US20110083966A1 - Electrode for lead-acid battery and method for producing such an electrode - Google Patents

Electrode for lead-acid battery and method for producing such an electrode Download PDF

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Publication number
US20110083966A1
US20110083966A1 US12/996,691 US99669108A US2011083966A1 US 20110083966 A1 US20110083966 A1 US 20110083966A1 US 99669108 A US99669108 A US 99669108A US 2011083966 A1 US2011083966 A1 US 2011083966A1
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Prior art keywords
lead
glassy carbon
carbon substrate
intermediate layer
electrode
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Abandoned
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US12/996,691
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English (en)
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Angel Zhivkov Kirchev
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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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
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
    • 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
    • H01M4/16—Processes of manufacture
    • H01M4/20—Processes of manufacture of pasted 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
    • H01M4/64—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
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • H01M4/685—Lead alloys
    • 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
    • H01M4/72—Grids
    • H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0433—Molding
    • 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 invention relates to an electrode for lead-acid battery comprising :
  • the invention also related to a method for producing such an electrode.
  • Lead-acid battery is known to include at least one positive current collector, at least one negative current collector and an electrolytic solution.
  • the negative and positive current collectors are lead grids or lead plates of various configurations (flat-plates, tubular-plates . . . ) and on which is disposed an active material paste in order to form an electrode. Storage and release of electrical energy in lead-acid batteries is enabled by chemical reactions that occur in the paste.
  • the main drawback of the lead-acid batteries is their low specific energy.
  • Flat-plate lead-acid battery has a specific energy about 30-35 Wh/kg whereas tubular-plate lead-acid battery has a specific energy about 20-25 Wh/kg.
  • the grid structure comprises:
  • the current collectors will show much higher electrical resistance and the plastic substrate is also unsuitable in a further cast on strap process also called COS process.
  • Another alternative consists to use graphite electrode-plate as mentioned in patent U.S. Pat. No. 5,512,390.
  • one of the plates forms a cathode and has a surface layer of lead in contact with the electrolyte whereas the other plate forms the anode and has a surface layer of manganese dioxide in contact with the electrolyte.
  • the article “Lead-acid cells with lightweight, corrosion-protected, flexible-graphite grids” of B. Hariprakash et al. proposes to use lightweight grids prepared from flexible graphite sheets of mass density 1.1 g.cm ⁇ 3 . The grids are then coated with a lead layer followed by a corrosion-resistant polyaniline layer. The corrosion-protected grids are then pasted with active materials.
  • the active material sheds easy from these grids or plates.
  • the electroplated polyaniline layer used in the article of B. Hariprakash et al. degrades fast under the high potential of the operation of the positive plate.
  • the graphite is a very soft material and its surface cannot withstand the changes mechanical stress during the charge and the discharge and the quality of the lead layer is poor, causing fast peeling.
  • the high-porous carbon can be carbon foam.
  • patent U.S. Pat. No. 6,979,513 describes a current collector formed from of a carbon foam material which may include carbon or carbon-based material that exhibit some degree of porosity.
  • the positive and negative plates include then a current collector made from carbon foam and packed or coated by a chemically active material including, for example, an oxide or salt of lead.
  • the carbon foam material can be obtained by subjecting various organic material to a carbonizing and/or graphitizing process. More particularly, at least of portion of carbon foam matrix is graphite.
  • the high-porous carbon can also be reticulated vitreous carbon also called RVC.
  • RVC reticulated vitreous carbon
  • patent U.S. Pat. No. 7,060,391 proposes current collector structures based on light-weight, porous, open pore, high specific surface area substrates coated with lead or lead-tin alloy.
  • the substrates can be reticulated vitreous carbon.
  • Lead or lead-tin alloy can be deposited by electroplating method. Lead or lead-tin alloy covers the surface of the substrates and also occupies the openings of the reticulated substrates.
  • the current collectors are subjected to pasting with any variety of lead oxide and/or lead sulfate based pastes in order to form electrodes.
  • Such current collectors have the following drawbacks:
  • a cathode active material is pasting on the surface of the film in order to form the corresponding electrode.
  • a cathode active material is pasting on the surface of the film in order to form the corresponding electrode.
  • Such a film is strongly bonded on the surface of the glassy carbon plate and does not separate from the plate even after long use.
  • the positive active material can easy loss the mechanical and electrical connection with the carbon support.
  • the object of the invention is to provide an electrode for lead-battery and a method for producing such an electrode remedying the shortcomings of the prior art.
  • one object of the invention is to provide an electrode for lead-acid battery comprising a glassy carbon substrate, an intermediate layer deposited on the glassy carbon substrate and an active layer of a lead-containing paste covering the intermediate layer, having improved mechanical and electrical connection between the lead-containing paste and the substrate and a stabilized interface between the substrate and the intermediate layer even if deep discharge conditions are applied.
  • the intermediate layer is a compact layer of lead or lead-based alloy and by the fact that the volume of the pores in the glassy carbon substrate is comprised between 0% and 10% of its apparent volume.
  • FIG. 1 represents a particular embodiment of an electrode according to the invention in cross section.
  • FIG. 2 schematically represents a glassy carbon substrate in the form of a comb in front view.
  • FIGS. 3 and 4 schematically represent a current collector consisting in the glassy carbon substrate according to FIG. 2 covering by an intermediate layer, respectively in front view and in cross section along A-A.
  • FIG. 5 schematically represents, in cross-section, an alternative embodiment of the current collector according to FIGS. 3 and 4 .
  • FIG. 6 represents cyclic voltammograms of an electrode consisting in glassy carbon substrate in the form of a rod covered by an intermediary layer of pure lead, immersed in sulfuric acid solution at 40° C., respectively at 100 and 1700 voltametric cycles.
  • FIG. 7 represents an optical micrograph of a glassy carbon substrate in the form of a rod electroplated by pure lead, after a corrosion test at 40° C. during 16 h.
  • FIGS. 8 and 9 represent the evolution of charge-discharge current and potential of tubular-plate electrodes, respectively assembled with lead-tin electroplated glassy carbon substrate in the form of a rod and with cast lead-2.8% wt antimony material in the form of a rod.
  • an electrode 1 for lead-battery comprises a current collector 2 covered by an active layer 3 of lead-containing paste.
  • the current collector 2 is formed by a glassy carbon substrate 4 on which is deposited an intermediate layer 5 .
  • the glassy carbon substrate 4 has preferably a thickness comprised between 1 mm and 3 mm whereas the thickness of the intermediate layer 5 is advantageously comprised between 50 ⁇ m and 200 ⁇ m.
  • the glassy carbon material is also called vitreous carbon, glassy polymeric carbon or vitreous polymeric carbon.
  • the glassy carbon is a special form of carbon. It is a low-porous carbon.
  • the glassy carbon substrate 4 comprises pores but the volume of these pores only represent between 0% and 10% of the apparent volume of the substrate. More particularly, the ratio between the volume of pores and the apparent volume is comprised between 1% and 6%.
  • the glassy carbon material presents high electric conductivity property and mechanical properties similar to those of the glasses (hardness, capacity to polish the surface, etc). It has also a very high chemical resistance and it is electrochemically stable in a wide range of polarization potentials.
  • Recycling of lead-acid batteries that comprise a glassy carbon substrate can be done by all existing technologies used for recycling of traditional lead-acid batteries.
  • the glassy carbon substrate can be separated and used in other applications in the form of powder or subjected to incineration together with the rest of the plastic components of the battery (boxes, separators, etc).
  • the document JP2158057 cited in the state of the art has already proposed an electrode for a bipolar lead-storage battery comprising a glassy carbon plate.
  • the surface of the glassy carbon plate is covered by a layer of SnO 2 or by a layer of Ti 4 O 7 presenting some major drawbacks.
  • an intermediate layer 5 made by lead or by a lead-based alloy allows remedying to the drawbacks of the document JP2158057.
  • the intermediate layer 5 must be a compact layer, i.e. a non-porous layer.
  • the preferred lead-based alloy is an alloy consisting in lead and tin and more particularly a lead-tin alloy comprising 2.5 weight percents in total weight of the elements containing in the intermediate layer.
  • Such an intermediate layer 5 improves the adhesion of the active material paste on the current collector 2 .
  • the electrode is also more stable when deep discharge conditions are applied.
  • the intermediate layer 5 contains tin is advantageous because tin prevents the electrode from the Predominant Capacity Loss (PCL) effect due to formation of highly resistive layer of PbO and PbO n with 1 ⁇ n ⁇ 2 in the corrosion layer.
  • PCL Predominant Capacity Loss
  • Sn(II) and Sn(IV) ions act as doping agents in the crystal lattice of PbO and PbO n with 1 ⁇ n ⁇ 2 and they decrease substantially the ohmic resistance of these two lead oxides that correspond to the compounds of the corrosion layer formed on the surface of the positive current collector during the implementation of the lead-acid battery.
  • the presence of tin in the intermediate layer 5 also improves its mechanical resistance.
  • the tin content in the intermediate layer 5 is preferably limited to 2.5 weight % because when the tin content in a lead-based alloy is more than 2.5%, its anodic corrosion rate increases markedly.
  • thermosetting resin can be a phenol-formaldehyde resin, a furfural alcohol resin, a polyester resin, an epoxy resin or a mixture of them. Carbonizing the thermosetting resin is achieved by heat treatment.
  • the surface treatment step comprises:
  • the tab of the glassy carbon substrate 4 used as connection element, is advantageously electroplated with copper. Electroplating the tab with copper ensures the quality of the cast on strap connection. In fact, the glassy carbon substrate cannot be wetted in liquid metals and copper has a melting temperature much higher than the lead and is nearly insoluble in it. Suitable conditions for the copper electroplating operation can be the following:
  • Suitable pulse current regime is for instance obtain by applying a cathodic current with a density of 60 mA/cm 2 during 6 s and then an anodic current with a density of 60 mA/cm 2 applied during 1 s.
  • An operation time of 30 min allows obtaining a copper layer deposited on the tab having a thickness of about 25 ⁇ m.
  • the tab electroplated by copper is then rinsed with water.
  • the intermediate layer 5 is then formed by electroplating at least the whole of the surface of the glassy carbon substrate 4 with lead or lead-based alloy. This step is the most critical operation of the process. It is in particular necessary to choose an electrolyte enabling the highest adhesion strength of the intermediate layer 5 to the glassy carbon substrate 4 and a constant thickness of the intermediate layer 5 to be obtained.
  • An intermediate layer 5 made of 2.5% Sn—Pb alloy can be formed by using an electrolyte comprising Pb(II) salt of the 4-hydroxybenzenesulfonic acid (Pb(p-C 6 H 4 OHSO 3 ) 2 ) and Sn (II) salt of the 4-hydroxybenzenesulfonic acid (Sn(p-C 6 H 4 OHSO 3 ) 2 ) and p-phenolsulfonic acid (p-C 6 H 4 OHSO 3 H).
  • the weight percent of the tin is about 2.5% of the total weight of metals containing in the electrolyte in the electrolyte.
  • the electrolyte can be obtained by mixing:
  • the electroplating step can be performed with:
  • the pulse current characteristics can be as follows:
  • the intermediate layer 5 has a thickness about 50 ⁇ m (+/ ⁇ 2%). This thickness is sufficient for a current collector used in a negative electrode.
  • the operation time can be doubled in order to deposit an intermediate layer 5 having a thickness between about 100 ⁇ m and 200 ⁇ m (+/ ⁇ 2%).
  • the current collector is rinsed with water and dried on air flow. Then, the active layer 3 can be formed on the intermediate layer 5 by depositing the lead-containing paste in order to form the electrode.
  • the lead-containing paste can be obtained by mixing PbO (75%) with H 2 O (15%) and H2SO 4 (10%).
  • Such a process presents the advantage to provide an electrode having improved mechanical and electrical connection between the lead-containing paste and the substrate.
  • the interface between the substrate and the intermediate layer is also stabilized even if deep discharge conditions are applied.
  • the electrodes for lead-acid battery can have any known shape.
  • the glassy carbon substrate can be in the form of grid or comb, in order to obtain electrodes in the form of flat plates or of tubular plates.
  • FIG. 2 represents more particularly a glassy carbon substrate 4 in the form of a comb designed to be used to obtain a tubular-plate electrode.
  • the glassy carbon substrate 4 comprises a plurality of parallel branches 4 a connected together by a base 4 b.
  • the base 4 b also comprises a tab 6 equipped with an opening 7 .
  • FIGS. 3 and 4 represent the glassy carbon substrate 4 covered by the intermediate layer 5 .
  • copper 8 has filled the opening 7 before the intermediate layer 5 is formed.
  • the typical diameter of the opening 7 is about 2-3 mm.
  • branches 4 a of the glassy carbon substrate 4 have a round cross-section as represented on FIG. 4 .
  • This is the traditional design of a current collector used for a tubular-plate electrode.
  • the cross-section of the branches 4 a can be of any type of form.
  • the branches 4 a can also have a rectangular cross-section as represented on FIG. 5 or a square cross-section or elliptic square cross-section.
  • the form of current collector represented on FIG. 5 is also called Strap Grid Tubular Plates (SGTP). This form is advantageous because it increases substantially the performance of the corresponding lead-acid battery in comparison with the traditional design (round cross-section): The load factor of the active material is much higher and the internal resistance is decreased.
  • manufacturing the SGTP current collectors from glassy carbon substrate as represented in FIG. 5 is also much cheaper than the corresponding traditional current collectors from glassy carbon substrate as represented in FIG. 4 .
  • the active material paste is encapsulated around each branch 4 a covered by an intermediate layer 5 , by means of a woven or non-woven textile tube.
  • This tube maintains a constant pressure on the active material and prevents its softening or its non-cohesion from the current collector.
  • a current collector formed by a glassy carbon rod (or branch or spine) having a diameter d of 3 mm and by an intermediate layer of pure lead having a thickness of 150 ⁇ m is immersed in sulfuric acid solution, H 2 SO 4 , at 40° C. with a density of 1.28 g/ml. It's testing in the 0.7V-1.6V potential interval vs. the potential of Ag/Ag 2 SO 4 .
  • FIG. 6 shows the corresponding cyclic voltammetry curves A and B, for 100 cycles and 1700 cycles. The curves A and B do not differ from the corresponding curves of a cast lead electrode used in the state of the art.
  • the intermediate layer of pure lead is subjected both to cathodic dissolution and anodic corrosion attack at elevated temperature.
  • the current collector is washed, dried and embedded in an epoxy resin 9 . Its cross-section is polished and subjected to a metallographic observation as represented in FIG. 7 . It can be seen that the intermediate layer 5 is homogeneous and intact.
  • the thickness of the corrosion layer 10 is also homogeneous and there aren't cracks and pits.
  • a same type of electrode is assembled by using spines cut off from commercial tubular-grids with a Pb-2.8 wt Sb alloy.
  • FIGS. 8 and 9 show the evolution of the current and of the positive plate potential (measured vs. Ag/Ag 2 SO 4 reference electrode) during the 28 th charge/discharge cycle. It can be seen that the electrochemical performance of the lead electroplated glassy-carbon tubular electrode is identical with the one of the lead-antimony cast spine.
  • the current collector can have the form of:
  • reticulated vitreous carbon is a high-porous carbon, in which the open porosity is about 90%-95% of its apparent volume.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Connection Of Batteries Or Terminals (AREA)
US12/996,691 2008-06-09 2008-06-09 Electrode for lead-acid battery and method for producing such an electrode Abandoned US20110083966A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB2008/002468 WO2009150485A1 (fr) 2008-06-09 2008-06-09 Electrode pour batterie plomb-acide et procédé de production de ladite électrode

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US (1) US20110083966A1 (fr)
EP (1) EP2313353B1 (fr)
JP (1) JP5362824B2 (fr)
CN (1) CN102056861A (fr)
AT (1) ATE530506T1 (fr)
BR (1) BRPI0822755A2 (fr)
ES (1) ES2374426T3 (fr)
PL (1) PL2313353T3 (fr)
WO (1) WO2009150485A1 (fr)

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US20140120429A1 (en) * 2011-06-24 2014-05-01 Commissariat A L'energie Atomique Et Aux Energies Alternatives High capacity gaseous diffusion electrode
WO2015103285A1 (fr) * 2013-12-30 2015-07-09 Gridtential Energy, Inc. Matériaux actifs architecturaux pour batteries d'accumulateurs au plomb
US9112231B2 (en) 2010-11-05 2015-08-18 Cabot Corporation Lead-acid batteries and pastes therefor
EP3196964A1 (fr) * 2011-01-04 2017-07-26 Exide Technologies Additif graphite avancé pour améliorer le cycle de vie des décharges profondes des batteries plomb-acide
US10014520B2 (en) 2012-10-31 2018-07-03 Exide Technologies Gmbh Composition that enhances deep cycle performance of valve-regulated lead-acid batteries filled with gel electrolyte
WO2022164802A1 (fr) * 2021-01-26 2022-08-04 Gridtential Energy, Inc. Plaque de batterie bipolaire et sa fabrication
WO2023079029A3 (fr) * 2021-11-03 2023-06-15 Norwegian University Of Science And Technology (Ntnu) Structures de carbone amorphe dimensionnellement stables

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US6274274B1 (en) 1999-07-09 2001-08-14 Johnson Controls Technology Company Modification of the shape/surface finish of battery grid wires to improve paste adhesion
CN101233635B (zh) 2005-05-23 2013-07-03 约翰逊控制技术公司 电池板栅
EP2122725B1 (fr) 2007-03-02 2014-04-09 Johnson Controls Technology Company Grille négative pour batterie
US9130232B2 (en) 2010-03-03 2015-09-08 Johnson Controls Technology Company Battery grids and methods for manufacturing same
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CN101908608A (zh) * 2010-08-13 2010-12-08 肇庆理士电源技术有限公司 一种铅酸铸焊蓄电池的汇流排及铅酸铸焊蓄电池
KR20140066709A (ko) * 2011-07-21 2014-06-02 더루우브리졸코오포레이션 카르복시 피롤리디논 및 이의 사용 방법
US9761883B2 (en) 2011-11-03 2017-09-12 Johnson Controls Technology Company Battery grid with varied corrosion resistance
US9299980B2 (en) * 2012-03-29 2016-03-29 Copperwatts Llc Electrodes, batteries, electrode production methods, and production methods
CN103022503A (zh) * 2012-12-24 2013-04-03 厦门大学 一种含有聚苯胺的铅酸蓄电池负极铅膏
DE102013111109A1 (de) 2013-10-08 2015-04-09 Johnson Controls Autobatterie Gmbh & Co. Kgaa Gitteranordnung für eine plattenförmige Batterieelektrode eines elektrochemischen Akkumulators sowie Akkumulator
DE102013111667A1 (de) 2013-10-23 2015-04-23 Johnson Controls Autobatterie Gmbh & Co. Kgaa Gitteranordnung für eine plattenförmige Batterieelektrode und Akkumulator
US20170155171A1 (en) * 2014-05-30 2017-06-01 Commissariat A L'energie Atomique Et Aux Energies Alternatives Lead-acid accumulator and method for manufacturing such an accumulator
CN104241658B (zh) * 2014-09-23 2016-05-18 浙江南都电源动力股份有限公司 一种铅酸蓄电池集流体的制造方法
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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3742101A (en) * 1969-10-02 1973-06-26 Agency Ind Science Techn Carbon-glass composite and manufacturing method therefor
US4098967A (en) * 1973-05-23 1978-07-04 Gould Inc. Electrochemical system using conductive plastic
US4782585A (en) * 1981-10-01 1988-11-08 Matsushita Electric Industrial Co., Ltd. Grid for lead storage battery and method for its production
US5114812A (en) * 1989-07-07 1992-05-19 Hoechst Aktiengesellschaft Electrodes for primary and secondary electric cells
EP0690149A1 (fr) * 1994-06-30 1996-01-03 Mitsubishi Materials Corporation Bain électrolytique pour la formation d'électrodes à protubérances en alliage plomb-étain sur la surface d'une pastille semi-conductrice
US5512390A (en) * 1994-07-21 1996-04-30 Photran Corporation Light-weight electrical-storage battery
US20030219653A1 (en) * 2002-05-22 2003-11-27 Caterpillar Inc. Carbon coated battery electrodes
US20040072074A1 (en) * 2001-01-19 2004-04-15 Partington Thomas John Electrode for a battery
US6979513B2 (en) * 2002-06-28 2005-12-27 Firefly Energy Inc. Battery including carbon foam current collectors
US7060391B2 (en) * 2001-09-26 2006-06-13 Power Technology, Inc. Current collector structure and methods to improve the performance of a lead-acid battery
US20060147792A1 (en) * 2004-07-22 2006-07-06 Solicore, Inc. Machining electrical power supply device for wire electrical discharge machining apparatus

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5859560A (ja) * 1981-10-01 1983-04-08 Matsushita Electric Ind Co Ltd 鉛蓄電池用格子体
JPS58126672A (ja) * 1982-01-21 1983-07-28 Matsushita Electric Ind Co Ltd 鉛蓄電池用格子体の製造法
JPH02158057A (ja) * 1988-12-12 1990-06-18 Furukawa Battery Co Ltd:The バイポーラ型鉛蓄電池用電極基板
JP3334421B2 (ja) * 1994-06-30 2002-10-15 三菱マテリアル株式会社 半導体ウエハ表面へのＰｂ−Ｓｎ合金突起電極形成用電気メッキ液
JPH08269776A (ja) * 1995-03-31 1996-10-15 Mitsubishi Materials Corp 半導体ウエハ表面へのＰｂ−Ｓｎ合金突起電極形成用電気メッキ液
CN1052117C (zh) * 1995-05-10 2000-05-03 中国科学院长春应用化学研究所 制备高稳定催化氧还原电极的热修饰法
GB0101401D0 (en) * 2001-01-19 2001-03-07 Atraverda Ltd Electrode for a battery

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3742101A (en) * 1969-10-02 1973-06-26 Agency Ind Science Techn Carbon-glass composite and manufacturing method therefor
US4098967A (en) * 1973-05-23 1978-07-04 Gould Inc. Electrochemical system using conductive plastic
US4782585A (en) * 1981-10-01 1988-11-08 Matsushita Electric Industrial Co., Ltd. Grid for lead storage battery and method for its production
US5114812A (en) * 1989-07-07 1992-05-19 Hoechst Aktiengesellschaft Electrodes for primary and secondary electric cells
EP0690149A1 (fr) * 1994-06-30 1996-01-03 Mitsubishi Materials Corporation Bain électrolytique pour la formation d'électrodes à protubérances en alliage plomb-étain sur la surface d'une pastille semi-conductrice
US5512390A (en) * 1994-07-21 1996-04-30 Photran Corporation Light-weight electrical-storage battery
US20040072074A1 (en) * 2001-01-19 2004-04-15 Partington Thomas John Electrode for a battery
US7060391B2 (en) * 2001-09-26 2006-06-13 Power Technology, Inc. Current collector structure and methods to improve the performance of a lead-acid battery
US20030219653A1 (en) * 2002-05-22 2003-11-27 Caterpillar Inc. Carbon coated battery electrodes
US6979513B2 (en) * 2002-06-28 2005-12-27 Firefly Energy Inc. Battery including carbon foam current collectors
US20060147792A1 (en) * 2004-07-22 2006-07-06 Solicore, Inc. Machining electrical power supply device for wire electrical discharge machining apparatus

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
Battlebury, "A High Performance Lead-Acid Battery for EV Applications", Journal of Power Sources (no month, 1999), Vol. 80, pp. 7-11. *
Karami et al., "Lead-Acid Bipolar Battery Assembled with Primary Chemically Formed Positive Pasted Electrode", Journal of Power Sources (no month, 2007), Vol. 164, pp. 896-904. *
Petersson et al., "Oxidation of Electrodeposited Lead-Tin Alloys in 5 M H2SO4", Journal of Power Sources (no month, 2000), Vol. 91, pp. 143-149. *
Ramamurthy et al., "Electrochemical Nucleation and Growth of Lead Dioxide on Glassy Carbon Electrodes", Journal of Electroanalytical Chemistry and Interfacial Electrochemistry (10 May 1982), Vol. 135, Issue 2, pp. 243-255. *
Ramamurthy et al., "Electrochemical Nucleation and Growth of Lead Dioxide on Glassy Carbon Electrodes", Journal of Electroanalytical Chemistry and Interfacial Electrochemistry" (10 May 1992), Vol. 135, Issue 2, pp. 243-255. *
Solokhina et al., "Electrolytic Deposition of a Lead-Tin Alloy on a Galvanic Copper Support", Poligraficheskoe Proizvodstvo (no month, 1947), No. 4, pp. 13-14. 1-page Abstract Only. *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8148938B2 (en) * 2009-05-28 2012-04-03 Panasonic Corporation Lead storage battery charging control method, charging control circuit, power source device, and lead storage battery
US8344698B2 (en) 2009-05-28 2013-01-01 Panasonic Corporation Lead storage battery charging control method, charging control circuit, power source device, and lead storage battery
US20110285357A1 (en) * 2009-05-28 2011-11-24 Tomoya Kikuchi Lead storage battery charging control method, charging control circuit, power source device, and lead storage battery
US9112231B2 (en) 2010-11-05 2015-08-18 Cabot Corporation Lead-acid batteries and pastes therefor
EP3196964A1 (fr) * 2011-01-04 2017-07-26 Exide Technologies Additif graphite avancé pour améliorer le cycle de vie des décharges profondes des batteries plomb-acide
US10340523B2 (en) 2011-01-04 2019-07-02 Exide Technologies Advanced graphite additive for enhanced cycle-life of deep discharge lead-acid batteries
US10224550B2 (en) 2011-01-04 2019-03-05 Exide Technologies Advanced graphite additive for enhanced cycle-life of lead-acid batteries
US20140120429A1 (en) * 2011-06-24 2014-05-01 Commissariat A L'energie Atomique Et Aux Energies Alternatives High capacity gaseous diffusion electrode
US9368802B2 (en) * 2011-06-24 2016-06-14 Commissariat à l'Energie Atomique et aux Energies Alternatives High capacity gaseous diffusion electrode
US10014520B2 (en) 2012-10-31 2018-07-03 Exide Technologies Gmbh Composition that enhances deep cycle performance of valve-regulated lead-acid batteries filled with gel electrolyte
WO2015103285A1 (fr) * 2013-12-30 2015-07-09 Gridtential Energy, Inc. Matériaux actifs architecturaux pour batteries d'accumulateurs au plomb
WO2022164802A1 (fr) * 2021-01-26 2022-08-04 Gridtential Energy, Inc. Plaque de batterie bipolaire et sa fabrication
TWI823239B (zh) * 2021-01-26 2023-11-21 美商古登修能源公司 雙極性電池胞元極板及其製造
WO2023079029A3 (fr) * 2021-11-03 2023-06-15 Norwegian University Of Science And Technology (Ntnu) Structures de carbone amorphe dimensionnellement stables

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