOH. Is characterized by maintaining the structure of ⁇ -NiOOH.
  • the nickel positive electrode for fiber battery of the present invention is obtained by charging the entire carbon fiber obtained by charging a fiber electrode formed by forming an active material layer of ⁇ -Ni (OH) 2 on the surface of the carbon fiber. It is characterized by being changed to NiOOH.
  • the active material layer is preferably composed of a normal phase and an irregular phase, and the proportion of the irregular phase is preferably 25 to 50%.
  • the nickel positive electrode for a fiber battery of the present invention is coated with nickel on carbon fiber, then negatively polarized in a nickel nitrate bath using the nickel-coated carbon fiber as a cathode, and then deposited on the surface of the carbon fiber by the negative polarization. It is characterized by being obtained by immersing the deposited precipitate in an aqueous caustic solution.
  • the single fiber constituting the carbon fiber has a diameter of 5 to 100 ⁇ m.
  • the carbon fiber is preferably in a state where 1000 to 20000 single fibers are bundled.
  • the carbon fiber is in a state where 2 to 10 single fibers are twisted.
  • the thickness of the nickel coating layer is preferably 0.5 to 15 ⁇ m.
  • the nickel coating step includes electroless nickel plating and then electrolytic nickel plating.
  • the precipitate deposited on the surface of the nickel-coated carbon fiber by dipping in a caustic aqueous solution is composed of a crystalline nickel hydroxide layer.
  • the crystalline nickel hydroxide layer is preferably concentric and has a thickness of 0.5 to 30 ⁇ m.
  • the nickel nitrate bath contains a cobalt salt.
  • the nickel nitrate bath contains at least one divalent metal salt excluding nickel ions.
  • an aluminum salt or a manganese salt is contained in the nickel nitrate bath.
  • the nickel positive electrode for fiber batteries of the present invention can achieve high output and high capacity in addition to long life when used as a positive electrode of a secondary battery.
  • FIG. 1 is a schematic view showing a state in which nickel hydroxide is electrolytically deposited on a carbon fiber having a large curvature (small radius).
  • FIG. 2 is a schematic view showing a state in which nickel hydroxide is electrolytically deposited on a conventional flat substrate.
  • FIG. 3 is a scanning electron microscope (SEM) photograph (10,000 times) showing the carbon fiber surface.
  • FIG. 4 is a diagram showing a schematic configuration of the electrolytic deposition apparatus.
  • FIG. 5 is a diagram showing a schematic structure of a nickel positive electrode for a fiber battery according to the present invention.
  • FIG. 6 is a SEM photograph of nickel hydroxide electrolytically deposited at a current density of 5 mA / cm 2 , and FIG.
  • FIG. 6 (a) shows a case where the electrolytic deposition time is 15 minutes (2000 times)
  • FIG. 6 (b). Is the case where the electrolytic deposition time is 30 minutes (2000 times)
  • FIG. 6C is the case where the electrolytic deposition time is 60 minutes (5000 times).
  • FIG. 7 is an X-ray diffraction pattern showing that the electrolytically deposited nickel hydroxide is improved in crystallinity by immersion in a 60 ° C. aqueous sodium hydroxide solution.
  • FIG. 8 is a diagram showing that the discharge characteristics of electrolytically deposited nickel hydroxide are greatly improved by the immersion treatment in a 60 ° C. sodium hydroxide aqueous solution.
  • FIG. 9 shows the X-ray diffraction pattern of the electrolytic precipitate in the nickel nitrate aqueous solution
  • FIG. 9A shows the X-ray diffraction pattern after the alkaline aqueous solution immersion treatment
  • FIG. 9B shows 110%.
  • FIG.9 (c) is a figure which shows the X-ray-diffraction pattern after discharge.
  • the measurement conditions are CuK ⁇ ray and ⁇ (X-ray wavelength) is 1.54056 mm.
  • FIG. 10 shows the X-ray diffraction pattern and crystal structure analysis result of the electrolytic precipitate in the nickel nitrate aqueous solution
  • FIG. 10 shows the X-ray diffraction pattern and crystal structure analysis result of the electrolytic precipitate in the nickel nitrate aqueous solution
  • FIG. 10 shows the X-ray diffraction pattern and crystal structure analysis result of the electrolytic precipitate
  • FIG. 10A shows the X-ray diffraction pattern and crystal structure analysis result after the alkaline aqueous solution immersion treatment.
  • FIG. 10B is a diagram showing an X-ray diffraction pattern and a crystal structure analysis result after charging
  • FIG. 10C is a diagram showing an X-ray diffraction pattern and a crystal structure analysis result after discharging.
  • the measurement conditions are Spring-8, BL19B2, and ⁇ is 0.7 mm.
  • FIG. 11 is a schematic cross-sectional view showing a state in which ⁇ -Ni (OH) 2 coated in a cylindrical shape on carbon fiber changes in volume with charge and discharge.
  • FIG. 12 shows the X-ray diffraction pattern of the electrolytic deposit in the nickel nitrate aqueous solution added with aluminum nitrate
  • FIG. 12 (a) shows the X-ray diffraction pattern after the alkaline aqueous solution immersion treatment
  • FIG. 12B shows an X-ray diffraction pattern after charging
  • FIG. 12C shows an X-ray diffraction pattern after discharge.
  • the measurement conditions are CuK ⁇ ray and ⁇ is 1.54056 ⁇ .
  • FIG. 13 is a schematic cross-sectional view showing how ⁇ -Ni (OH) 2 coated in a cylindrical shape on carbon fiber changes in volume with charge / discharge in the electrode D obtained in Example 4 of the present invention. It is.
  • FIG. 13 is a schematic cross-sectional view showing how ⁇ -Ni (OH) 2 coated in a cylindrical shape on carbon fiber changes in volume with charge / discharge in the electrode D obtained in Example 4 of the present invention. It is.
  • FIG. 14 is a diagram showing a 1C discharge curve after charging 110% with 1C for Examples 1 to 4 (electrodes A to D) and a reference example (electrode E).
  • FIG. 15 is a diagram showing a discharge curve of 1C to 500C after charging 110% at 1C for Example 1 (electrode A).
  • FIG. 16 is a plot of utilization rates from 1C to 500C after 110% charge at 1C for Example 1 (electrode A) and Comparative example 3 (electrode C ′).
  • FIG. 17 is a diagram showing a 1C discharge curve of Example 1 (electrode A) after 110% charge at 1C to 500C.
  • FIG. 18 is a graph plotting the utilization rate in 1C discharge after charging 110% at 1C up to 2000 cycles for Example 1 (electrode A).
  • FIG. 19 is a diagram showing discharge curves from 1C to 200C after charging 110% at 1C for Example 3 (electrode C).
  • the diameter of carbon fibers (including graphite fibers) used in the present invention is not particularly limited, but when used as a current collector, the thickness of a general-purpose nickel positive electrode current collector is a standard. Specifically, the current collector of the sintered or foamed nickel positive electrode is 400 ⁇ m or more, and it is preferable that the current collector is considerably thinner in the present invention. From such a viewpoint, the diameter of the single fiber constituting the carbon fiber is preferably 5 to 100 ⁇ m, and more preferably 5 to 50 ⁇ m.
  • the diameter of the single fiber is small, such as less than 5 ⁇ m, its mechanical strength is insufficient, and the single fiber is cut due to tightening when being bundled with a crimp terminal or the weight of the active material that has precipitated. There is a risk that.
  • the diameter is small, the electrical conductivity is lowered, and it may be difficult to deposit the active material uniformly.
  • the diameter of the single fiber increases and exceeds 100 ⁇ m, the active material deposited on the single fiber is likely to be peeled off and dropped, and the charge / discharge cycle life may be reduced. This is related to the curvature of the carbon fiber side surface.
  • nickel hydroxide has a property that a crystal tends to grow in a spherical shape.
  • a plurality of spherical nickel hydroxide crystal nuclei are electrolytically deposited and connected to each other to grow into a cylindrical shape.
  • nickel hydroxide crystals 2 precipitated in the circumferential direction tend to be connected to form a cylindrical shape. Even if there is a volume change associated with the discharge, it is considered that peeling becomes difficult.
  • FIG. 1 shows that there is a volume change associated with the discharge, it is considered that peeling becomes difficult.
  • nickel hydroxide 3a deposited on the upper surface side of a conventional flat plate-like substrate 1b made of nickel or the like (when the curvature is very small) and deposited on the lower surface side of the flat substrate 1b.
  • the nickel hydroxide 3b is not connected to each other, and it is considered that peeling and dropping are likely to occur when there is a volume change associated with crystallization or charge / discharge of nickel hydroxide.
  • the active material electrolytically deposited on a smooth flat plate is not only charged and discharged, but also due to the volume change accompanying the crystallization of nickel hydroxide that occurs during the caustic immersion treatment. It will fall off completely.
  • a cylindrical active material is deposited on the surface of the single fiber by electrolytic deposition, and does not easily peel off even when swollen or contracted by charge / discharge, and has excellent contact. Showing gender. Thereby, charge / discharge of 2000 cycles or more is attained.
  • the carbon fiber used may be a single fiber or an aggregate of a plurality of single fibers is effective. In the case of assembling, it is preferable that 1000 to 20000 single fibers are bundled, more preferably 2000 to 6000 bundles.
  • One electrode is formed by fixing one end of the fiber bundle with a crimp terminal or the like.
  • Nitrate ions in the nickel nitrate bath near the current collector are reduced to ammonium ions by electrolysis, so that the pH shifts to the alkali side and nickel hydroxide is precipitated.
  • the phenomenon is used. Therefore, in a state where 1000 or more carbon fibers are bundled, nickel hydroxide can be uniformly deposited between the fibers that can suppress the movement of the solution, which is more preferable. When the number of fibers is less than 1000, the solution between the fibers diffuses too quickly, and the electrodeposition efficiency may be reduced.
  • the number of single fibers to be bundled is increased to 20000, the diameter of the cross section becomes about 10 mm. However, if this size is exceeded, the diffusion of the plating solution inside the fiber bundle is remarkably hindered. There is a tendency that the thickness of the object becomes non-uniform. In particular, a thick electrolytic deposit accumulates on the inner side of the fiber bundle capable of suppressing the movement of the solution, and a region that is not sufficiently collected tends to be generated, resulting in a decrease in utilization rate. For this reason, in order to deposit nickel hydroxide uniformly on each fiber, the number of fibers is preferably 1000 to 20000, more preferably 2000 to 6000.
  • electrolytic nickel plating As a method for coating nickel on the carbon fiber, electrolytic nickel plating, electroless nickel plating, a method of depositing nickel by thermal decomposition of nickel carbonyl, and the like can be applied, but each carbon fiber bundle of 1000 or more is applied to each fiber.
  • a method for uniformly coating nickel the most excellent method is to apply a thin nickel coating by electroless nickel plating and then perform electrolytic nickel plating.
  • Electroless nickel plating is a method in which nickel metal is deposited by a chemical reduction action, and since there is no need for energization, the conductivity is insufficient, and even in a bundle of carbon fibers having a complicated and intricate shape, it is uniform. A film having a film thickness can be formed. For this reason, if a thin nickel film is formed on a bundle of carbon fibers by electroless nickel plating before electrolytic nickel plating, it can be used as a base for forming a nickel plating layer having a more uniform thickness. . Furthermore, by improving the conductivity of the carbon fiber surface, the plating efficiency is improved when electrolytic nickel plating is applied, and high mass productivity can be realized.
  • Electroless nickel plating on carbon fiber uses the well-known nickel-phosphorus alloy plating (phosphorus content 5-12%) precipitation method using hypophosphite as a reducing agent and the reduction action of dimethylamine borane.
  • Nickel-boron alloy plating (boron content 0.2 to 3%) may be performed by the precipitation method. It is sufficient that the thickness of the electroless nickel plating layer is 0.1 to 0.5 ⁇ m. Then, the electroless nickel plating on the electroless nickel-plated carbon fiber may be performed by a well-known Watt bath.
  • the thickness of the plating layer including electroless nickel plating and electrolytic nickel plating is preferably 0.5 to 15 ⁇ m, and more preferably 1 to 8 ⁇ m.
  • the thickness of the nickel plating layer is less than 0.5 ⁇ m, sufficient conductivity may not be obtained. If the nickel plating layer has a thickness of 0.5 to 15 ⁇ m, sufficient conductivity can be obtained, and nickel plating reflecting fine irregularities on the surface of the carbon fiber as shown in FIG. 3 can be performed.
  • the electrolytic deposit enters the uneven portion, an effect of improving the adhesion of the active material is obtained by the anchor effect.
  • the nickel plating layer becomes thicker, the unevenness decreases, and when it exceeds 15 ⁇ m, the surface becomes almost smooth. In this case, the adhesion of the active material is lowered. Therefore, the thickness of the plating layer including electroless nickel plating and electrolytic nickel plating is preferably 0.5 to 15 ⁇ m.
  • the deposited nickel hydroxide has low adhesion and cannot be used as a current collector for an electrode of a fiber battery. Therefore, it is effective that the nickel plating is porous and exhibits an anchor effect and can maintain conductivity, and the surface of the carbon fiber having fine irregularities is electrolessly and then electrolyzed, preferably 0.5 to By forming a nickel plating layer of 15 ⁇ m, more preferably 1 to 8 ⁇ m, it is possible to form a current collector for an electrode of a fiber battery that exhibits an excellent function.
  • electrolysis is performed using carbon fiber as a cathode and a nickel plate as an anode, and a substance substantially corresponding to nickel hydroxide is electrolytically deposited on the surface of the carbon fiber (filling of active material).
  • FIG. 1 An electrolytic deposition apparatus that can be used in the active material filling step is shown in FIG.
  • a fibrous current collector was used as a cathode 5 and a nickel plate was used as an anode 6 in an aqueous nickel nitrate solution 4.
  • the concentration of the aqueous nickel nitrate solution used for electrolytic deposition is preferably 0.05 to 1.5 mol / liter, more preferably 0.3 to 1 mol / liter.
  • the current density during the electrolytic deposition is preferably from 0.1 ⁇ 30mA / cm 2, and more preferably 1 ⁇ 20mA / cm 2.
  • the thickness of the deposited active material is preferably 0.5 to 30 ⁇ m, and more preferably 5 to 15 ⁇ m.
  • the thickness of the active material is less than 0.5 ⁇ m, sufficient battery capacity may not be maintained.
  • the thickness of the active material exceeds 30 ⁇ m, the thickness of the active material layer becomes non-uniform, and the active material may easily fall off when the active material expands due to charge / discharge.
  • the conductive agent is dispersed in a plating bath, and the conductive agent is electro-deposited on the carbon fiber current collector, thereby conducting the active material.
  • the output characteristics can be further improved.
  • the binder is dispersed in the plating bath, and the binder is eutectoid plated on the carbon fiber current collector. Since it plays the role of improving, it is possible to further improve the output characteristics and cycle life of the generated active material. Therefore, by dispersing the conductive agent and binder in the plating bath and eutectically plating the conductive agent and binder on the carbon fiber current collector, the conductivity, output characteristics and cycle life of the generated active material are further improved. It is possible.
  • fluorine resin such as polytetrafluoroethylene (PTFE) is the most excellent.
  • PTFE polyvinyl alcohol
  • PE polyethylene
  • PP polypropylene
  • General-purpose materials can also be used.
  • PTFE has water repellency, in order to disperse
  • the surfactant is not particularly limited, and saponin, phospholipid, peptide, Triton (manufactured by Union Carbide) and the like can be used.
  • the addition amount of the surfactant is preferably about 0.01 to 3% by weight based on the weight of the nickel nitrate bath.
  • binders PTFE, PE, PP and the like excellent in alkali resistance and oxidation resistance are preferable, and PTFE, which is a fluororesin, exhibits the best cycle life characteristics.
  • PTFE which is a fluororesin
  • the range of usable resins such as polyvinyl alcohol (PVA) and rubber binders with excellent binder properties Spreads.
  • the content of the binder with respect to the weight of nickel nitrate in the nickel nitrate bath is preferably 0.5 to 20% by weight, and more preferably 1 to 10% by weight.
  • a binder is added, the effect of increasing the active material holding power can be obtained only by adding the binder.
  • the binder is too much, the resistance in the electrode of the positive electrode is increased and the high rate discharge characteristics are deteriorated.
  • the conductive agent examples include metal powder, carbon black (acetylene black (AB), ketjen black (KB), furnace black, etc.), a particulate carbon material, and a conductive polymer.
  • the metal powder should just be a metal which has alkali resistance and oxidation resistance, and powders, such as Ni, Au, and SUS, are preferable.
  • the metal powder since the metal powder has a large specific gravity, it is necessary to be careful to disperse it well. If the amount of the metal powder added is increased, the weight energy density of the obtained positive electrode is lowered.
  • the content of the metal powder with respect to the weight of nickel nitrate is preferably 1 to 5% by weight.
  • carbon black, particulate carbon materials, conductive polymers, etc. are preferable from the viewpoint of weight energy density because of their low specific gravity, but they are inferior in oxidation resistance and are not suitable for applications where overcharging is performed. That is, it is considered that the cause is that it is oxidized by the oxygen gas generated when the alkaline secondary battery is overcharged.
  • particulate carbon materials that have been treated at high temperature in a vacuum have special properties that cannot be distinguished from either carbonaceous carbonaceous materials or graphitic carbonaceous materials. It is known (see JP 2006-054084 A). Therefore, the particulate carbon material obtained in this manner is suitable as the conductive agent of the present application, and is preferable as the conductive agent because it is excellent in weight energy density and hardly oxidized by overcharge.
  • carbon black can be easily prepared by heat treatment.
  • the heat treatment temperature here is not generally stipulated by factors such as the type and properties of the particulate carbon material, but it is usually preferable to set the heat treatment temperature at 1800 to 2600 ° C. for 2 hours.
  • the heat treatment time at the temperature depends on the size of the container used during the heat treatment, but is preferably set to at least 2 hours, and more preferably set to 3 hours or more. When the heat treatment time is less than 2 hours, it is difficult to uniformly heat the inside, and a particulate carbon material exhibiting electrolytic durability may not be obtained.
  • the obtained particulate carbon material includes a carbonaceous carbon material having a degree of graphitization (G value) exceeding 0.8 and a graphitic carbon material having a degree of graphitization (G value) of less than 0.3. Show different specific oxidation resistance.
  • a preferred degree of graphitization (G value) is 0.4 to 0.7, which indicates a specific degree of graphitization.
  • the content of the conductive material relative to the weight of nickel nitrate in the nickel nitrate bath is preferably 0.1 to 40% by weight, more preferably 1 to 30% by weight, and even more preferably 3 to 20% by weight. If the content of the conductive agent is less than 0.1% by weight, the effect of adding the conductive agent cannot be expected significantly. When the content of the conductive agent exceeds 40% by weight, the active material layer tends to drop off, resulting in a decrease in the capacity of the fiber-like nickel positive electrode. Therefore, when the content of the conductive material with respect to the weight of nickel nitrate in the nickel nitrate bath is 0.1 to 40% by weight, a sufficient effect of improving the conductivity can be obtained, and the decrease in the capacity of the positive electrode can be minimized.
  • the nickel electrode active material discharge state
  • a cobalt compound that is effective in improving the utilization factor and life of the active material may be added.
  • a cobalt salt such as cobalt nitrate is preferably added in a molar ratio of 0.5 to 10%, more preferably 3 to 6% in a nickel nitrate bath, followed by electrolytic deposition. What is necessary is just to immerse in caustic aqueous solution.
  • cobalt compound on the surface of the active material layer, it is effective to deposit nickel hydroxide, immerse it in an aqueous cobalt salt solution, and then immerse it in an aqueous caustic solution. Further, when heated in air with caustic adhered, preferably at 80 to 120 ° C., more preferably 90 to 110 ° C., the cobalt hydroxide changes to cobalt oxyhydroxide, which increases the utilization rate of the positive electrode. An effect that does not decrease is obtained.
  • the active material on the nickel electrode may be substituted with a divalent element (for example, Zn, Mg, Ca, Sr) in order to extend the life of the charge / discharge cycle of the active material.
  • a divalent element for example, Zn, Mg, Ca, Sr
  • zinc nitrate, magnesium nitrate, calcium nitrate and strontium nitrate are added in a molar ratio, preferably 2 to 20%, more preferably 3 to 10%, in a nickel nitrate bath.
  • electrolytic deposition may be performed, and then immersed in an aqueous caustic solution.
  • Nickel in nickel hydroxide changes in valence from 2+ to 3+ by charging, and further changes to 4+ by further charging.
  • hydrogen present between layers of nickel hydroxide having a layered structure becomes ions and is released one after another into the electrolytic solution. Due to this, the bonding force between the layers gradually weakens, causing expansion in the stacking direction.
  • Replacing a part of the nickel site with the above-mentioned elements (for example, Zn, Mg, Ca, Sr) that do not change from divalent to trivalent during charging prevents hydrogen release and suppresses expansion of the active material in the stacking direction. As a result, peeling and dropping can be suppressed, and the life of the cycle characteristics can be extended.
  • an aluminum compound or a manganese compound that is effective for achieving a high capacity of the active material may be added in the present application.
  • an aluminum salt such as aluminum nitrate or a manganese salt such as manganese nitrate is preferably added in a molar ratio of 2 to 40%, more preferably 5 to 30% in a nickel nitrate bath.
  • the analysis can be performed and then immersed in an aqueous caustic solution.
  • the nickel positive electrode for a fiber battery of the present application has a long life and can have a high capacity.
  • the amount of nickel hydroxide deposited on the fiber-like current collector is determined by the current density and It can be easily controlled by changing the time.
  • the nickel positive electrode for a fiber battery thus formed becomes ⁇ -NiOOH when charged 100%, and ⁇ -NiOOH is formed when charged more.
  • the diameter of the fiber can be changed, high output is possible by reducing the diameter of the current collector and thinning the active material layer.
  • the deposition efficiency when electrolytically deposited on a sintered nickel substrate made of a porous metal using a nickel nitrate bath is 20% or less.
  • a fiber-shaped current collector is used. It has been clarified that the deposition efficiency when electrolytic deposition is performed on an aggregate of the body is improved to about twice or more of the former.
  • the sintering type it is electrolytically deposited in the pores of the porous body, but in the present application, it is the precipitation on the fiber and between the fibers.
  • the change of nickel nitrate to ammonia and the precipitation of nickel hydroxide It is presumed that this is due to the fact that the process proceeds more smoothly than the sintered type.
  • Example 1 As the graphite fiber constituting the current collector (graphite of a twisted yarn using two commercially available polyacrylonitrile fibers), one having an average diameter of 12 ⁇ m was used. The average diameter of each single fiber constituting this was 6 ⁇ m.
  • the graphite fiber was subjected to electroless nickel plating by a nickel-boron alloy plating (boron 1%) precipitation method using the reducing action of dimethylamine borane, followed by electrolytic nickel plating.
  • the electrolytic bath for nickel plating was a so-called Watt bath containing nickel sulfate 350 g / liter, nickel chloride 45 g / liter and boric acid 42 g / liter as main components.
  • 3000 graphite fibers having a length of 50 mm were fixed by sandwiching them between two foamed nickel pieces, and placed in a watt bath as a terminal.
  • a nickel plate having a thickness of 2 mm was used as a counter electrode.
  • Nickel plating was performed on the fiber surface so that the average thickness of the plating layer including electroless plating and electrolytic plating was 5 ⁇ m, and a fiber (fibrous) current collector was obtained.
  • the electroplating conditions were such that the current density was 20 mA / cm 2 and the energization time was 10 minutes.
  • the fibrous current collector was used as a cathode, a nickel plate was used as an anode, and a polypropylene non-woven fabric was placed between both electrodes as a separator to perform electrolytic deposition.
  • the electrodeposition conditions were a current density of 20 mA / cm 2 and an electrodeposition time of 6 minutes.
  • the average thickness of nickel hydroxide electrolytically deposited on the fibrous current collector is 12 ⁇ m, and nickel hydroxide is deposited to a thickness of approximately 15 ⁇ m between the single fibers constituting the fibrous current collector.
  • the electrodeposition efficiency of nickel hydroxide was about 45%.
  • the fibrous current collector on which nickel hydroxide was deposited was immersed in a 20 wt% aqueous sodium hydroxide solution at 60 ° C. for 1 hour. Subsequently, it washed with water and dried and obtained the nickel positive electrode for fiber batteries of this invention.
  • the packing density of the active material was 620 mAh / cc including the current collector. This is referred to as an electrode A.
  • FIG. 5 shows a schematic structure of the nickel positive electrode for a fiber battery manufactured as described above.
  • 7 is carbon fiber
  • 8 is metallic nickel
  • 9 is nickel hydroxide.
  • the entire thickness of the electrode including the active material layer can be reduced to 7 ⁇ m. By reducing the thickness, excellent high output characteristics can be obtained.
  • the active material layer may be thickened.
  • Example 1 SEM photographs of nickel hydroxide electrolytically deposited on a fibrous current collector at a current density of 5 mA / cm 2 in electrolytic deposition using a nickel nitrate bath are shown in FIGS. Shown in (c).
  • the electrodeposition times are 15 minutes and 30 minutes, respectively, and the nickel hydroxide coating is insufficient and the electrodeposition time is 60 minutes.
  • the fibrous current collector could be uniformly coated with nickel hydroxide so as to cover the entire fibrous current collector.
  • FIGS. 6A and 6B it can be seen that the nickel hydroxide crystals are connected and grow into a cylindrical shape as described above.
  • Nickel hydroxide produced by electrolytic deposition (in Example 1 above, nickel hydroxide deposited on the fibrous current collector before being immersed in a 60 ° C. sodium hydroxide aqueous solution) is composed of nickel nitrate and ammine complex. As shown in FIG. 7A, the specific diffraction peak was broad. Even if charging / discharging is performed in this state, the utilization rate remains at about 30% as shown in FIG. As a result of examining various treatment methods, such as heat treatment and pH adjustment of the electrolytic deposition bath, in order to sufficiently function the electrolytic deposit as a positive electrode active material, immersion treatment in a high-temperature caustic aqueous solution is the most effective. It turned out. Therefore, in the electrode A obtained as described above, as shown in FIG. 7B, the electrolytic precipitate is transferred to crystalline nickel hydroxide, and as shown in FIG. 8B. 100% utilization in a one-electron reaction was achieved.
  • the half width of the X-ray diffraction peak is 5 ° or less in terms of diffraction angle.
  • impurities such as nitrate radicals that disturb the atomic arrangement of the crystal.
  • the function of nickel hydroxide as an active material is hindered, and the utilization rate is greatly reduced.
  • the diffraction angle is 5 ° or less, it is considered that impurities that disturb the atomic arrangement and impede the function as the active material are almost removed, and the utilization rate in the one-electron reaction of the positive electrode is close to 100%. A value can be obtained.
  • sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. can be used, and mixed aqueous solutions of these can also be used, but crystalline nickel hydroxide can be obtained in a short time. Therefore, sodium hydroxide is particularly preferable.
  • the concentration of the caustic in the aqueous solution is not particularly limited from a very small amount to a saturated amount, but a concentration of 10 to 30% by weight is preferable.
  • the immersion temperature and immersion time are not limited, but the immersion time is preferably 40 to 110 ° C. and the immersion time is 10 minutes to 24 hours, and the immersion time is preferably 60 to 80 ° C. and 1 to 5 hours.
  • nitrate radicals are known to cause self-discharge, they are very effective in suppressing self-discharge because nitrate radicals are removed by immersion in a caustic aqueous solution. This is a particularly important process for applications where self-discharge is a problem, such as intermittent discharge.
  • a nickel coating layer is first formed on carbon fibers, and then nickel hydroxide is electrolytically deposited uniformly on the surface of each fiber in a nickel nitrate bath. Thereafter, by immersing in a caustic aqueous solution to form a highly crystalline nickel hydroxide layer, a nickel battery positive electrode for a fiber battery exhibiting a long life and excellent high output characteristics can be produced.
  • the line diffraction pattern is shown in FIG. 9 and 10 are X-ray diffraction patterns of fibrous nickel hydroxide obtained by electrolytic deposition, and a ⁇ -type structure ( ⁇ -Ni (OH) 2 ) was formed.
  • the active material layer shrinks by changing from ⁇ -Ni (OH) 2 to ⁇ -NiOOH with charge, and the carbon fiber 10 (shown by a black circle) ) Will not drop off.
  • the charge exceeds one electron reaction
  • ⁇ -NiOOH is formed immediately outside the carbon fiber 10 as shown in FIG. This reaction is conversely accompanied by a volume expansion of 30-40%.
  • the nickel positive electrode of the present invention has a long life and can have a charge / discharge cycle life of 2000 times or more. The reason is that the cylindrical ⁇ -NiOOH layer formed on the outer peripheral portion of the active material layer exhibits the action of preventing the ⁇ -NiOOH layer on the inner side from falling off.
  • the X-ray diffraction pattern was analyzed for the crystal structure by the Rietveld method.
  • the normal phase (Ideal Phase) was obtained for the electrode A of Example 1 that had been subjected to alkali immersion treatment after electrolytic deposition.
  • ⁇ -Ni (OH) 2 was 65% by weight, but it was found that 35% by weight of ⁇ -Ni (OH) 2, which is a fault phase, was contained.
  • the normal phase refers to generally well-known general nickel hydroxide
  • the irregular phase refers to (2/3, 1/3) from (0, 0, 0) where the nickel atom site is in the normal phase. , 0) Nickel hydroxide having a structure shifted to 0).
  • the proportion of the irregular phase is preferably 25 to 50%.
  • the irregular phase is less than 25%, the active material layer is more likely to be distorted than when it is 25% or more. For this reason, the active material layer easily peels off and drops with expansion / contraction during charge / discharge, and the cycle life is shortened.
  • the ratio of the normal phase is large, as will be described later, it is easy to change from ⁇ -NiOOH to ⁇ -NiOOH when charged more than one-electron reaction, but ⁇ -NiOOH is changed to ⁇ - The rate of returning to Ni (OH) 2 also increases, and the rate of stable presence as ⁇ -Ni (OH) 2 in the discharged state decreases.
  • the lattice constant in the ⁇ -phase stacking direction was about 10% larger than that of a normal powdery material. This is considered to be because the ⁇ -NiOOH layer on the outer peripheral portion also expanded in accordance with the volume expansion of the inner ⁇ -NiOOH.
  • the ⁇ -NiOOH layer has a function of flexibly expanding and contracting in accordance with the change in the inner volume and preventing the active material from falling off.
  • the entire active material layer forms ⁇ -NiOOH.
  • it may be used at a charge amount of 100% or less for applications such as a standby power supply for power failure that does not require a high capacity.
  • the lifetime is particularly long. Therefore, it is optimal for applications that have a long life and do not require a very high capacity.
  • the proportion of ⁇ -Ni (OH) 2 in the discharged state is about 10% by weight.
  • the atomic arrangement of ⁇ -Ni (OH) 2 is equal to ⁇ -NiOOH, and the difference between them is only the lattice constant value. In other words, this is because a part of ⁇ -NiOOH formed by charging is discharged while maintaining its atomic arrangement, and does not return to ⁇ -Ni (OH) 2 after discharge, but changes to ⁇ -Ni (OH) 2 . This is because it has metastasized.
  • the weight percentage of the normal phase in ⁇ -NiOOH is larger than the weight percentage of the irregular phase, and the normal phase tends to change from ⁇ -NiOOH to ⁇ -NiOOH by 1.5 electron reaction. I can find it.
  • ⁇ -Ni (OH) 2 after discharge consisted only of an irregular phase.
  • the weight percent of ⁇ -NiOOH in the irregular phase observed in Table 2 is approximately equal to the weight percent of ⁇ -Ni (OH) 2 observed in Table 3. From these, the irregular phase tends to be less likely to change from ⁇ -NiOOH to ⁇ -NiOOH than the normal phase, but once changed to ⁇ -NiOOH, ⁇ -Ni (OH) 2 passes through ⁇ -NiOOH. It was found that the structure of ⁇ -Ni (OH) 2 was retained.
  • ⁇ -Ni (OH) 2 As described above, a part of ⁇ -Ni (OH) 2 is stably present, so that ⁇ -NiOOH is easily formed upon recharging. As a result, a high voltage exceeding 1.3 V and a discharge exceeding 100% are possible.
  • the proportion of the irregular phase contained in the ⁇ phase does not change even after repeated charge and discharge, which suggests that the cylindrical active material layer is retained.
  • the lattice volume was about 5 to 10% smaller than that of a normal powder sample, and an ⁇ -Ni (OH) 2 layer having a higher density than that of the conventional powder sample was formed.
  • the nickel hydroxide electrolytically deposited in a cylindrical shape is a different material in which the proportion of the irregular phase and the volume of the crystal lattice are different from those of conventional powdered nickel hydroxide. It was also found that a long cycle life can be maintained by a unique charge / discharge mechanism that reflects the shape of the cylinder, such as the ⁇ -phase and ⁇ -phase forming a two-layer structure.
  • Example 2 In order to investigate the effect of adding aluminum hydroxide to nickel hydroxide, 5000 g of water was added to 1600 g of nickel nitrate (hexahydrate) and 420 g of aluminum nitrate (9 hydrate), and the pH was adjusted to 5 for electrolytic deposition. A solution was obtained.
  • a nickel-plated fibrous current collector obtained in the same manner as in Example 1 was used as a cathode, a nickel plate as an anode, and a polypropylene non-woven fabric as a separator was disposed between both electrodes to perform electrolytic deposition.
  • the electrodeposition conditions were a current density of 20 mA / cm 2 and an electrodeposition time of 10 minutes.
  • nickel hydroxide and aluminum hydroxide were electrodeposited, and the electrodeposition efficiency was about 42%.
  • the content of aluminum hydroxide was 22 mol% in terms of metal (that is, as aluminum with respect to nickel).
  • the average thickness of the mixed layer of nickel hydroxide and aluminum hydroxide electrolytically deposited on the fibrous current collector is 21 ⁇ m, and the thickness is also between the single fibers constituting the fibrous current collector.
  • the mixed layer was deposited to about 11 ⁇ m.
  • the fibrous current collector on which the mixed layer was deposited was immersed in a 20 wt% aqueous sodium hydroxide solution at 60 ° C. for 1 hour. Subsequently, it washed with water and dried and obtained the nickel positive electrode for fiber batteries of this invention.
  • the active material packing density including the current collector was about 600 mAh / cc. This is referred to as an electrode B.
  • nickel hydroxide having an ⁇ -type structure is formed. It changes only to ⁇ -NiOOH by charging, and returns to only ⁇ -Ni (OH) 2 after discharging.
  • ⁇ -Ni (OH) 2 becomes only ⁇ -NiOOH by this charging, as shown in FIG. 13, the active material phase contracts 30% toward the center of the carbon fiber 10 due to the volume contraction of the active material phase. It became clear that the adhesion between the substance and the current collector was improved. In this case, even if volume expansion occurs in the discharge process, the volume only returns to the initial state, so that it is considered that the separation and dropping of the active material layer from the current collector can be suppressed. Therefore, even in this case, a cycle life of 2000 times or more is possible.
  • ⁇ -NiOOH produced mainly by charging exceeding one electron reaction is capable of 1.5 to 2 electron reaction, and the capacity density calculated by changing nickel hydroxide to ⁇ -NiOOH is 289 mAh / g. Is also improved by 120 to 150%.
  • Example 3 In order to investigate the effect of adding a conductive agent and a binder to nickel hydroxide, add 5000 g of water to 2000 g of nickel nitrate (hexahydrate), 85 g of particulate carbon material and 21 g of PVA, and adjust the pH to 5 for electrolytic deposition. A solution was obtained.
  • a nickel-plated fibrous current collector obtained in the same manner as in Example 1 was used as a cathode, a nickel plate as an anode, and a polypropylene non-woven fabric as a separator was disposed between both electrodes to perform electrolytic deposition.
  • the electrodeposition conditions were a current density of 20 mA / cm 2 and an electrodeposition time of 10 minutes.
  • the particulate carbon material and PVA were deposited, and the electrodeposition efficiency was about 39%.
  • the content of the particulate carbon material was 20% by weight.
  • the average thickness of the mixed layer of nickel hydroxide, particulate carbon material, and PVA electrolytically deposited on the fibrous current collector is 13 ⁇ m, and even between the single fibers constituting the fibrous current collector, The mixed layer was deposited to a thickness of about 15 ⁇ m.
  • the fibrous current collector on which the mixed layer was deposited was immersed in a 20 wt% aqueous sodium hydroxide solution at 60 ° C. for 1 hour. Subsequently, it washed with water and dried and obtained the nickel positive electrode for fiber batteries of this invention.
  • the active material packing density including the current collector was about 500 mAh / cc. This is referred to as an electrode C.
  • Example 4 To investigate the effect of adding cobalt hydroxide to nickel hydroxide, add 5000 g of water to 2000 g of nickel nitrate (hexahydrate) and 120 g of cobalt nitrate (hexahydrate), and adjust the pH to 5 for electrolytic deposition. A solution was obtained. To this solution, a nickel-plated fibrous current collector obtained in the same manner as in Example 1 was used as a cathode, a nickel plate as an anode, and a polypropylene non-woven fabric as a separator was disposed between both electrodes to perform electrolytic deposition. . The electrodeposition conditions were a current density of 20 mA / cm 2 and an electrodeposition time of 10 minutes.
  • nickel hydroxide and cobalt hydroxide were electrodeposited, and the electrodeposition efficiency was about 42%.
  • the content of cobalt hydroxide was 5.3 mol% in terms of metal (that is, as cobalt with respect to nickel).
  • the average thickness of the mixed layer of nickel hydroxide and cobalt hydroxide electrolytically deposited on the fibrous current collector is 13 ⁇ m, and the thickness is also between the single fibers constituting the fibrous current collector.
  • the mixed layer was deposited to about 15 ⁇ m.
  • the fibrous current collector on which the mixed layer was deposited was immersed in a 20 wt% aqueous sodium hydroxide solution at 60 ° C. for 1 hour. Subsequently, it washed with water and dried and obtained the nickel positive electrode for fiber batteries of this invention.
  • the active material packing density including the current collector was about 600 mAh / cc. This is referred to as an electrode D.
  • the effect of coating the surface of nickel hydroxide with cobalt hydroxide was examined. That is, 5000 g of water was added to 2100 g of nickel nitrate (hexahydrate) and adjusted to pH 5 to obtain a solution for electrolytic deposition.
  • a nickel-plated fibrous current collector obtained in the same manner as in Example 1 was used as a cathode, a nickel plate as an anode, and a polypropylene non-woven fabric as a separator was disposed between both electrodes to perform electrolytic deposition.
  • the electrodeposition conditions were a current density of 20 mA / cm 2 and an electrodeposition time of 8 minutes. In this case, the electrodeposition efficiency of nickel hydroxide was about 45%.
  • the average thickness of nickel hydroxide electrolytically deposited on the fibrous current collector is 12 ⁇ m, and nickel hydroxide is deposited to a thickness of approximately 15 ⁇ m between the single fibers constituting the fibrous current collector.
  • a nickel positive electrode for a fiber battery equivalent to that in Example 1 was produced. Subsequently, the surface cobalt compound formation process was performed. That is, the nickel positive electrode for a fiber battery was immersed in an aqueous solution obtained by dissolving 500 g of cobalt nitrate (7 hydrate) in 3000 g of water, and then dried at 80 ° C. for 20 minutes. Subsequently, after being immersed in a 20% by weight sodium hydroxide aqueous solution, oxidation treatment was performed for 1 hour in a thermostatic chamber at 105 ° C. to obtain a nickel positive electrode for a fiber battery of the present invention.
  • the active material packing density including the current collector was about 590 mAh / cc.
  • Comparative Examples 1 to 3 a commercially available foamed nickel with a porosity of 95% was used as a current collector, and after adjusting the thickness to 600 ⁇ m, nickel hydroxide was slurried using carboxymethyl cellulose as a thickener. Using the foamed nickel current collector, 620 mAh / cc was filled so as to have the same packing density as that of the electrode A of Example 1, and the pressure was increased to 400 ⁇ m with a roller press, and the electrode A ′ (nickel electrode). (Comparative Example 1).
  • the current collector was filled with 600 mAh / cc so as to have the same packing density as the electrode D of Example 4, and pressed to 400 ⁇ m with a roller press to obtain an electrode B ′ (nickel electrode) (Comparative Example 2).
  • the foamed nickel current collector Filled with 590 mAh / cc so as to have the same packing density as the electrode E of the reference example, further coated with cobalt hydroxide under the same conditions as those of the electrode E of the reference example, and pressurized to 400 ⁇ m with a roller press machine, the electrode C ′ (Nickel electrode) was obtained (Comparative Example 3).
  • a cell for characteristic test evaluation was constructed by placing a hydrophilic nonwoven fabric with a thickness of 150 ⁇ m and a porosity of 50% as a separator between both electrodes.
  • As an electrolytic solution a solution in which 1.5% by weight of lithium hydroxide was dissolved in 30% by weight of potassium hydroxide aqueous solution was used.
  • the present invention aims at high output in addition to the lifetime, the high rate discharge characteristics of each battery were measured at an ambient temperature of 30 ° C. The results are shown in FIGS. 14 to 16 and Table 4.
  • the charge amount was 110%, and the final discharge voltage was 0.8V.
  • charging is controlled by the ⁇ V method or the ⁇ T method, and the charging is completed at 100% of one electron reaction. It was found that the battery of the present application can also control charging by such a method, but the battery is charged more than 100%, for example, 110% as described above to obtain high capacity and high output.
  • the amount of charge is 110% this time, by charging to 120 to 160%, more ⁇ -NiOOH phases are formed, and it is possible to further increase the capacity. This is because the structural advantage of the fiber electrode that the ⁇ -NiOOH phase is formed inside the active material layer and the ⁇ -NiOOH phase exists outside is utilized.
  • FIG. 14 shows an example of discharge curves of Examples 1 to 4 (electrodes A to D) and a reference example (electrode).
  • the charge and discharge rates were each 1C, and the battery was charged to 110% of the discharge capacity.
  • a two-stage discharge curve consisting of a flat portion of 1.3 V and 1.15 V was observed.
  • the discharge curves of the electrode D of Example 4 and the electrode E of the reference example show one-stage discharge curves of about 1.18V and about 1.15V, respectively.
  • the electrode B of Example 2 and the electrode C of Example 3 show a discharge curve with good flatness in one stage of 1.3V.
  • Electrodes A to C The high output characteristics of 1.3 V observed in Examples 1 to 3 (electrodes A to C) are proportional to the generation rate of the ⁇ -NiOOH phase generated with charging.
  • electrode D of Example 4 and the reference electrode E ⁇ -NiOOH was mainly generated by charging, and thus a discharge voltage of 1.3 V was hardly observed.
  • the average discharge voltage of the nickel positive electrode (electrodes A to D) of the example is higher than that of the comparative example (electrodes A ′ to C ′). It turned out that the one shows the outstanding high output characteristic.
  • the capacity can be increased by a 1.5 to 2 electron reaction, and a discharge of 100% or more can be achieved. Is possible. Actually, the discharge amount after 115% charge was 110%, and the discharge amount after 130% charge was 120%. Also in the electrode A of Example 1, since the ⁇ phase is partially stable, discharge exceeding 100% is possible. In fact, in FIG. 14, it can be confirmed that 108% is discharged after 110% charging.
  • the utilization rate decreased to 80% for electrode A 'at 850 cycles, electrode B' at 950 cycles, and electrode C 'at 1010 cycles. From this, it was found that the electrode of the present invention has a long life. The reason for this is that the nickel electrode of the present invention has an active material layer formed in a cylindrical shape around the fibrous current collector. Even when the material repeatedly expands and contracts during charge and discharge, the contact between the current collector and the active material is remarkably excellent.
  • the discharge voltage of the electrode D and the electrode E is slightly lower than those of the electrode A and the electrode B, it can be expected that the cycle life is improved.
  • This is related to the fact that the conductivity of the active material is improved by the addition of cobalt and the whole is uniformly charged, so that the generation of locally overcharged regions is suppressed.
  • it is possible to prevent the generation of ⁇ -NiOOH accompanied by a large volume expansion of the active material layer, so that the cycle life is considered to be particularly long.
  • FIG. 15 and FIG. 16 the measurement results of the high rate discharge characteristics of 1C to 500C for the electrode A are shown in FIG. 15 and FIG. 16, and the measurement results of the high rate discharge characteristics of 1C to 10C for the electrode C ′ are shown in FIG.
  • the numerical values in FIG. 15 indicate the discharge rate.
  • the charge rate was 1 C, and the battery was charged to 110% of the battery capacity (one electron reaction was assumed to be 100%).
  • the final voltage was 0.8V.
  • a high discharge voltage of 1.3 V was maintained even with 10 C discharge.
  • the discharge voltage gradually decreases, but even at 100 C, a relatively high voltage of 1.2 V, which is equivalent to the conventional plate electrode, is maintained.
  • the discharge capacity of the electrode A decreases as the discharge rate increases, but 50% of the total capacity can be discharged even at 100C.
  • the electrode C ′ shown in Comparative Example 3 achieves 1000 cycles although it does not reach the electrode A in terms of cycle life. However, in the high output characteristics of the electrode C ', the discharge rate is remarkably reduced to 10% or less at 10C. From this, it can be seen that the fiber-like nickel positive electrode can improve not only the cycle life but also the high output characteristics as compared with the conventional plate electrode.
  • the fiber-like positive electrode A exhibits excellent rapid charge characteristics. This was an experiment using the electrode A, and the charge amount was assumed to be 110% of the battery capacity. After charging at each charge rate of 1 C to 500 C, the discharge characteristics of 1 C were measured to obtain a final voltage of 0.8V. From FIG. 17, it can be seen that 100% discharge is possible at 1C even when rapid charging is performed at 500C. This charging characteristic can be said to be a region of a high-capacity capacitor. Therefore, it can be said that the present invention is suitable for a capacitor as well as for an alkaline secondary battery.
  • FIG. 19 shows the measurement results of the high rate discharge characteristics of 1C to 200C for the electrode C of Example 3.
  • the charge rate was 1 C, and the battery was charged to 110% of the discharge capacity.
  • the final voltage was 0.8V.
  • a high discharge voltage of 1.3 V was maintained even with 10 C discharge.
  • the electrode C of Example 3 has a two-stage plateau in the discharge curve of 30C to 100C, and the first plateau has a high discharge voltage of 1.3 to 1.2V. It was found that In particular, a discharge voltage of 1.2 V can be maintained at 100 C and 60% of the total capacity can be discharged, and a discharge voltage of 1.1 V can be maintained even at 200 C and 50% of the total capacity can be discharged.
  • the nickel positive electrode for fiber battery of the present invention has particularly remarkable effects with respect to output characteristics and cycle life characteristics. That is, the positive electrode characteristic has an extremely excellent effect that cannot be predicted even by those skilled in the art based on the content disclosed in the prior art.
  • the nickel positive electrode for a fiber battery of the present invention described in detail above is in the form of a fiber, and the alkaline secondary battery using this fiber-like nickel positive electrode is used for portable, mobile, spare, etc.
  • the alkaline secondary battery using this fiber-like nickel positive electrode is used for portable, mobile, spare, etc.
  • it is excellent as a power source that requires high output and high capacity in addition to long life.
  • it is possible to design a battery capable of rapid charging, for example, 500 C, which cannot be considered with a general-purpose secondary battery, and the industrial effect is extremely large, such as being able to be a high-capacity capacitor.

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PCT/JP2009/006205 2008-11-19 2009-11-18 ファイバー電池用ニッケル正極 WO2010058574A1 (ja)

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011007548A1 (ja) * 2009-07-14 2011-01-20 川崎重工業株式会社 ファイバー電極を備える蓄電デバイス及びその製造方法
WO2011007549A1 (ja) * 2009-07-14 2011-01-20 川崎重工業株式会社 ファイバー電極及びファイバー電池、並びにその製造方法、ファイバー電極及びファイバー電池の製造設備
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JP2011249216A (ja) * 2010-05-28 2011-12-08 Fdk Energy Co Ltd リチウム電池
JP2012099275A (ja) * 2010-10-29 2012-05-24 National Institute Of Advanced Industrial & Technology アルカリ蓄電池正極用粉末およびその製造方法
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JP2013089465A (ja) * 2011-10-18 2013-05-13 Kawasaki Heavy Ind Ltd 一次電池用ファイバー状電極およびそれを用いた一次電池
US10775644B2 (en) 2012-01-26 2020-09-15 Johnson & Johnson Vision Care, Inc. Ophthalmic lens assembly having an integrated antenna structure
JP2013206623A (ja) * 2012-03-27 2013-10-07 Kawasaki Heavy Ind Ltd ファイバー電極及びファイバー電極を有するファイバー電池
JP2015502011A (ja) * 2012-08-30 2015-01-19 エルジー・ケム・リミテッド ケーブル型二次電池用パッケージ、及びそれを含むケーブル型二次電池
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JP2015144057A (ja) * 2014-01-31 2015-08-06 川崎重工業株式会社 アルカリ二次電池用正極及びその製造方法、アルカリ二次電池及びその製造方法
US10361405B2 (en) 2014-08-21 2019-07-23 Johnson & Johnson Vision Care, Inc. Biomedical energization elements with polymer electrolytes
US10367233B2 (en) 2014-08-21 2019-07-30 Johnson & Johnson Vision Care, Inc. Biomedical energization elements with polymer electrolytes and cavity structures
US10374216B2 (en) 2014-08-21 2019-08-06 Johnson & Johnson Vision Care, Inc. Pellet form cathode for use in a biocompatible battery
US10381687B2 (en) 2014-08-21 2019-08-13 Johnson & Johnson Vision Care, Inc. Methods of forming biocompatible rechargable energization elements for biomedical devices
US10386656B2 (en) 2014-08-21 2019-08-20 Johnson & Johnson Vision Care, Inc. Methods and apparatus to form separators for biocompatible energization elements for biomedical devices
US10361404B2 (en) 2014-08-21 2019-07-23 Johnson & Johnson Vision Care, Inc. Anodes for use in biocompatible energization elements
US10558062B2 (en) 2014-08-21 2020-02-11 Johnson & Johnson Vision Care, Inc. Methods and apparatus to form biocompatible energization primary elements for biomedical device
US10598958B2 (en) 2014-08-21 2020-03-24 Johnson & Johnson Vision Care, Inc. Device and methods for sealing and encapsulation for biocompatible energization elements
US10627651B2 (en) 2014-08-21 2020-04-21 Johnson & Johnson Vision Care, Inc. Methods and apparatus to form biocompatible energization primary elements for biomedical devices with electroless sealing layers
US10345620B2 (en) 2016-02-18 2019-07-09 Johnson & Johnson Vision Care, Inc. Methods and apparatus to form biocompatible energization elements incorporating fuel cells for biomedical devices

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US20110287320A1 (en) 2011-11-24
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