WO2022070791A1 - バイポーラ型鉛蓄電池 - Google Patents

バイポーラ型鉛蓄電池 Download PDF

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Publication number
WO2022070791A1
WO2022070791A1 PCT/JP2021/032702 JP2021032702W WO2022070791A1 WO 2022070791 A1 WO2022070791 A1 WO 2022070791A1 JP 2021032702 W JP2021032702 W JP 2021032702W WO 2022070791 A1 WO2022070791 A1 WO 2022070791A1
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WO
WIPO (PCT)
Prior art keywords
lead
positive electrode
layer
bipolar
adhesive
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/JP2021/032702
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English (en)
French (fr)
Japanese (ja)
Inventor
広樹 田中
康雄 中島
健一 須山
彩乃 小出
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.)
Furukawa Electric Co Ltd
Furukawa Battery Co Ltd
Original Assignee
Furukawa Electric Co Ltd
Furukawa Battery Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Furukawa Electric Co Ltd, Furukawa Battery Co Ltd filed Critical Furukawa Electric Co Ltd
Priority to CN202180062043.0A priority Critical patent/CN116250097A/zh
Priority to JP2022553727A priority patent/JPWO2022070791A1/ja
Priority to EP21875093.3A priority patent/EP4224569A4/en
Priority to AU2021353160A priority patent/AU2021353160A1/en
Priority to BR112023004630A priority patent/BR112023004630A2/pt
Publication of WO2022070791A1 publication Critical patent/WO2022070791A1/ja
Priority to US18/190,690 priority patent/US20230238654A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
    • 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
    • H01M10/06—Lead-acid accumulators
    • H01M10/18—Lead-acid accumulators with bipolar 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
    • H01M4/14—Electrodes for lead-acid 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
    • H01M4/36—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
    • H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
    • 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
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/42—Acrylic resins
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/029—Bipolar electrodes
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a bipolar lead-acid battery.
  • a bipolar lead-acid battery is provided with a bipolar electrode having a positive electrode formed on one surface and a negative electrode formed on the other surface.
  • the positive electrode of the conventional bipolar electrode has a lead layer 220 for a positive electrode arranged on one surface of a resin substrate 210 via an adhesive layer 240, and is used for the positive electrode. It is configured by arranging a positive electrode active material layer (not shown) on the lead layer 220.
  • the lead layer 220 for the positive electrode is corroded by the sulfuric acid contained in the electrolytic solution, and a film 260 of a corrosion product (lead oxide) is formed on the surface of the lead layer 220 for the positive electrode (lead oxide).
  • a corrosion product lead oxide
  • the lead layer 220 for the positive electrode may be stretched (growth) due to the growth of the coating 260 of the corrosion product.
  • the lead layer 220 for the positive electrode and the adhesive layer 240 are peeled off by the growth, the electrolytic solution infiltrates the interface between the lead layer 220 for the positive electrode and the adhesive layer 240, and the lead layer 220 for the positive electrode is further corroded by sulfuric acid. There was a risk of progress (see (c) in FIG. 9). As a result, when the corrosion reaches, for example, the back surface of the lead layer 220 for the positive electrode (the surface facing the substrate 210), a short circuit may occur and the performance of the battery may deteriorate.
  • An object of the present invention is to provide a bipolar lead-acid battery.
  • the bipolar lead storage battery is a bipolar lead storage battery including a bipolar electrode having a positive electrode formed on one surface of a substrate and a negative electrode formed on the other surface, wherein the positive electrode is lead or A lead layer for a positive electrode made of a lead alloy and arranged on the one surface of the substrate, an active material layer for a positive electrode arranged on a lead layer for a positive electrode, and one surface of the substrate and lead for a positive electrode.
  • An adhesive layer arranged between the layers and adhering the one surface of the substrate to the lead layer for a positive electrode is provided, the substrate is formed of a thermoplastic resin, and the adhesive layer is a main agent containing an epoxy resin.
  • the electrolytic solution even if the lead layer for the positive electrode grows due to corrosion by the sulfuric acid contained in the electrolytic solution, the electrolytic solution does not easily penetrate into the interface between the lead layer for the positive electrode and the adhesive layer, and the battery performance is deteriorated. It is unlikely to occur.
  • FIG. 3 is an enlarged cross-sectional view of a bipolar electrode for explaining the structure of a main part of the bipolar lead-acid battery of FIG. 1.
  • the bipolar lead-acid battery shown in FIG. 1 even if the lead layer for the positive electrode grows due to corrosion by the sulfuric acid contained in the electrolytic solution, the electrolytic solution is suppressed from entering the interface between the lead layer for the positive electrode and the adhesive layer. It is a figure explaining how it is done.
  • the bipolar lead-acid battery 1 of the first embodiment has a first plate unit in which a negative electrode 110 is fixed to a flat plate-shaped first plate 11, and a second plate in which an electrolytic layer 105 is fixed inside a frame plate-shaped second plate 12.
  • It has a fourth plate unit in which 120 is fixed to a flat fourth plate 14.
  • the substrate 111 is made of a thermoplastic resin.
  • the second plate unit and the third plate unit are alternately laminated between the first plate unit and the fourth plate unit to form a bipolar lead-acid battery 1 having a substantially rectangular parallelepiped shape.
  • the number of each of the second plate unit and the third plate unit to be stacked is set so that the storage capacity of the bipolar lead-acid battery 1 becomes a desired value.
  • a negative electrode terminal 107 is fixed to the first plate 11, and the negative electrode 110 fixed to the first plate 11 and the negative electrode terminal 107 are electrically connected to each other.
  • a positive electrode terminal 108 is fixed to the fourth plate 14, and the positive electrode 120 fixed to the fourth plate 14 and the positive electrode terminal 108 are electrically connected to each other.
  • the electrolytic layer 105 is composed of, for example, a glass fiber mat impregnated with an electrolytic solution containing sulfuric acid.
  • the first to fourth plates 11, 12, 13, 14 are formed of, for example, a well-known molding resin.
  • the first to fourth plates 11, 12, 13, and 14 are fixed to each other so that the inside is sealed by an appropriate method so that the electrolytic solution does not flow out.
  • the positive electrode 120 includes a lead layer 101 for a positive electrode made of lead or a lead alloy and arranged on the one surface of the substrate 111, and an active material layer 103 for a positive electrode arranged on the lead layer 101 for a positive electrode. It is provided with an adhesive layer 140 that is arranged between the one surface of the substrate 111 and the lead layer 101 for the positive electrode and adheres the one surface of the substrate 111 to the lead layer 101 for the positive electrode. That is, the adhesive layer 140, the lead layer 101 for the positive electrode, and the active material layer 103 for the positive electrode are placed on the one surface of the substrate 111 (the surface facing upward on the paper surface in FIGS. 2 and 3) in the order of description. It is laminated.
  • the negative electrode 110 includes a lead layer 102 for a negative electrode made of lead or a lead alloy and arranged on the other surface of the substrate 111, and an active material layer 104 for a negative electrode arranged on a lead layer 102 for a negative electrode.
  • An adhesive layer (not shown) arranged between the other surface of the substrate 111 and the lead layer 102 for the negative electrode and adhering the other surface of the substrate 111 and the lead layer 102 for the negative electrode is provided.
  • the positive electrode 120 and the negative electrode 110 are electrically connected by an appropriate method. In the cross-sectional views of the bipolar electrodes including FIGS. 2 and 3, the negative electrode 110 and the positive electrode active material layer 103 are not shown.
  • the substrate 111, the lead layer 101 for the positive electrode, the active material layer 103 for the positive electrode, the lead layer 102 for the negative electrode, and the active for the negative electrode constitutes the bipolar electrode 130.
  • the bipolar electrode is an electrode having both positive and negative functions with one electrode.
  • a plurality of cell members having an electrolytic layer 105 interposed between the positive electrode 120 and the negative electrode 110 are alternately laminated and assembled, so that the cell members are connected in series. It has a connected battery configuration.
  • the adhesive layer 140 arranged between the one surface of the substrate 111 and the lead layer 101 for the positive electrode contains an epoxy resin-containing main agent and an amine compound. It is formed of a cured product of a reaction-curing adhesive that cures by reacting with the contained curing agent. This cured product is not easily attacked by sulfuric acid (hereinafter, the property of being resistant to sulfuric acid is sometimes referred to as "sulfuric acid resistance”), and the adhesive layer 140 has a concentration of 38% by mass and a temperature of 60 ° C.
  • the sulfuric acid does not infiltrate the interface between the lead layer 101 for the positive electrode and the adhesive layer 140, so that the cured product will decompose, deteriorate, corrode, etc. even if it comes into contact with the electrolytic solution. It is unlikely to occur. Therefore, since the lead layer 101 for the positive electrode and the adhesive layer 140 are firmly adhered to each other, even if the lead layer 101 for the positive electrode grows due to corrosion by the sulfuric acid contained in the electrolytic solution, the lead layer 101 for the positive electrode and the lead layer 101 for the positive electrode are used. The infiltration of the electrolytic solution into the interface with the adhesive layer 140 is suppressed.
  • the adhesive layer 140 is not easily attacked by sulfuric acid, the lead layer 101 for the positive electrode and the adhesive layer 140 are firmly adhered in FIG. 3A. Therefore, as shown in FIG. 3B, even if a corrosion product (lead oxide) film 160 is formed on the surface of the positive electrode lead layer 101, the growth of the corrosion product film 160 grows on the adhesive layer 140. The film 160 of the corrosion product is suppressed from infiltrating into the interface between the lead layer 101 for the positive electrode and the adhesive layer 140.
  • the lead layer 101 for the positive electrode grows due to the corrosion caused by the sulfuric acid contained in the electrolytic solution, the lead layer 101 for the positive electrode and the adhesive layer 140 are unlikely to peel off, so that the lead layer 101 for the positive electrode adheres to the lead layer 101.
  • the infiltration of the electrolytic solution into the interface with the agent layer 140 is suppressed. Therefore, it is unlikely that corrosion due to sulfuric acid will reach the back surface of the lead layer 101 for the positive electrode (the surface facing the substrate 111) and cause a short circuit, resulting in deterioration of battery performance.
  • thermoplastic resin forming the substrate 111 examples include acrylonitrile-butadiene-styrene copolymer (ABS resin) and polypropylene. These thermoplastic resins have excellent moldability and sulfuric acid resistance. Therefore, even if the electrolytic solution comes into contact with the substrate 111, decomposition, deterioration, corrosion, etc. are unlikely to occur on the substrate 111.
  • the adhesive layer 140 is formed of a cured product obtained by curing a reaction-curing adhesive
  • the reaction-curing adhesive is a mixture of a main agent containing an epoxy resin and a curing agent containing an amine compound. It is a type of adhesive that cures by reacting the main agent and the curing agent. Since such a reaction-curable adhesive can be cured at room temperature (for example, 20 ° C. or higher and 40 ° C. or lower), it is a lead or lead alloy metal that forms the lead layer 101 for the positive electrode and the lead layer 102 for the negative electrode. It can be cured at a temperature that does not easily affect the structure. Further, the reaction-curing adhesive is less likely to adversely affect the thermoplastic resin forming the substrate 111.
  • reaction-curing adhesive has advantages such as high adhesiveness and long pot life.
  • the compounding ratio of the main agent and the curing agent in the reaction-curing adhesive is preferably 44 parts by mass or less of the curing agent with respect to 100 parts by mass of the main agent.
  • Examples of the epoxy resin contained in the main agent include at least one of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin. One type of epoxy resin may be used alone, or two or more types may be used in combination.
  • Examples of the amine compound contained in the curing agent include an aliphatic polyamine compound, an alicyclic polyamine compound, and an aromatic polyamine compound. One of these amine compounds may be used alone, or two or more thereof may be used in combination.
  • aliphatic polyamine compound examples include aliphatic primary amines such as triethylenetetramine (C 6H 18 N 4 ) and aliphatic secondary amines such as triethylenetetramine.
  • aliphatic primary amines such as triethylenetetramine (C 6H 18 N 4 )
  • aliphatic secondary amines such as triethylenetetramine.
  • alicyclic polyamine compound examples include alicyclic primary amines such as isophorone diamine (C 10 H 22 N 2 ).
  • aromatic polyamine compound include aromatic primary amines such as diaminodiphenylmethane (C 13 H 14 N 2 ).
  • the bipolar lead-acid battery of the second embodiment will be described in detail with reference to FIG. However, since the configuration and operation / effect of the bipolar lead-acid battery of the second embodiment are almost the same as those of the first embodiment, only the different parts will be described, and the description of the same parts will be omitted.
  • the adhesive layer 140 is located between the one surface of the substrate 111 and the lead layer 101 for the positive electrode (that is, on the surface of both sides of the lead layer 101 for the positive electrode facing the substrate 111). ), And was not arranged on the surface of the positive electrode lead layer 101 on the side facing the positive electrode active material layer 103.
  • the second embodiment as shown in FIG.
  • the adhesive layer 140 is the active material for the positive electrode on both sides of the lead layer 101 for the positive electrode from between the substrate 111 and the lead layer 101 for the positive electrode. It extends to the peripheral edge portion 101a of the surface facing the layer 103, adheres to the peripheral edge portion 101a, and covers the peripheral edge portion 101a.
  • the adhesive layer 140 covers the peripheral edge portion 101a of the side surface of the positive electrode lead layer 101 on the side facing the positive electrode active material layer 103. Even if the lead layer 101 for the positive electrode grows due to corrosion by the sulfuric acid contained in the electrolytic solution, the infiltration of the electrolytic solution into the interface between the lead layer 101 for the positive electrode and the adhesive layer 140 is further suppressed. ..
  • the peripheral edge portion 101a is an outer portion of both sides of the positive electrode lead layer 101 on the side facing the positive electrode active material layer 103, and has a frame shape.
  • the above effect is obtained if the adhesive layer 140 arranged on the surface of both sides of the positive electrode lead layer 101 facing the positive electrode active material layer 103 covers a part of the frame-shaped peripheral edge portion 101a. However, it is more preferable to cover the entire frame-shaped peripheral edge portion 101a, the above effect will be further exhibited, and the performance of the battery will not be extremely deteriorated. That is, the adhesive layer 140 arranged on the surface of the positive electrode lead layer 101 on the side facing the positive electrode active material layer 103 has a frame shape as shown in FIG. More preferred. In FIG. 5, the positive electrode active material layer 103 is not shown.
  • the adhesive layer 140 covering the peripheral edge portion 101a may be integrated with the adhesive layer 140 arranged between the one surface of the substrate 111 and the lead layer 101 for the positive electrode. good. That is, the end portion of the adhesive layer 140 arranged between the one surface of the substrate 111 and the lead layer 101 for the positive electrode on the peripheral edge portion 101a side may extend to the peripheral edge portion 101a.
  • the adhesive layer 140 covering the peripheral edge portion 101a is not continuous with the adhesive layer 140 arranged between the one surface of the substrate 111 and the lead layer 101 for the positive electrode, and is a separate body. May be good.
  • the adhesive layer 140 covers the peripheral edge portion 101a of the surface facing the active material layer 103 for the positive electrode on both sides of the lead layer 101 for the positive electrode, but in the third embodiment, the adhesive layer 140 covers the peripheral edge portion 101a.
  • the covering member 150 is further arranged on the adhesive layer 140 covering the peripheral edge portion 101a. The covering member 150 will be fixed to the substrate 111 via the adhesive layer 140. At this time, it is more preferable that the covering member 150 is arranged so as to press the lead layer 101 for the positive electrode.
  • the covering member 150 may have sulfuric acid resistance that is not easily corroded by sulfuric acid, and examples of the material of the covering member 150 include sulfuric acid-resistant resins, metals (for example, stainless steel), and ceramics.
  • the substrate 111 has a flat plate shape, but in the fourth embodiment, the substrate 111 has a shape having a flange-shaped frame 170 at the tip of the peripheral edge. That is, as shown in FIG.
  • a plate-shaped portion extends from the peripheral end edge of the substrate 111 in a direction orthogonal to the one surface of the substrate 111 and the other surface, and this plate-shaped portion is the frame 170. Therefore, the frame 170 is arranged so as to surround the peripheral end end 101b of the positive electrode lead layer 101. Further, the frame 170 is made of resin.
  • the covering member 150 is fixed to the frame 170 via the adhesive layer 140. Therefore, it is easy to arrange the covering member 150 so as to press the lead layer 101 for the positive electrode. If the covering member 150 is arranged so as to press the lead layer 101 for the positive electrode, the growth of the coating film 160 of the corrosion product to the peripheral edge portion 101a is further suppressed.
  • the covering member 150 and the frame 170 can be fixed by an adhesive layer made of an adhesive. As shown in FIG. 7, the adhesive layer for fixing the covering member 150 and the frame 170 and the adhesive layer 140 for adhering the substrate 111 and the lead layer 101 for the positive electrode may be integrated, but they are separate bodies. You may. Further, the frame 170 and the substrate 111 may be an integral member as shown in FIG. 7, but may be a separate member.
  • the covering member 150 is a member separate from the frame 170, but in the fifth embodiment, the covering member 150 is a member integrated with the frame 170. Therefore, the covering member 150 is made of the same resin as the frame 170. From such a configuration, it is easier to arrange the covering member 150 so as to press the lead layer 101 for the positive electrode.
  • Various adhesions are made between the ABS resin plate-shaped member that can be used as the substrate 111 in the bipolar lead-acid batteries of the first to fifth embodiments and the lead foil-shaped member that can also be used as the lead layer 101 for the positive electrode.
  • a test piece was prepared by adhering with an agent, and a test was conducted to evaluate the sulfuric acid resistance of the test piece. That is, after heating sulfuric acid having a concentration of 38% by mass to 60 ° C. and immersing the test piece in the test piece for 1, 2 or 4 weeks, the state of adhesion of the test piece was observed and the plate-shaped member made of ABS resin was made of lead. The peel strength at the time of peeling off the foil-like member was measured.
  • the coefficient of thermal expansion of the cured product of the adhesive was measured using a thermomechanical analyzer (TMA) manufactured by METTLER TOLEDO.
  • TMA thermomechanical analyzer
  • the measurement conditions are an applied load of 0.05 N, a temperature range of ⁇ 50 to 150 ° C., and a heating rate of 10 ° C./min.
  • the length of the sample is 20 mm, the width is 2 mm, and the thickness is 0.1 mm.
  • the measurement was performed by the tensile method with a distance between the marked lines of 10 mm, but if the sample is small, the measurement may be performed by the compression method.
  • the temperature range to be measured is preferably set to be equal to or higher than the operating temperature range of the bipolar lead-acid battery.
  • the coefficient of thermal expansion was calculated from the slope of the temperature range of ⁇ 15 to 60 ° C. using the following formula. The results are shown in Table 1.
  • ⁇ L ⁇ (T2-T1) L
  • ⁇ L the amount of thermal expansion (mm)
  • ⁇ the coefficient of thermal expansion (ppm)
  • T1 is the temperature before change (° C)
  • T2 is the temperature after change (° C)
  • L is the length of the sample (mm).
  • the dynamic viscoelasticity of the cured product of the adhesive was measured using a dynamic viscoelasticity measuring device (DMA) trade name RSA-G2 manufactured by TA Instruments, and the glass transition point was measured from the tan ⁇ peak.
  • the measurement conditions were a temperature range of ⁇ 50 ° C. to 150 ° C., a frequency of 1 Hz, a marked line interval of 20 mm, a strain amount of 0.2%, and a heating rate of 5 ° C./min, and the measurement was performed by a tensile method.
  • the results are shown in Table 1. Since the operating temperature range of the bipolar lead-acid battery is ⁇ 15 to 60 ° C., the glass transition point is preferably 60 ° C. or higher.
  • the test for evaluating the sulfuric acid resistance of the test piece and the measurement of the thermal expansion coefficient and dynamic viscoelasticity of the cured product of the adhesive were carried out using a Fourier transform infrared spectrophotometer to cure the cured product of the adhesive. I went after checking the degree. This will be described below.
  • the reaction rate of the epoxy group in the cured product of the adhesive was measured by the attenuation total reflection method (ATR method: Attenated Total Reflection) using a Fourier transform infrared spectrophotometer 660/610 manufactured by Azilent Technology Co., Ltd. As a result, the degree of curing of the cured product of the adhesive was determined.
  • Diamond was used as the crystal of the ATR method, and a silver-cadmium-tellurium compound (MCT) detector was used as the detector.
  • the measurement conditions were a scan speed of 25 kHz, an incident angle of 45 degrees, and a resolution of 4 cm -1 .
  • the intensity of the absorption peak of the CO expansion and contraction vibration of the epoxy group (913 cm -1 ) and the intensity of the absorption peak of the CC expansion and contraction vibration of the phenyl group (1508 cm -1 ) were obtained, and the ratio of these intensities ([ The degree of curing of the cured product of the adhesive was determined from [Strength of 913 cm -1 ] / [Strength of 1508 cm -1 ]). Then, after confirming that the degree of curing is 0.15 or less and the cured product is sufficiently cured, a test for evaluating the sulfuric acid resistance of the test piece and the heat of the cured product of the adhesive are performed. The coefficient of expansion and dynamic viscoelasticity were measured. Examples and comparative examples will be described below.
  • Epoxy adhesive Epiform (registered trademark) K-9487 manufactured by SOMAR Corporation contains a bisphenol A type epoxy resin, and the content of the epoxy resin in the main agent is 80 to 90% by mass.
  • the curing agent K-9487B contains a modified aromatic polyamine compound and 4,4'-methylenedianiline, and the content of the modified aromatic polyamine compound in the curing agent is 65 to 75% by mass, 4,4'-methylenedianiline. The content of is 25 to 35% by mass.
  • the compounding ratio of the main agent and the curing agent is 44 parts by mass of the curing agent with respect to 100 parts by mass of the main agent.
  • the pot life of this adhesive at 25 ° C. was 60 min, which facilitated the bonding work. Further, when the adhesive state of the test piece after 4 weeks of immersion in sulfuric acid was observed, sulfuric acid did not penetrate into the interface between the lead foil-like member and the adhesive layer, and the adhesive state was good. Furthermore, when the peel strength was measured, the interface between the lead foil-like member and the adhesive layer was peeled off, and there was almost no difference in the peel strength before and after immersion in sulfuric acid.
  • Example 2 Epoxy adhesive A manufactured by Nagase ChemteX Corporation
  • the main agent XNR3114 contains a bisphenol A type epoxy resin and a parallel butyl phenyl glycidyl ether, and the content of the epoxy resin in the main agent is 80 to 90% by mass, and the content of the parallel butyl phenyl glycidyl ether. Is 10 to 20% by mass.
  • the curing agent XNH3114 contains a modified aliphatic polyamine compound, nonylphenol, m-xylylenediamine, triethylenetetramine, and isophoronediamine.
  • the content of the modified aliphatic polyamine compound in the curing agent is 32% by mass
  • the content of nonylphenol is 7.4% by mass
  • the content of m-xylylene diamine is 11% by mass
  • the content of triethylenetetramine is 15% by mass.
  • the content of isophorone diamine is 35% by mass.
  • the compounding ratio of the main agent and the curing agent is 25 parts by mass of the curing agent with respect to 100 parts by mass of the main agent.
  • the pot life of this adhesive at 25 ° C. was 60 min, which facilitated the bonding work. Further, when the adhesive state of the test piece after 4 weeks of immersion in sulfuric acid was observed, sulfuric acid did not penetrate into the interface between the lead foil-like member and the adhesive layer, and the adhesive state was good. Furthermore, when the peel strength was measured, the interface between the lead foil-like member and the adhesive layer was peeled off, and there was almost no difference in the peel strength before and after immersion in sulfuric acid.
  • the main agent XNR3106 contains a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a parallel butylphenyl glycidyl ether.
  • the content of the bisphenol A type epoxy resin in the main agent is 40 to 50% by mass
  • the content of the bisphenol F type epoxy resin is 30 to 40% by mass
  • the content of the parallel butylphenyl glycidyl ether is. It is 10 to 20% by mass.
  • the curing agent XNH3103 contains a modified polyamine compound, phenol, nonylphenol, m-xylylenediamine, triethylenetetramine, and isophoronediamine.
  • the content of the modified polyamine compound in the curing agent is 25% by mass, the content of phenol is 4% by mass, the content of nonylphenol is 11% by mass, the content of m-xylylene diamine is 11% by mass, and the content of triethylenetetramine is contained.
  • the amount is 23% by mass, and the content of isophoronediamine is 26% by mass.
  • the compounding ratio of the main agent and the curing agent is 25 parts by mass of the curing agent with respect to 100 parts by mass of the main agent.
  • the pot life of this adhesive at 25 ° C. was 20 min, which was a short time for the bonding work. Further, when the adhesive state of the test piece after 4 weeks of immersion in sulfuric acid was observed, sulfuric acid did not penetrate into the interface between the lead foil-like member and the adhesive layer, and the adhesive state was good. Furthermore, when the peel strength was measured, the interface between the lead foil-like member and the adhesive layer was peeled off, and there was almost no difference in the peel strength before and after immersion in sulfuric acid.
  • the main agent AV138 contains a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and silica.
  • the curing agent HV998 contains a polyamide amine compound and diethylenetriamine. The compounding ratio of the main agent and the curing agent is 40 parts by mass of the curing agent with respect to 100 parts by mass of the main agent.
  • the pot life of this adhesive at 25 ° C. was 35 min, which was a short time for the bonding work. Further, when the adhesive state of the test piece was observed one week after the immersion in sulfuric acid, the interface of the adhesive layer was eroded by sulfuric acid. Further, when the peel strength was measured, the interface between the plate-shaped member made of ABS resin and the adhesive layer was peeled off, and the peel strength was greatly reduced by immersion in sulfuric acid. Further, when the adhesion state of the test piece after 4 weeks of immersion in sulfuric acid was observed, the adhesion between the lead foil-like member and the adhesive layer was not maintained.
  • Epoxy adhesive main agent Epotac (trade name) AD-45 manufactured by Pernox Co., Ltd. contains a bisphenol A type epoxy resin and crystalline silica.
  • the curing agent Percure (trade name) HQ-1W contains an aliphatic polyamine compound, triethylenetetramine and titanium dioxide.
  • the compounding ratio of the main agent and the curing agent is 30 to 70 parts by mass of the curing agent with respect to 100 parts by mass of the main agent.
  • the pot life of this adhesive at 25 ° C. was 120 min, which facilitated the bonding work. Further, when the adhesive state of the test piece was observed one week after the immersion in sulfuric acid, the interface of the adhesive layer was eroded by sulfuric acid. Further, when the peel strength was measured, the interface between the plate-shaped member made of ABS resin and the adhesive layer was peeled off, and the peel strength was greatly reduced by immersion in sulfuric acid. Further, when the adhesion state of the test piece after 4 weeks of immersion in sulfuric acid was observed, the adhesion between the lead foil-like member and the adhesive layer was not maintained.
  • the adhesive used for the double-sided adhesive tape is an acrylic adhesive.
  • Bipolar lead-acid battery 101 Lead layer for positive electrode 101a ... Peripheral portion 101b ... Peripheral tip 102 ... Lead layer for negative electrode 103 ... Active material layer for positive electrode 104 ... Negative electrode Active material layer 105 ⁇ ⁇ ⁇ Electrode layer 110 ⁇ ⁇ ⁇ Negative electrode 111 ⁇ ⁇ ⁇ Substrate 120 ⁇ ⁇ ⁇ Positive electrode 130 ⁇ ⁇ ⁇ Bipolar electrode 140 ⁇ ⁇ ⁇ Adhesive layer 150 ⁇ ⁇ ⁇ Coating member 170 ⁇ ⁇ ⁇ Frame

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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)
  • Materials Engineering (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Secondary Cells (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Saccharide Compounds (AREA)
PCT/JP2021/032702 2020-09-30 2021-09-06 バイポーラ型鉛蓄電池 Ceased WO2022070791A1 (ja)

Priority Applications (6)

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CN202180062043.0A CN116250097A (zh) 2020-09-30 2021-09-06 双极型铅蓄电池
JP2022553727A JPWO2022070791A1 (https=) 2020-09-30 2021-09-06
EP21875093.3A EP4224569A4 (en) 2020-09-30 2021-09-06 BIPOLAR LEAD-ACID BATTERY
AU2021353160A AU2021353160A1 (en) 2020-09-30 2021-09-06 Bipolar lead-acid battery
BR112023004630A BR112023004630A2 (pt) 2020-09-30 2021-09-06 Bateria de chumbo-ácido bipolar
US18/190,690 US20230238654A1 (en) 2020-09-30 2023-03-27 Bipolar Lead-Acid Battery

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JP2020-165685 2020-09-30
JP2020165685 2020-09-30

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4513060A (en) * 1984-02-08 1985-04-23 E. I. Du Pont De Nemours And Company Chlorosulfonated polyethylene coating composition
WO1994019837A1 (en) * 1993-02-24 1994-09-01 Trojan Battery Company An electrode plate construction
JP2585847B2 (ja) * 1990-07-27 1997-02-26 新神戸電機株式会社 薄形密閉形蓄電池
WO2005101550A1 (ja) * 2004-03-31 2005-10-27 Ntt Data Ex Techno Corporation 蓄電池用被覆集電体、該被覆集電体の製造方法、および被覆集電体を有する蓄電池
JP2010003446A (ja) * 2008-06-18 2010-01-07 Gs Yuasa Corporation 鉛蓄電池
CN104752673A (zh) * 2013-12-27 2015-07-01 松下蓄电池(沈阳)有限公司 铅蓄电池

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4510219A (en) * 1983-11-14 1985-04-09 California Institute Of Technology Battery plate containing filler with conductive coating
US5800946A (en) * 1996-12-06 1998-09-01 Grosvenor; Victor L. Bipolar lead-acid battery plates
JP2001068115A (ja) * 1999-08-27 2001-03-16 Hitachi Chem Co Ltd 非水溶媒系バインダ組成物、電極の製造法、電極及び非水溶媒系二次電池

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4513060A (en) * 1984-02-08 1985-04-23 E. I. Du Pont De Nemours And Company Chlorosulfonated polyethylene coating composition
JP2585847B2 (ja) * 1990-07-27 1997-02-26 新神戸電機株式会社 薄形密閉形蓄電池
WO1994019837A1 (en) * 1993-02-24 1994-09-01 Trojan Battery Company An electrode plate construction
WO2005101550A1 (ja) * 2004-03-31 2005-10-27 Ntt Data Ex Techno Corporation 蓄電池用被覆集電体、該被覆集電体の製造方法、および被覆集電体を有する蓄電池
JP2010003446A (ja) * 2008-06-18 2010-01-07 Gs Yuasa Corporation 鉛蓄電池
CN104752673A (zh) * 2013-12-27 2015-07-01 松下蓄电池(沈阳)有限公司 铅蓄电池

Non-Patent Citations (1)

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Title
See also references of EP4224569A4 *

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EP4224569A4 (en) 2025-06-25
JPWO2022070791A1 (https=) 2022-04-07
US20230238654A1 (en) 2023-07-27
CN116250097A (zh) 2023-06-09
EP4224569A1 (en) 2023-08-09
AU2021353160A9 (en) 2025-03-20
AU2021353160A1 (en) 2023-06-08

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