EP3149790A1 - Accumulateur au plomb-acide et procédé de fabrication d'un tel accumulateur - Google Patents
Accumulateur au plomb-acide et procédé de fabrication d'un tel accumulateurInfo
- Publication number
- EP3149790A1 EP3149790A1 EP15729544.5A EP15729544A EP3149790A1 EP 3149790 A1 EP3149790 A1 EP 3149790A1 EP 15729544 A EP15729544 A EP 15729544A EP 3149790 A1 EP3149790 A1 EP 3149790A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sheet
- μιτι
- negative
- lead
- active material
- 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.)
- Withdrawn
Links
Classifications
-
- 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
- H01M10/12—Construction or manufacture
- H01M10/125—Cells or batteries with wound or folded electrodes
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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
-
- 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
- H01M10/12—Construction or manufacture
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or 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
- H01M4/36—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
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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
- H01M4/64—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
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/531—Electrode connections inside a battery casing
- H01M50/534—Electrode connections inside a battery casing characterised by the material of the leads or tabs
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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
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/531—Electrode connections inside a battery casing
- H01M50/538—Connection of several leads or tabs of wound or folded electrode stacks
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- 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 lead-acid type battery used as an electrochemical energy storage system, particularly in the automotive field, and a method of manufacturing a lead-acid battery.
- a lead-acid battery comprises a positive electrode and a negative electrode immersed in a liquid electrolyte based on sulfuric acid.
- Each electrode conventionally comprises a lead current collector on which is disposed an active material based on lead, typically porous lead dioxide for the positive electrode and porous lead for the negative electrode.
- the current collector for example in the form of a grid or a plate, serves as a mechanical support for the active material and provides the electrical connection between the active material of the electrode and a terminal of the accumulator.
- the chemical reactions taking place in the discharge accumulator convert the lead dioxide (Pb0 2 ) of the positive electrode and the lead (Pb) of the negative electrode into lead sulphate (PbSO 4 ), and conversely into charge.
- This type of electrochemical accumulator is particularly robust, but its specific energy density (also called specific energy) is low, of the order of 30 to 40 Wh / kg.
- This value of the energy density results from the significant weight of lead current collectors and a limited use of active materials.
- the coefficients of use of the positive and negative active materials in discharge ie the conversion rates of lead and lead dioxide to lead sulphate
- the coefficients of use of the positive and negative active materials in discharge are between 30% and 50% for current collectors in the form of grid and a moderate discharge current (for example C n / 10h, where C n is the nominal capacity of the battery in Ah).
- C n the nominal capacity of the battery in Ah
- the positive electrode and the negative electrode each comprise a thin lead sheet (about 50 ⁇ thick) coated on both sides with a layer of active material (about 100 ⁇ thickness).
- the positive and negative electrodes are wound spirally, with a glass microfiber separator sheet disposed between the two electrodes.
- Two cylindrical lead connectors, forming the positive and negative terminals of the accumulator, are then molded at both ends of the winding over the entire length of the projecting strips.
- the utilization coefficients of the positive and negative active materials are greater than 80%.
- the life of the accumulator is limited.
- the current collector of the positive electrode is subject to a corrosion phenomenon, the lead gradually becoming lead dioxide.
- lead dioxide is fragile, which may involve a loss of dimensional stability.
- the use of large lead connectors limits the specific energy density of the battery (of the order of 30 Wh / kg).
- the energy density can be improved by replacing the lead of the positive current collector with a lighter metal, such as titanium, nickel, tin or molybdenum.
- a titanium gate 250 ⁇ thick is the current collector of the positive electrode.
- This grid has an electrical resistance comparable to that of a conventional lead grid, but its weight is less.
- the titanium grid is coated with a layer protective metal semiconductor oxide (for example Sn0 2 doped with fluorine) and a dense layer of lead dioxide (Pb0 2 ), before being coated with active material (porous lead oxide Pb0 2 , 10 ⁇ to 10 mm thick).
- the semiconductor metal oxide layer prevents contact between the sulfuric acid electrolyte and the titanium grid.
- the titanium current collector is thus protected from oxidation and the life of the accumulator is increased.
- the dense layer of Pb0 2 connects the active material to the current collector and reduces the voltage drops in the electrode.
- the patent US4326017 describes two negative electrodes each comprising a lead sheet. Due to the use of lead as a negative current collector, the specific energy of such a lead accumulator is only partially improved.
- the patent EP2313353 describes a lead-acid battery electrode comprising a flexible carbon sheet, having a thickness of between 60 ⁇ and 180 ⁇ , covered on both sides with a layer of active material of 200 ⁇ to 250 ⁇ thick.
- the electrode further comprises a hook layer containing lead and tin between the carbon sheet and each layer of active material. Two electrodes of this type are spirally wound to form a lead-acid battery.
- this battery has a limited life because the positive electrode degrades over the charging and discharging cycles.
- US Pat. No. 4,606,982 describes a method of manufacturing a lead battery electrode.
- a paste of active material is first deposited on both sides of a lead grid.
- a sheet of paper of porous material is glued on each face of the grid covered with paste, to form a stack of layers stratified.
- Each sheet of paper adheres to the grid by exerting sufficient pressure for the paste of active material to impregnate the porous material.
- the electrode is assembled with one or more other multilayer electrodes of opposite polarity.
- the two sheets of paper are made of glass microfibers and are stored in the final structure of the battery, where they act as a separator with electrodes of opposite polarity.
- a negative electrode comprising:
- a current collector formed of a carbon sheet having a thickness of between 50 ⁇ and 200 ⁇ and preferably between 130 ⁇ and 200 ⁇ ; first and second lead layers respectively covering first and second faces of the carbon sheet; and
- first and second layers of an active material containing lead having a thickness of between 100 ⁇ and 500 ⁇ and preferably between 300 ⁇ and 400 ⁇ , and disposed on either side of the carbon sheet, respectively on the first and second lead layers;
- a positive electrode comprising:
- a current collector formed of a titanium sheet having a thickness of between 50 ⁇ and 250 ⁇ and preferably between 100 ⁇ and 150 ⁇ ; first and second electrically conductive metal oxide layers respectively covering first and second faces of the titanium foil; and
- first and second layers of an active material containing lead having a thickness between 100 ⁇ and 500 ⁇ and preferably between 130 ⁇ and 200 ⁇ , and arranged on either side of the sheet of titanium, respectively on the first and second metal oxide layers.
- the negative electrode and the positive electrode are separated by at least one sheet of porous electrically insulating material and held together so that the porous material is compressed.
- the negative electrode, the positive electrode and two sheets of porous material form a multilayer stack, said multilayer stack being wound on itself to give the accumulator a spiral shape.
- the negative and positive electrodes each comprise projecting collector portions not coated with the first and second layers of active material, the protruding portions of each of the negative and positive electrodes being distributed along the 'a radius of the spiral.
- one of the negative and positive electrodes comprises a plurality of electrode portions.
- Two sheets of porous material and the other of negative and positive electrodes form a multilayer stack, said multilayer stack being folded into a coil to receive, under each fold, one of the electrode portions.
- the negative and positive electrodes each comprise projecting collector portions not coated with the first and second layers of active material, the protruding portions of the negative electrode being aligned on one side with the serpentine stack and the protruding portions of the positive electrode being aligned on an opposite side of the serpentine stack.
- the accumulator may also have one or more of the following characteristics considered individually or in any technically feasible combination: the first and second lead-based layers of the negative electrode have a thickness of between 10 ⁇ and 20 ⁇ ;
- the first and second metal oxide layers of the positive electrode have a thickness of between 0.5 ⁇ and 2 ⁇ ;
- each of the first and second active material layers of the negative electrode and the positive electrode is covered with a sheet of fiberglass or cellulose-based paper;
- the negative electrode further comprises first and second copper layers disposed on either side of the carbon sheet, between each of the first and second lead layers and the carbon sheet;
- the positive electrode further comprises first and second lead oxide layers disposed on either side of the titanium foil, respectively between the first metal oxide layer and the first layer of active material, and between the second layer metal oxide and the second layer of active material;
- the accumulator further comprises a lead connector electrically connected to a portion of the carbon sheet and a titanium connector electrically connected to a portion of the titanium sheet, the lead and titanium connectors respectively forming the negative and positive terminals. the accumulator;
- the lead and titanium connectors partly occupy only one face of the accumulator
- the carbon sheet is a graphite sheet, flexible carbon paper or a carbon fabric
- the titanium sheet is provided with through openings, preferably of square, round or diamond-shaped section.
- the invention also relates to a method of manufacturing such a lead acid battery comprising the following steps:
- a negative electrode by successively depositing on each of the two faces of a carbon sheet, with a thickness of between 50 ⁇ and 200 ⁇ , a lead-based layer and a layer of active material containing lead, of a thickness of between 100 ⁇ and 500 ⁇ ;
- a positive electrode by successively depositing on each of the two faces of a sheet of titanium, with a thickness of between 50 ⁇ and 250 ⁇ , an electrically conductive metal oxide layer and a layer of active material containing lead, of thickness between 100 ⁇ and 500 ⁇ ;
- the assembly of the negative and positive electrodes comprises the following steps:
- the sheets of porous material are partially impregnated with water during the winding of the multilayer stack.
- the assembly of the negative and positive electrodes comprises the following steps:
- the negative electrode and the positive electrode are, during the step of assembly, distributed in the form of continuous and flexible bands, driven by rotary cylinders and shaped in parallel with each other.
- the shaping of the negative and positive electrodes may comprise a brushing step and a step of cutting a portion of the carbon sheet and a portion of the titanium foil, so as to form connecting tabs on each negative and positive electrodes, said portions being devoid of active material.
- each of the negative and positive electrodes of the lead accumulator comprises the following steps:
- the current collector sheet of the negative electrode being made of the carbon sheet coated on each of the two faces of the lead-based layer and the current collector current sheet of the positive electrode consisting of the titanium foil coated on each of the two faces of the electrically conductive metal oxide layer;
- the first sheet of caliper paper to a first face of the current collecting sheet and the second sheet of calving paper to a second opposite face of the current collecting sheet.
- an electrode may also have one or more of the following characteristics, considered individually or in any technically possible combination:
- the current collecting sheet is in the form of a vertically oriented strip and each of the first and second blanking paper sheets is brought into contact with the current collecting sheet in a direction perpendicular to the current collecting sheet;
- the first and second sheets of squirting paper are shaped strips, each band being carried by a belt conveyor during the deposition step of the active material;
- the first and second sheets of serration paper move at a speed of between 5 cm / s and 1 m / s and preferably between 5 cm / s and 50 cm / s;
- the first and second sheets of stripping paper are glued to the current collector sheet by means of two calendering rolls exerting a pressure on either side of the current collector sheet; each of the negative and positive electrodes is furthermore laminated by means of two rolling rolls arranged on either side of the current collecting sheet;
- the first and second sheets of stripping paper have a thickness of between 20 ⁇ and 200 ⁇ ;
- the active material is spread on each of the first and second blanking paper sheets by means of a spreading cylinder and smoothed by means of a doctor blade;
- the active material is laid in cords on each of the first and second blanking paper sheets by means of a plurality of coating nozzles and spread during the pressing step of said sheet of blanking paper against the current collector sheet.
- FIG. 1 is a cross-sectional view of a negative electrode for a lead accumulator according to the invention
- FIG. 2 is a cross-sectional view of a positive electrode for a lead accumulator according to the invention
- FIGS. 3A and 3B show a first embodiment of a lead-acid accumulator according to the invention, in which the negative electrodes and positive of Figures 1 and 2 are spirally wound;
- FIG. 4 is a front view of the negative electrode of FIGS. 3A and 3B, arranged in the form of a strip before its spiral winding;
- FIG. 5 represents a second embodiment of a lead-acid accumulator according to the invention, in which the negative and positive electrodes of FIGS. 1 and 2 are assembled into a prismatic cell;
- FIG. 6 shows a front view of the negative electrode and the positive electrode of Figure 5, before they are respectively folded and cut to be assembled in the form of Figure 5;
- FIGS. 7, 8A and 8B show a first electrical connector fixed to the connection elements projecting from a negative electrode and forming the negative terminal of a lead-acid battery
- FIG. 9 shows a second electrical connector, forming the positive terminal of a lead accumulator
- FIGS. 10A and 10B show two modes of attachment of the connector of FIG. 9 to the connection elements projecting from a positive electrode
- FIG. 1 1 shows a preferred embodiment of a method of manufacturing an electrode, type "roll-to-roll"
- FIGS. 12A to 12C show an alternative embodiment of the etching step of the electrode of FIG. 11.
- FIG. 13 represents a preferred mode of implementation of the step of assembling a spiral accumulator, of the "roll-to-roll” type.
- FIGS. 1 and 2 respectively represent a negative electrode 1 and a positive electrode 2 of a lead-acid accumulator having a specific energy density (or specific energy) and a high power density (or specific power).
- Each electrode consists of a multilayer stack constructed symmetrically around a current collector in the form of a sheet, i.e. a thin and flexible plate.
- This sheet is the support of two layers of active material, hereinafter referred to as Negative Active Material (NAM) for the negative electrode and positive active material (PAM) for the positive electrode.
- a layer of active material covers each side of the sheet.
- the current collector 10 is carbon-based. It is preferably formed of a glassy carbon or graphite sheet, as opposed to carbon foams which generally contain a large volume of pores. Alternatively, it may consist of carbon or graphite fibers, in the form of a flexible paper (ie the fibers are cut and held by a binder - they are not woven) or of a fabric (ie the fibers are woven ).
- the thickness of the collector 10 made of carbon is between 50 ⁇ and 200 ⁇ , and preferably between 130 ⁇ and 200 ⁇ .
- a graphite foil (known under the Anglo-Saxon term “graphite foil”) may have a density of the order of 1 g. cm "3 to 2 g cm “ 3 .
- the carbon sheet 10 also has a thermal conductivity ten times greater than that of lead, which allows the use of the battery in high power applications.
- the carbon sheet 10 comprises two main and parallel faces 10a and 10b, each coated with a thin layer of lead or a lead alloy (for example lead and tin).
- a first lead-based layer 11a is thus disposed on the face 10a and a second layer 1 1b made of lead is disposed on the face 10b.
- the layers 1 1 a and 1 1 b allow a better grip of the negative active material, also based on lead, on the current collector 10. In addition, they improve the electrical conductivity and the mechanical strength of the collector 10 carbon.
- the layers 1 1 a and 1 1 b cover the entire surface of carbon sheet 10 and their thickness is between 10 ⁇ and 20 ⁇ , so that they are devoid of holes.
- the negative electrode 1 of Figure 1 further comprises two layers of negative active material (NAM) 12a and 12b respectively disposed on the layers 1 1a and 1 1b lead-based.
- the layers of NAM 12a and 12b have a thickness of between 100 ⁇ and 500 ⁇ , and preferably between 300 ⁇ and 400 ⁇ . Layers 12a and 12b thicker would make the electrode less flexible and complicate its assembly with the positive electrode to form an electrochemical cell, while a lower thickness would cause less use of the active material.
- the negative active material is preferably porous lead.
- the sheets 13a and 13b prevent the layers of active materials 12a and 12b and crack during assembly of the electrodes and flake during operation of the accumulator.
- the negative electrode 1 comprises two copper intermediate layers 14a and 14b, preferably having a thickness of between 5 ⁇ and 10 ⁇ , and disposed on either side of the carbon sheet 10, between each of the layers
- These copper layers 14a, 14b considerably improve the electrical conductivity of the carbon sheet 10, with a minimum of additional weight given their small thickness.
- the positive electrode 2 shown in FIG. 2 comprises a sheet of titanium 20 with a thickness of between 50 ⁇ and 250 ⁇ , and preferably between 100 ⁇ and 150 ⁇ .
- This sheet 20 may be solid (i.e. not pierced) or provided with through openings, for example of square, round or diamond-shaped section (in the latter case, it is called expanded titanium, "expanded foil").
- the size of the openings i.e. their side or diameter
- the titanium constituting the sheet 20 is preferably more than 99% pure (class 1 and / or class 2). It is thus soft and ductile, facilitating its implementation in the lead accumulator as current collector of the positive electrode.
- Each of the two faces 20a and 20b of the titanium foil 20 is coated with electrically conductive metal oxide layer 21a and 21b respectively, for example tin dioxide Sn0 2 .
- the layers 21a and 21b preferably cover the current collector 20 in their entirety. They constitute artificial corrosion layers and protect the titanium from oxidation, thus avoiding the formation of an electrically resistive TiO 2 titanium oxide that is poorly soluble in the electrolyte. Thus, the titanium current collector 20 with positive potentials can withstand the electrolyte longer.
- the metal oxide is preferably a semiconductor doped with fluorine (F), antimony (Sb) or ions of a transition metal, in order to increase its electrical conductivity. Its thickness in the layers 21a and 21b is advantageously between 0.5 ⁇ and 2 ⁇ , so that they contain a minimum of defects.
- Two layers of positive active material (PAM) 22a and 22b are disposed on either side of the titanium foil 20 coated with the semiconductor metal oxide 21a-b.
- the layer 22a covers the layer 21a of metal oxide and the layer 22b, located on the other side of the electrode with respect to the titanium sheet 20, covers the layer 21b.
- the PAM layers 22a and 22b have a thickness of between 100 ⁇ and 500 ⁇ , and preferably between 130 ⁇ and 200 ⁇ .
- the positive active material of the layers 22a and 22b is preferably porous lead dioxide (Pb0 2 ).
- each of the layers 22a and 22b Pb0 2 of the positive electrode 2 may be covered with a sheet of paper fiberglass or cellulose-based. These layers bear respectively the references 23a and 23b in FIG.
- the positive electrode 2 advantageously comprises two dense layers of lead dioxide 24a and 24b (ie devoid of pores, unlike the PAM layers).
- These layers 24a and 24b of Pb0 2 whose thickness is between 5 ⁇ and 20 ⁇ , are arranged on either side of the titanium foil 20, respectively between the semiconductor metal oxide layer 21 a and the PAM layer 22a, and between the semiconductor metal oxide layer 21b and the PAM layer 22b.
- the PAM material adheres better to the titanium current collector 20 (covered with artificial corrosion layers 21a-21b).
- the negative electrode comprises a current collector formed of a carbon sheet, coated on each of its two faces with a lead-based layer, then with a layer of a lead-containing active material having a thickness between 100 ⁇ and 500 ⁇ .
- the positive electrode is formed of a titanium foil successively coated on both sides with an electrically conductive layer made of metal oxide and with a layer of a lead-containing active material having a thickness of between 100 ⁇ . and 500 ⁇ .
- the coefficients of use of the positive and negative active materials are particularly high, of the order of 90%. This is partly due to the low occupancy rates of the active materials on the current collectors (expressed as mass of active material per unit area). In fact, given the thicknesses of the active material layers and the geometry of the current collectors, this occupancy rate, also called ⁇ coefficient, is less than 0.5 g / cm 2 for each of the positive and negative electrodes. In addition, the mass ratio of the active material on the current collector is high, between 3 and 7 for each of the electrodes.
- the coefficients of use and the aforementioned mass ratios provide, after assembly of the negative and positive electrodes, high values of mass densities of energy and power, respectively from 60 Wh / kg to 90 Wh / kg approximately and 1 kW / kg to about 10 kW / kg.
- the energy density of an accumulator comprising thin lead collectors is less than 30 Wh / kg.
- each of the electrodes is designed to resist corrosion by the electrolyte.
- the negative carbon current collector is insensitive to the sulfuric acid electrolyte at negative potentials while the positive current collector is protected over its entire surface in contact with the electrolyte by the semiconductor metal oxide layers. . This ensures a long life to the lead accumulator comprising these two electrodes.
- the charge acceptance (synonymous with charge efficiency) and the high current discharge capacity of the battery are high, because the positive and negative electrodes are thin compared to those of conventional lead-acid batteries.
- These high electrical performances are mainly due to a rapid diffusion of sulfate ions through the layers of active material and a low electrical resistance of the layers of active material.
- the total thickness of the electrodes does not exceed 0.8 mm.
- the negative and positive electrodes of Figures 1 and 2 are joined, interposing between them at least one sheet of a porous electrically insulating material.
- This porous material is intended to contain the electrolyte of the accumulator, typically sulfuric acid, and to electrically isolate the two electrodes.
- the electrodes are advantageously assembled so that the porous material of the separator sheet is compressed. This compression is measured by a reduction in the thickness of the separator sheet of about 20%. It can further increase the life of the battery, the active materials are less likely to soften and flake over time.
- Several forms of assembly of the negative and positive electrodes can be envisaged.
- the negative and positive electrodes 1 and 2 are stacked with two separator sheets 3 formed of the porous and insulating material.
- This multilayer stack is wound on itself to give the accumulator a spiral shape.
- the sheets 3 are arranged so that at any point of the winding, one of them separates the negative electrodes 1 and positive 2. Thus, no short circuit between the electrodes 1 and 2 is possible and the Utilization coefficient of the electrolyte is maximum.
- the two separator sheets 3 are for example disposed on either side of the positive electrode 2 in FIG. 3A.
- the separator sheets 3 are preferably AGM ("Adsorptive Glass Mat”), that is, microporous glass fiber layers. This type of separator is commonly used in Valve-Regulated Lead-Acid (VRLA) batteries to store electrolyte and keep the active material on the electrodes.
- the sheets 3 preferably have a thickness (before compression) of the order of 2 mm for a battery of high energy density. For a battery of high power density, the thickness of the sheets 3 is advantageously between 0.8 mm and 1 mm. In both cases, the separator sheets 3 can store a sufficient volume of electrolyte to achieve active material utilization coefficients (positive and negative) of about 90%.
- the spiral accumulator of FIGS. 3A and 3B further comprises two sets of projecting connecting tabs, for example on the side of the upper face of the stack.
- Each series of tongues allows the attachment of an electrical connector, preferably metal.
- the tongues 15 belong to the negative electrode 1 (FIG. 3A) and are fixed to a connector 16 (FIG. 3B), whereas the tongues 25 belong to the positive electrode 2 and are fixed to a connector 26.
- each of the connectors 16, 26 connect the connection tongues 15, 25 electrically in parallel
- the connectors 16 and 26 respectively form the negative and positive terminals, which extend to the outside of the accumulator. They will be described in detail in connection with FIGS. 7, 8A-8B, 9 and 10A-10B.
- connection tongues of each electrode ensure the transport of the electric current between the collector of this electrode and the corresponding electrical terminal of the accumulator. They are advantageously aligned and distributed along a radius of the spiral, as shown in FIG. 3A. This configuration of the tabs simplifies the geometry of the connectors 16, 26 and facilitates their attachment to the spiral stack.
- FIG. 4 shows an arrangement of the connection tabs 15 of the negative electrode 1 before its assembly with the positive electrode 2.
- the tabs 15 each consist of a projecting portion of the carbon sheet coated with the layers lead-based 1 1 a and 1 1 b. They extend on the same side of the electrode 1 and, unlike the rest of the electrode, they are not covered layers of active material 12a and 12b.
- the connecting tabs 15 are advantageously spaced two by two by a distance that varies by increasing (looking from left to right in Figure 4). More specifically, the spacing between the tongues 15 is chosen so that after winding the electrode 1 with the electrode 2 and the separators 3, the tongues 15 are aligned. In addition, the length L of the tongues 15 increases as one moves away from the center of the spiral (FIG. 3), at the same time as the increase in their spacing (FIG. It is thus intended to obtain a positioning of the tongues in a cone, which has the highest angle possible, for example 90 °.
- the spacing of the tongues 15 is such that each tab is positioned centrally on the same radius of the spiral at each spiral turn.
- This arrangement of the tongues 15 is particularly suitable for high power electrochemical cells, which require a large number of these connection elements (> 7) in order to better distribute the current.
- a tab will appear only every second turn and the spacing can be chosen accordingly.
- connection tongues 25 of the positive electrode 2 each consist of a portion of the titanium current collector covered with the metal oxide layers, but not coated with active material. They are preferably arranged in the same way as the tongues 15.
- the lead accumulator comprises a negative electrode of the type of FIG. 1 and a positive electrode of the type of FIG. 2, stacked with two AGM separators 2 mm thick.
- the electrodes have, regardless of the connection tabs, a rectangular surface equal to 10 cm x 150 cm. Each electrode thus exposes a surface of active material of the order of 3000 cm 2 .
- the wound stack occupies a cylinder 10.5 cm in diameter and 10 cm high, which corresponds approximately to 8 turns of winding.
- the number of tongues of each electrode is equal to 7.
- the winding of electrodes and separators is arranged in a cylindrical housing, about 1 1 cm in diameter and 12 cm in height, closed by a cover.
- Housing and cover both made of polypropylene, have walls approximately 2.5 mm thick.
- a lead connector and a titanium connector respectively form the negative and positive terminals of the accumulator.
- the remaining volume of the cylindrical housing is filled with a solution having a sulfuric acid (fully charged) concentration of 5 mol / L and a density of 1.285 g / mL.
- Table 1 below lists the components of this spiral accumulator and gives, for each of them, its thickness and weight. It should be noted that the thickness values indicated in the table concern the thickness of a single copy of the component, and not the cumulative thickness of several copies of the same component (if several copies exist). On the other hand, the weight values represent the total weight of all the copies of the same component. These remarks are valid for the layers of NAM, PAM, Pb, PbO 2 and AGM (2 copies each).
- AGM [400g / m 2 ] 2.2mm * 120g 2mm AGM + 2x0.1mm glass fiber paper
- the current collector is a graphite sheet with a thickness of 100 ⁇ and a density of around 1.2 g / cm 3 .
- the layers of negative active material (NAM) consist of lead in the pure state (4 g / cm 3 ) and have a thickness of 300 ⁇ .
- the galvanic lead coatings on the carbon collector have a thickness of 15 ⁇ and the paper layers have a thickness of 100 ⁇ (the paper layers are assimilated to AGM in Table 1).
- the occupancy rate of the negative active material YNAM is equal to approximately 0.12 g / cm 2 (compared with values ranging from 2 to
- Table 1 above gives the capacities (expressed in Ah) relative to each active material and to the electrolyte, as well as the energy (expressed in Wh) developed by their combination.
- the latter is, in the last lines of Table 1, relative to the total weight and the volume of the cell to give respectively the mass energy density and the density of energy density.
- this example of a spiral accumulator shows utilization coefficients of NAM and PAM respectively of 90% and 85%, which results in an energy density of 73Wh / kg (mass) or 147. Wh / L (volumetric), more than twice as much as the accumulators of the prior art.
- the power density delivered by the accumulator is close to 2 kW / kg (or 4 kW / L).
- FIG. 5 represents, in top view, a second embodiment of a lead-acid accumulator, in which the electrodes 1 and 2 are assembled in a corrugated form, in the manner of a coil.
- the electrochemical accumulator thus configured resembles a prismatic cell, where the positive (s) and negative (s) electrodes are arranged parallel to each other in a parallelepipedal housing.
- One of the positive and negative electrodes here the negative electrode 1, is disposed between two layers of separators 3, preferably AGM type.
- the multilayer stack thus obtained is folded in the form of a coil, that is to say, repeatedly and in opposite directions of a fold 4 to another. Under each fold 4 is disposed a portion 2 'of positive electrode. These portions 2 'are for example obtained after cutting a positive electrode 2 of larger dimensions.
- the electrodes of the accumulator also have, in this second embodiment, tongues or connecting elements 15 and 25 protruding. These tongues extend in a direction parallel to the bends of the negative electrode 1, perpendicular to the plane of FIG. 5.
- the tabs of each electrode can be, here too, aligned to facilitate the design and implementation of connectors (not shown).
- the tongues 15 of the continuous negative electrode 1 extend above the folding zones 5 of the stack 3-1 -3, these zones 5 being situated on the same side of the coil assembly.
- the tabs 25 of the positive electrode which is "exploded" in several portions 2 ', are located on the opposite side of the assembly, in the immediate vicinity of the folding zones 6.
- the zones 6 result from the folding of the stack in a direction contrary to that of zones 5.
- Figure 5 the configuration of Figure 5 can be reversed.
- the positive electrode 2 is then stacked with the AGM separators 3, then folded, and the negative electrode 1 is subdivided into a plurality of portions arranged under the folds of the positive electrode 2.
- FIG. 6 represents the electrodes 1 and 2 before their assembly in the form of FIG. 5, and more particularly the arrangement of their connecting tongues 15 and 25.
- the electrodes 1 and 2 are in the form of strips, that is to say long and narrow. Their composition is identical to that described in relation with FIG. 1 or 2.
- the tongues 15 and 25 are formed of portions of the current collector (respectively of carbon and titanium), projecting from the same side of the electrode and not covered by the layers of active material (NAM and PAM respectively).
- NAM and PAM active material
- the tongues 15 are located at the fold zones 5 of the electrode, shown schematically by dashed lines in FIG. 6. They are preferably centered on these fold lines 5. In addition, two successive tongues 15 are separated by a folding zone 6, also reduced to a dashed line. In other words, there are no tongues 15 in the folding zones 6, as is also visible in FIG. 5.
- the positive electrode 2 is shown in FIG. 6 before being cut into portions 2 '.
- the electrode portions 2 ' are delimited by cutting lines 7.
- they are the same size and each have a connecting tab 25.
- the tabs 15 of the negative electrode 1 on the one hand, and the tongues 25 of the negative electrode 2 on the other hand, are regularly spaced along the strips 1 and 2 (as the lines folding 5 and 6). All the tongues 15 of the negative electrode 1 have the same size, unlike those of FIG. 4. Similarly, the positive electrode tongues 25 are all identical, their area being for example equal to half that of a negative electrode tab.
- the prismatic accumulator Compared to a spiral accumulator, the prismatic accumulator has the advantage of being more compact (the density of energy is slightly higher). However, maintaining compression in this configuration requires a casing with mechanically reinforced sidewalls, which makes it heavier (hence lower mass density of energy than in the spiral accumulator).
- Figures 7 and 9 show preferred embodiments of the electrical connectors 16 and 26, respectively forming the negative and positive terminals of the battery. These terminals connect the negative and positive electrodes (and more particularly their current collector) to an external electrical circuit, for example a load to supply energy.
- the connectors 16 and 26, which are described in connection with these figures, are compatible with the lead accumulator according to the invention whatever its configuration - for example spiral or prismatic. Their composition and processing technique vary, because the nature of the current collector to which they are attached differs depending on whether this collector belongs to the positive electrode or the negative electrode.
- the negative connector 16 of FIG. 7 is preferably formed of a single piece of lead obtained by a molding process around the connection tabs 15 of the negative electrode ("Cast-On-Strap" process, COS ).
- the choice of lead as a material ensures a secure attachment of the connector 16 to the connection tabs 15, which are also covered with lead (layers 1 1 a-1 1 b).
- the cylindrical accumulator is turned over so that the connecting tongues 15, arranged projecting parallel to one another, are placed in a mold.
- the mold is filled with a molten metal, here lead, then cooled to release the molded part.
- the mold contains the final shape of the negative connector 16, shown in FIG.
- FIGS. 8A and 8B are further views of the negative connector 16 of FIG. 7, taken from the front and from the side, and showing more clearly the connection tabs 15 of the negative electrode.
- the connector 16 comprises a first flat portion 16a molded around the tongues 15 and a second flat portion 16b, in the extension of the first portion 16a.
- the tabs 15 extend perpendicularly to the plane of the portion 16a.
- the thickness of the portion 16a is advantageously between 5 mm and 20 mm.
- the second flat portion 16b also extends in a direction perpendicular to the plane of the portion 16a, but in a direction opposite to that of the tongues 15. Its thickness is advantageously between 5 mm and 15 mm.
- the portion 16b of the connector 16 leaves the housing and constitutes the negative terminal of the accumulator.
- connection tongues 15 each comprise a hole 15 'of so that during the molding step, it is filled with lead. This strengthens the mechanical and electrical connections between the tongues 15 and the connector 16.
- the positive connector 26 of FIG. 9 is advantageously made of titanium, ideally of the same quality (class 1 and / or 2).
- the connector 26 is, for example, obtained by punching a titanium sheet having a thickness of between 0.5 mm and 3 mm, depending on the power of the accumulator (a high thickness is provided in the case of a strong electrical capacity and a high electrical power, and vice versa).
- the connector 26 comprises a first portion 26a and a second portion 26b, which, after folding of the titanium sheet along the axis 260 shown in dotted lines, extends perpendicularly to the portion 26a.
- the portion 26a includes notches 261 for receiving the connection tabs of the positive electrode.
- the notches 261 have a width denoted "I” slightly greater than the thickness of the tongues and their length "L '" substantially corresponds to the length "L” of the tongues (Fig.4).
- Their shape may be rectilinear, as shown in FIG.
- the radius of curvature of the notches 261 then corresponds to the radius of curvature of each tongue, cf. Figs.3A-3B).
- the notches 261 are preferably arranged parallel to each other in the portion 26a.
- Figures 10A and 10B show two modes of attachment of the positive connector 26 on the connection tabs 25 of the positive electrode.
- each tongue end 25 of the positive electrode is inserted into the slots 261 of the connector 26, and then folded so that their free end is pressed against the surface of the portion 26a. Then, each tongue end 25 is attached to the connector portion 26a by a plurality of resistance weld points 262 distributed along each slot 261.
- each tongue 25 is inserted in the slots 261, then cut so that they do not exceed the surface of the portion 26a. Then, each tongue 25 is welded to the portion 26a of the titanium connector along the entire length of the edge inserted in the slots 261. This welding is performed using a laser under an atmosphere comprising a shielding gas, for example argon.
- a shielding gas for example argon.
- the portion 16a of the negative connector 16 and the portion 26a of the positive connector 26 have a trapezoidal shape adapted to connection tongues of variable length. This shape is therefore more particularly suitable for connecting tongues of the spiral accumulator (see Figs.3A-3B).
- the portions 16a and 26a may have a rectangular shape, more suited to connecting tongues of the same length (the slots 261 of the connector 26 are in this case the same length).
- the connectors 16 and 26 of FIGS. 7 to 10 are designed to occupy only a portion of the upper face of the accumulator (FIGS. 3B and 5). Their negative impact on the specific energy and the specific power of the accumulator is thus limited.
- other forms of connectors 16 and 26 than those shown in FIGS. 7 and 9 can be envisaged.
- the outer edge of connector portions 16a and 26a may be rounded, rather than straight, and so coincide with the cylindrical housing of the spiral accumulator.
- the negative electrode 1 of Figure 1 is deposited successively on each of the two faces 10a and 10b of the carbon sheet 10, a lead-based layer (layers 1 1 a-1 1 b) and a layer of active material containing lead (layers 12a-12b).
- the lead-based layers 11a and 11b can be formed by electrodeposition of lead or a lead alloy on the surface of the carbon current collector, for example by applying the operating conditions described in patent EP2313353.
- the copper layers 14a and 14b are electro-deposited on the surface of the carbon sheet 10, before the deposition of the lead-based layers 11a and 11b, according to a procedure also described herein.
- the carbon sheet 10 undergoes, prior to the deposition of the lead layers 11a and 11b, a treatment aimed at increasing its surface roughness.
- a treatment aimed at increasing its surface roughness.
- This treatment can be carried out mechanically, by polishing, brushing or sanding, chemically by thermal treatment with oxygen or by immersion in an oxidizing solution, or electro-chemically by anodic etching (by dipping the carbon sheet in an electrolyte and applying a potential positive).
- NAM negative active material
- the paste of NAM preferably contains lead oxide (PbO), water, sulfuric acid and one or more additives, for example known under the name Anglo-Saxon "expander” and formed of lignosulphonates, BaSO 4 or fine carbon particles.
- the carbon sheet covered with the layers of dough 12a-12b can be laminated with the two sheets of paper 13a and 13b made of glass fibers or of cellulose.
- the dough layers 12a and 12b having a low viscosity can be partially dried before the step of rolling the paper sheets 13a-13b.
- a drying step is not necessary because the paper sheets 13a and 13b absorb excess moisture in the dough.
- Pastes of active material are thixotropic mixtures whose viscosity depends on the mixing speed, between 0.5 and 5 revolutions / s, for example 1 turn / s.
- the formation of the positive electrode 2 comprises successively, on each of the faces 20a-20b of the titanium foil 20 (FIG. 2), the deposition of a layer of semiconducting metal oxide (layers 21a-21b). , then possibly the deposition of a dense layer of lead oxide Pb0 2 (layers 24a-24b) and finally the deposition of a layer of active material containing lead (layers 22a-22b).
- the titanium foil 20 is treated to increase its surface roughness, before receiving the semiconductor metal oxide layers 21a-21b.
- This treatment may be carried out mechanically, by sanding or brushing, and / or chemically by immersion in a solution of hydrochloric acid or oxalic acid (for example for 2 min to 5 min in a boiling solution of 10% hydrochloric acid or for 30 minutes to 60 minutes in a boiling solution of 10-15% oxalic acid).
- the deposition of the semiconductor metal oxide layers 21a-21b can be achieved in various ways, in particular by spray-pyrolysis.
- the solution sprayed onto the substrate contains a solution of SnCl 2 at 0.5 mol / L, a solution of SbCl 3 at 0.05 mol / L and a solution of 0.1 mol / L HCl in a mixture of ethanol and water (40% ethanol, 60% water).
- the layers 24a-24b of lead oxide Pb0 2 are preferably formed by electrodeposition, by mixing a source of dopants in the plating bath, for example NaF for fluorine doping.
- the galvanic bath comprises a solution of lead methanesulfonate (II) at 0.1 ⁇ 1 mol / L, a solution of methanesulfonic acid at 0.1 -0.2 mol / L, a solution containing a cetrimonium salt (bromide, chloride or cetrimonium tosylate tosylate) at 0.05 mol / L and a solution of NaF at 0.01 mol / L.
- PAM paste conventionally comprises lead oxide (PbO), water and sulfuric acid. It is spread on both sides of the titanium sheet covered with Sn0 2 and Pb0 2 layers, for example by squeegee.
- two sheets of paper 23a and 23b made of glass fibers or of cellulose are advantageously laminated on the two active material paste layers 22a and 22b.
- an edge of the carbon sheet and an edge of the titanium foil are not covered with the paste of active material. These edges are intended to form the connecting tongues of each electrode.
- the negative and positive electrodes are in the form of long continuous and flexible strips and are manufactured according to a "roll-to-roll” process, starting from a current collecting sheet (for example carbon or titanium) stored as a coil.
- a current collecting sheet for example carbon or titanium
- This type of process is particularly well suited to the formation of thin film battery electrodes and achieves a high production efficiency.
- FIG. 11 represents a preferred embodiment of this electrode manufacturing method, in which a sheet of paper, serving as a support for the active material of the electrode, is carried on each of the faces of the collector current.
- Two sheets of paper 30a and 30b are, independently of one another, coated with a paste of active material (PAM or NAM depending on the nature of the electrode to be manufactured).
- the paper of the sheets 30a and 30b is commonly known as calving paper because it is suitable for depositing a paste of active material. It is preferably formed of glass fibers, with a structure identical to that of the AGM separators used in lead batteries. Alternatively, it may be formed of fibers of a material other than glass (cellulose, polyester) or a mixture of glass fibers and fibers of this other material.
- the sheets of paper 30a and 30b preferably have a thickness of between 50 ⁇ and 200 ⁇ .
- the steps of squatting the sheets of paper 30a and 30b are preferably carried out simultaneously using two belt-pressing machines.
- the strip-shaped sheets 30a and 30b are each carried by a belt conveyor during the deposition of the active material paste.
- the paper web 30a, coming from a roll 300a is driven by a conveyor belt 40a and covered with a layer of dough 31a, by means of a coating device 41a.
- the paper web 30b, coming from the roll 300b is driven by a conveyor belt 40b and covered with a layer of dough 31b, by means of a coating device 41b.
- the movement of the belts 40a-40b has the effect of progressively unrolling the paper rolls 300a-300b.
- the dough layers 31a and 31b preferably have a thickness of between 100 ⁇ and 500 ⁇ .
- the sheets of paper 30a and 30b are then glued on either side of the current collection sheet 32, by means of the paste of active material.
- the layers 31a and 31b play the role of glue for respectively fixing the paper sheet 30a on a first face of the sheet 32 and the paper sheet 30b on a second opposite face of the sheet 32.
- a pressure can be exerted on the sheets of paper 30a-30b to reinforce this bonding, for example by passing the sheets 30a, 30b and 32 between two calendering rolls 42a-42b.
- the cylinders 42a-42b rotate in opposite directions.
- the sheets of paper 30a-30b are (on one side only) entirely covered with paste of active material and have a width less than that of the current collecting sheet 32.
- an edge of the sheet 32 is devoid of paste of active material (on both sides) and will be used to form the electrode connection tabs.
- the current collecting sheet 32 may be formed of different materials and possibly covered with adhesion and / or anticorrosive layers. Its thickness is preferably between 20 ⁇ and 200 ⁇ .
- the sheet 32 is preferably carbon (negative electrode) or titanium (positive electrode), and the active material paste contains lead.
- the current collecting sheet 32 is a continuous and flexible strip, from a coil 301 and oriented vertically.
- the sheets of paper 30a-30b coated with paste are brought into contact with the sheet 32, in a direction perpendicular to the sheet 32. This arrangement makes it possible to exert an identical pressure on either side of the sheet 32.
- the paste layers 31a and 31b have after bonding substantially the same thickness.
- the sheets of paper 30a-30b thus move toward the sheet 32 in opposite directions.
- the speed of displacement of the sheet 30a on the conveyor 40a is preferably equal to that of the sheet 30b on the conveyor 40b and between 5 cm / s and 1 m / s, advantageously between 5 cm / s and 50 cm. / s.
- the sheet 32 is driven at the same speed of movement by the paper strips 30a and 30b.
- the stack of sheets 30a-31a-32-31b-30b constitutes a multilayer electrode strip, ready for assembly in an accumulator.
- This stack is advantageously laminated, passing it between another pair of cylinders 43a-43b disposed on either side of the current collecting sheet 32.
- This operation is carried out if it is desired to reduce the thickness of the strip electrode, for example when the pressure exerted by the cylinders 42a-42b is not sufficient to achieve the desired thickness. Thus, it is easier to adjust the thickness of the electrode and perfect the adhesion between the different layers of the stack.
- Another optional step of the manufacturing method consists in sticking against the multilayer electrode strip a separator sheet 33, in preparation for the assembly of the positive and negative electrodes of the accumulator.
- the separator sheet 33 is preferably an AGM-type strip from a roll 302. It is pressed against the electrode strip by means of a pair of calendering rolls 44a-44b.
- the electrode strip (with or without AGM separator 33) can also be wound into a coil 303 immediately after its manufacture.
- the electrode coil 303 can be wound with an adhesive and then placed in an oven at 60-120 ° C for 12-24 hours in order to dry and bake the paste of active material.
- This electrode manufacturing process makes it possible to deposit, quickly and with good precision (+/- 50 ⁇ ), two layers of paste of active material on either side of a current collecting sheet.
- battery electrodes of large capacity having a total thickness of between 100 ⁇ and 1000 ⁇ , and preferably between 200 ⁇ and 600 ⁇ , can be produced in large quantities and at a lower cost.
- each coating device 41 a-41 b comprises a dough tank 410, a spreading roll 41 1 and at least one mixer 412 arranged in the tank 410.
- a doctor blade 413 is disposed at the output of the coating device to adjust the thickness of the paste layer deposited on the moving paper sheet.
- the paste of active material is, in this embodiment of the step of flattening, spread on each of the paper sheets 30a and 30b by means of the spreading cylinder 41 1 and smoothed by the doctor blade 413.
- the active material paste is deposited on the sheets of flattening paper 30a-30b in the form of rectilinear cords 31 '.
- the coating devices 41a-41b comprise a plurality of coating nozzles 414, instead of the spreading roll 41 1 and the doctor blade 413.
- the nozzles 414 are aligned perpendicular to the direction of rotation. moving the paper strips 30a-30b, symbolized by the arrows 45, so that the dough strips 31 'are parallel to each other.
- the nozzles 414 are fed with paste of active material through the tank 410.
- This implementation variant is more suitable for pastes of high viscosity than the method called "Doctor Blade" shown in Figure 1 1. Since the scroll speed of the sheets of paper 30a-30b and the flow of dough in the nozzles 414 are constant, it is possible to precisely control the dough load (ie the basis weight per unit area) deposited on each sheet. In addition, this technique makes it easier to interrupt, that is to say at any time, the deposit of paste of active material. This is particularly advantageous when it is desired that one end of the paper sheets, and therefore of the electrode strip, is not covered with paste. For example, in a spiral electrode assembly (see FIG.
- the step of assembling the positive and negative electrodes consists in pressing the electrodes against each other, separating them from at least one sheet of porous and electrically insulating material, and shaping the stack that results this plating, for example by folding, cutting, winding ... During this assembly step, one can also proceed to shaping the connection elements of the electrode. All these operations can also be performed within the same assembly equipment.
- FIG. 13 represents a preferred embodiment of the step of assembling a spiral accumulator, in which the negative electrode 1 and the positive electrode 2 have the form of continuous and flexible bands, respectively provided by storage coils 303 and 303 '.
- the coils 303 and 303 ' which are loaded into the equipment, each contain a winding of a single electrode, positive or negative.
- the lower coil 303 contains the negative electrode strip 1, while the upper coil 303 'contains the positive electrode strip 2.
- the negative electrode coil 303 and the positive electrode coil 303' have, preferably, was produced during the step of Figure 1 1.
- a separator sheet 3 is adhered to each electrode, by means of the active material of the electrode. This bonding may have been performed immediately after the manufacture of the electrode, as mentioned previously in connection with FIG.
- the separator sheets 3 are then contained in the coils 303 and 303 '.
- An alternative is to provide four coils (instead of two): two coils containing only the positive and negative electrode strips and two additional coils for the separator sheets. The four coils are unwound simultaneously in pairs, each separator sheet being laminated on an electrode strip. As the coils 303 and 303 'are unwound, the electrode strips 1 and 2 progress in the assembly machine and are processed in parallel with each other. This treatment comprises in particular the brushing and cutting of the electrode portions without active material, to form the connection tabs on each of the electrodes.
- Each electrode-separator pair may optionally pass between a pair of rolling rolls 45, in order to reduce its thickness.
- the electrode strips 1 and 2 are pressed against each other, interposing between them one of the two sheets 3 of porous material.
- the electrode strips 1-2 and their associated separator sheets 3 are introduced between two calendering rolls 46.
- the stack of electrodes 1-2 and separator sheets 3 is wound on itself, so as to compress the porous material.
- the porous material of the sheet 3 disposed between the two electrode strips 1-2 impregnates positive and negative active materials, which definitively binds the two electrodes.
- the sheets 3 of porous material are partially impregnated with water during this step. This makes it possible to achieve a high level of compression - and thus to improve the life of the accumulator - because the porous material is less elastic while being wet.
- the stack can be held firmly wound by an adhesive tape or a plastic film, before being placed in a cylindrical housing.
- the electrode manufacturing method of FIGS. 11-12 and the assembly step of FIG. 13 are obviously applicable to the lead accumulator technology described with reference to FIGS. 1 to 6, notably using a sheet titanium collector for the positive electrode and a carbon collector foil for the negative electrode.
- the titanium collector sheet may be coated on both sides of the semiconductor metal oxide layer (Sn0 2 ) and advantageously the dense layer of lead oxide (Pb0 2 ), as indicated above.
- the carbon collecting sheet may be covered on both sides with the lead-based layer and advantageously with the copper layer.
- the assembly of the electrodes is followed by an electrode activation step, where the NAM paste and the PbO-based PAM paste are converted into lead sulphate PbSO 4 , after which the accumulator can be used normally ( starting with a training load).
- Ni-Zn with nickel oxide or hydroxide on one side and zinc oxide on the other;
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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FR1454930A FR3021810B1 (fr) | 2014-05-30 | 2014-05-30 | Accumulateur au plomb-acide, procede de fabrication d'un tel accumulateur et procede de fabrication d'une electrode |
FR1454933A FR3021812B1 (fr) | 2014-05-30 | 2014-05-30 | Accumulateur au plomb-acide, procede de fabrication d'un tel accumulateur et procede de fabrication d'une electrode |
PCT/FR2015/051417 WO2015181508A1 (fr) | 2014-05-30 | 2015-05-29 | Accumulateur au plomb-acide et procédé de fabrication d'un tel accumulateur |
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EP3149790A1 true EP3149790A1 (fr) | 2017-04-05 |
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EP15729544.5A Withdrawn EP3149790A1 (fr) | 2014-05-30 | 2015-05-29 | Accumulateur au plomb-acide et procédé de fabrication d'un tel accumulateur |
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US (1) | US20170155171A1 (fr) |
EP (1) | EP3149790A1 (fr) |
JP (1) | JP2017517131A (fr) |
WO (1) | WO2015181508A1 (fr) |
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JP6756223B2 (ja) * | 2016-10-03 | 2020-09-16 | 株式会社Gsユアサ | 鉛蓄電池及びその製造方法 |
IT201700019129A1 (it) * | 2017-02-21 | 2018-08-21 | Manz Italy Srl | Apparato e metodo di lavorazione |
IT201700019147A1 (it) * | 2017-02-21 | 2018-08-21 | Manz Italy Srl | Apparato e metodo di lavorazione |
HUE061135T2 (hu) * | 2017-02-21 | 2023-05-28 | Manz Italy Srl | Megmunkáló berendezés és eljárás |
DK3450356T3 (da) * | 2017-08-28 | 2023-05-08 | Laitram Llc | Separering af produkter, som transporteres ved hjælp af elektroadhæsion |
CN113196517A (zh) * | 2018-11-15 | 2021-07-30 | 高级电池概念有限责任公司 | 可用于平衡电池组件的功率和能量密度的活性材料 |
KR102424556B1 (ko) * | 2020-08-20 | 2022-07-25 | 한국앤컴퍼니 주식회사 | 표면적이 증가된 납축전지용 기판 제조 방법 |
CN113224312B (zh) * | 2021-04-15 | 2022-07-29 | 淄博火炬能源有限责任公司 | 钛/铜基长寿命高功率铅酸蓄电池及其制备方法 |
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-
2015
- 2015-05-29 WO PCT/FR2015/051417 patent/WO2015181508A1/fr active Application Filing
- 2015-05-29 EP EP15729544.5A patent/EP3149790A1/fr not_active Withdrawn
- 2015-05-29 JP JP2017514981A patent/JP2017517131A/ja active Pending
- 2015-05-29 US US15/314,819 patent/US20170155171A1/en not_active Abandoned
Non-Patent Citations (2)
Title |
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None * |
See also references of WO2015181508A1 * |
Also Published As
Publication number | Publication date |
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US20170155171A1 (en) | 2017-06-01 |
WO2015181508A1 (fr) | 2015-12-03 |
JP2017517131A (ja) | 2017-06-22 |
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