WO2021034455A1 - Procédé de commande d'une couche de corrosion - Google Patents

Procédé de commande d'une couche de corrosion Download PDF

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Publication number
WO2021034455A1
WO2021034455A1 PCT/US2020/043679 US2020043679W WO2021034455A1 WO 2021034455 A1 WO2021034455 A1 WO 2021034455A1 US 2020043679 W US2020043679 W US 2020043679W WO 2021034455 A1 WO2021034455 A1 WO 2021034455A1
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grid
cathode
carbon nanotubes
battery
corrosion layer
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Jeremy Meyers
Catherine MCCARRELL
Paul Everill
Steven SWOGGER
Kurt W. Swogger
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Molecular Rebar Design LLC
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Molecular Rebar Design LLC
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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
    • H01M4/20—Processes of manufacture of pasted electrodes
    • H01M4/21—Drying 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/12—Construction or manufacture
    • H01M10/128—Processes for forming or storing electrodes in the battery container
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/446—Initial charging measures
    • 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
    • H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H01M4/22—Forming of electrodes
    • H01M4/23—Drying or preserving electrodes after forming
    • 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

  • Corrosion is a significant problem for the battery industry, particularly in very hot climates close to the equator.
  • lead acid batteries through their intrinsic reduction/oxidation (redox) chemistries, must corrode to a certain extent throughout life, runaway corrosion of the positive electrode’s (cathode’s) current collector (the “grid”) can lead to premature failure of the battery as the electrode decomposes, losing the contact it has with the active material, rendering it incapable of continuing electrochemical reactions.
  • Corrosion can be exacerbated in high temperature situations when the usual corrosion of the grid becomes intensified through simple thermodynamic principles (i.e. more heat energy, more corrosion). When this happens the grid thins, active material and grid pieces can become detached, and sections of the electrode can fall off and cause either shorting or premature capacity loss, both of which will end the battery’s service.
  • the thinning of the grid can also lead to migration of the grid alloys towards the negative electrode (anode) where they can combine to trigger adverse side reactions, such as water loss or gassing.
  • Antimony is one such example of this detrimental migration effect, with what is termed Antimony Poisoning being a well-established issue in certain applications which have not yet moved away from antimony-based grid designs.
  • the corrosion layer is the outer most layer of the current collector, or grid, which is in direct contact with the active material (lead compounds and acid). It is the glue that holds the active material onto the grid.
  • the layer begins to take shape during the curing stages of battery production where the active material-coated grids are exposed to high heat and humidity for prolonged periods, often 2-4 days, but it is not until the battery’s first charge, or “formation”, that the layer achieves its final form through acid-based corrosion of the grid itself.
  • the production of a corrosion layer is a necessary step in battery formation since without a firm connection between active material and grid, the material will slough off and lead to Premature Capacity Loss as the active compounds detach from the current collector.
  • This corrosion layer is also the first line of defense against further corrosion of the grid since it forms a sheath around the grid, albeit it frequently imperfect. Many factors affect the structure and composition of the corrosion layer and, if well prepared, that structure/composition can help to ensure strong adhesion between the grid and the active material. A thin corrosion layer can make the plates prone to paste shedding or delamination. Grids made with low calcium, high tin, or silver alloys are so resistant to corrosion that it is difficult to get proper attachment (Prengaman). Alterations of the corrosion layer, or the way in which it corrodes would directly manipulate the way that the active material and grid function together and, in the right circumstances, provide enhancements to corrosion resistance.
  • Mahato simulated the cyclic corrosion of a positive grid by linearly sweeping both pure Pb and Pb-Sb alloys through the potential range that the positive plate is expected to experience.
  • This cyclically corroded positive grid developed a multiphase corrosion layer with a b-PbOi rich exterior and a tet-PbO + a-PbCh inner layer.
  • Presence of antimony in the alloy reduces the intensity of stress cracking, and this might explain why there is a difference between steady-state corrosion on overcharge and corrosion during cycling.
  • the bulk positive active material also undergoes changes with cycling.
  • Lailler noted that the PbCh grain size grows during battery life.
  • XRD spectra shows that the a-PbCh tends to disappear during cycling; the a phase is unstable at low pH, so the formation of b-PbOi is easier during charging. They suggest that the microstructural evolution halts when the b-PbOi crystallites become too large. They lose contact with the positive plate and no longer take part in the electrochemical reactions.
  • Rogatchev and Pavlov state that the composition of the corrosion layer is non-stoichiometric lead oxide, PbO n , where n varies between 1.4 and 1.95. This implies that the crystal lattice of the oxide contains both Pb 2+ and Pb 4+ ions.
  • Corrosion failures are typically addressed by alloy changes, ground-up changes to the grid design or method of manufacture or, less frequently, with inorganic salts added directly to the paste like SnSCri or NaTkBCri whose mechanism of action is poorly understood. Alloys can be changed from Pb-Sb to Pb-Sn-Ca or Pb-Ag or more exotic compositions utilizing barium, for example. This is expensive and hard to implement correctly and can negatively affect the chargeability and life of the battery.
  • Preferred grid designs for automotive batteries are typically very thin and produced via certain equipment to give a “punched”, “concasted”, “conrolled”, or “expanded” design, referring to how the gaps in the grid are developed. These are traditionally poorly corrosion resistant with some manufacturers preferring older “book molded” grid designs which have better corrosion resistance at the expense of manufacturability and production speed.
  • the positive corrosion issue can be intensified through both overworking of positive electrode (higher degree of corrosion) or increased side reactions in the negative electrode which can lead to higher water loss from the battery and, therefore, concentration of the acid which further increases corrosion of the positive electrode (Maleschitz).
  • concentration of the acid which further increases corrosion of the positive electrode (Maleschitz).
  • the present disclosure in various embodiments, describes a process for controlling a corrosion layer in a lead acid battery, comprising at least one anode and at least one cathode, the anode grid and the cathode grid in at least partial contact with respective mixtures of leady oxide paste, where the process comprising the steps of: a) incorporating a plurality of discrete carbon nanotubes at a concentration from about 0.01 to about 0.10 weight percent in a leady oxide mixture comprising 60-85 % PbO and 15-40% Pb paste, b) charging/forming the resultant lead-acid battery using a net quantity of charge of about 1.5*C2o to about 4*C2o Amp hour at a current rate between about C2o/20h and C2o/3h, where C20 is the amount of charge the battery was designed to maximally discharges over 20 h in units of Amphour, c) thereby forming on at least one anode grid and/or at least one cathode grid, a corrosion layer with
  • the process describes the formation of a corrosion layer formed only on the cathode grid of a lead acid battery.
  • the process describes a plurality of carbon nanotubes which are only in leady oxide paste material contacting the cathode grid prior to formation.
  • the process describes the formation of a corrosion layer formed only on the anode grid.
  • the process describes a plurality of carbon nanotubes which are only in the mixture of 60-85 % PbO and 15-40% Pb paste material contacting the anode grid.
  • One embodiment of the process comprises a carbon nanotube concentration from about 0.03 to about 0.10 weight percent with respect to the mixture of 60-85 % PbO and 15-40% Pb.
  • a yet further embodiment of the process comprises a method for first charging, or forming the lead-acid battery using a net quantity of charge from 1.5*C2o to 4*C2o Amphours, more optimally between 2.0*C2o and 3.5*C2o Amphours, and more optimally between 2.1*C2o and 3.0*C2o Amp hours (where C20 is the amount of charge the battery was designed to maximally discharge over 20 h in units of Amp hour).
  • a plurality of discrete carbon nanotubes that have at least 1% total oxidation, but with more than 20% greater oxidation percentage on the outer surface of the carbon nanotube than the inner surface of the innermost wall, can be utilized.
  • the process describes a plurality of discrete carbon nanotubes which are single-walled carbon nanotubes.
  • the process describes a plurality of discrete carbon nanotubes which are multi-walled carbon nanotubes.
  • Another embodiment of the process utilizes at least one anode or at least one cathode which does not comprise an alloy selected for the group consisting of Pb-Sb, Pb-Ca/Sn, Pb-Ag, combinations thereof and derivatives thereof.
  • the process describes an improvement for a lead acid battery comprising of at least one cathode grid having a corrosion layer from about 10 to about 250 microns thickness wherein the cathode material comprises a reaction product from the process of Claim 1 comprising >75% PbCh and less than .01 weight of carbon nanotubes.
  • the process describes an improvement for a lead acid battery comprising of at least one cathode grid having a corrosion layer from about 10 to about 250 microns thickness wherein the cathode material comprises a reaction product from the process of Claim 1 comprising >75% PbCh and a non-detectable weight of carbon nanotubes.
  • the process forms a corrosion layer which is monophasic, consisting of only one clearly-defined, visible, and uniform region of acid and/or oxygen ingress.
  • the process produces a plate which is at least 10% more resistant to mechanical stresses, such as vibrating or crushing.
  • Another embodiment of the process produces a battery which is at least 10% more resistant to corrosion on the cathode grid as defined by standard life cycling techniques.
  • Another embodiment of the process produces a plate with at least 20% improved grid-mass adhesion in the pre-charged/formed state.
  • the process produces a plate with at least 20% improved grid-mass adhesion in the post-charged/formed state.
  • Another embodiment of the process comprises a method to reduce metal released from the cathode grid.
  • the mixture of 60-85 % PbO and 15-40% Pb paste is substituted for a mixture containing 10-50% red lead (Pb304), 10-70% PbO, and 15-40% Pb.
  • the process is applied to monopolar battery design.
  • the process is applied to bipolar battery designs.
  • the process is applied to a lead-acid battery in which at least one of the anodes comprises a capacitive carbon coating.
  • Figure 1A shows the positive plate failure mode results.
  • Figure IB shows a control corrosion layer and a experimental corrosion layer.
  • Figure 2A shows a comparison of pore area.
  • Figure 2B shows a comparison of pore size.
  • Figure 3A shows a view of batteries built with control positives.
  • Figure 3B shows a view of batteries built with positive electrodes which included discrete carbon nanotubes.
  • Figure 3C shows an evaluation of the plates post-cycling.
  • Figure 4A shows an Energy-Dispersive X-Ray (EDX) Spectroscopy reading.
  • Figure 4B shows an Energy -Dispersive X-Ray (EDX) Spectroscopy reading.
  • Figure 4C shows an Energy -Dispersive X-Ray (EDX) Spectroscopy reading.
  • Figure 4D shows an Energy-Dispersive X-Ray (EDX) Spectroscopy reading.
  • nanotubes that may be useful herein and their methods of preparation are described in, for example, U.S. Patent No. 10,414,656 which is incorporated herein by reference. Useful nanotubes and their methods of preparation are also described in U.S. Patent No. 9,636,649 which is incorporated herein by reference.
  • a mixture of 0.5% to 5% carbon nanotubes, preferably 3%, by weight is prepared with CNano grade Flotube 9000 carbon nanotubes and 65% nitric acid. While stirring, the acid and carbon nanotube mixture is heated to 70 to 90 degrees C. for 2 to 4 hours. The formed oxidized carbon nanotubes are then isolated from the acid mixture. Several methods can be used to isolate the oxidized carbon nanotubes, including but not limited to centrifugation, filtration, mechanical expression, decanting and other solid-liquid separation techniques. The residual acid is then removed by washing the oxidized carbon nanotubes with an aqueous medium such as water, preferably deionized water, to a pH of 3 to 4.
  • an aqueous medium such as water, preferably deionized water
  • the carbon nanotubes are then suspended in water at a concentration of 0.5% to 4%, preferably 1.5% by weight.
  • the solution is subjected to intensely disruptive forces generated by shear (turbulent) and/or cavitation with process equipment capable of producing energy densities of 106 to 108 Joules/m.sup.3.
  • Equipment that meet this specification includes but is not limited to ultrasonicators, cavitators, mechanical homogenizers, pressure homogenizers and microfluidizers (Table 1).
  • One such homogenizer is shown in U.S. Pat. No. 756,953, the disclosure of which is incorporated herein by reference.
  • the oxidized carbon nanotubes are discrete and individualized carbon nanotubes.
  • a plurality of discrete oxidized carbon nanotubes results from this process, preferably at least about 60%, more preferably at least about 75%, most preferably at least about 95% and as high as 100%, with the minority of the tubes, usually the vast minority of the tubes remaining entangled, or not fully individualized.
  • a mixture of 0.5% to 5% carbon nanotubes, preferably 3%, by weight is prepared with CNano Flotube 9000 grade carbon nanotubes and an acid mixture that consists of 3 parts by weight of sulfuric acid (97% sulfuric acid and 3% water) and 1 part by weight of nitric acid (65-70 percent nitric acid).
  • the mixture is held at room temperature while stirring for 3-4 hours.
  • the formed oxidized carbon nanotubes are then isolated from the acid mixture.
  • Several methods can be used to isolate the oxidized carbon nanotubes, including but not limited to centrifugation, filtration, mechanical expression, decanting and other solid-liquid separation techniques.
  • the acid is then removed by washing the oxidized carbon nanotubes with an aqueous medium, such as water, preferably deionized water, to a pH of 3 to 4.
  • an aqueous medium such as water, preferably deionized water
  • the oxidized carbon nanotubes are then suspended in water at a concentration of 0.5% to 4%, preferably 1.5% by weight.
  • the solution is subjected to intensely disruptive forces generated by shear (turbulent) and/or cavitation with process equipment capable of producing energy densities of 106 to 108 Joules/m.sup.3.
  • Equipment that meet this specification includes but is not limited to ultrasonicators, cavitators mechanical homogenizers, pressure homogenizers and microfluidizers (Table 1).
  • the oxidized carbon nanotubes become oxidized, discrete carbon nanotubes.
  • a plurality of discrete oxidized carbon nanotubes results from this process, preferably at least about 60%, more preferably at least about 75%, most preferably at least about 95% and as high as 100%, with the minority of the tubes, usually the vast minority of the tubes remaining entangled, or not fully individualized.
  • Embodiments of nanotubes with targeted oxidation may include: 1.
  • a composition comprising a plurality of discrete carbon nanotubes, wherein the discrete carbon nanotubes comprise an interior and exterior surface, each surface comprising an interior surface oxidized species content and an exterior surface oxidized species content, wherein the interior surface oxidized species content differs from the exterior surface oxidized species content by at least 20%, and as high as 100%.
  • the composition of embodiment 1 wherein the interior surface oxidized species content is up to 3 weight percent relative to carbon nanotube weight, preferably from about 0.01 to about 3 weight percent relative to carbon nanotube weight, more preferably from about 0.01 to about 2, most preferably from about 0.01 to about 1. 4.
  • composition of embodiment 1 wherein the exterior surface oxidized species content is from about 1 to about 6 weight percent relative to carbon nanotube weight, preferably from about 1 to about 4, more preferably from about 1 to about 2. 5.
  • the composition of embodiment 1 wherein the interior and exterior surface oxidized species content totals from about 1 to about 9 weight percent relative to carbon nanotube weight.
  • a composition comprising a plurality of discrete carbon nanotubes, wherein the discrete carbon nanotubes comprise an interior and exterior surface, each surface comprising an interior surface and an exterior surface oxidized species content, wherein the interior surface oxidized species content comprises from about 0.01 to less than about 1 percent relative to carbon nanotube weight and the exterior surface oxidized species content comprises more than about 1 to about 3 percent relative to carbon nanotube weight. 7.
  • composition of embodiment 6 wherein the discrete carbon nanotubes comprise a plurality of open ended tubes. 8. The composition of embodiment 6 wherein the plurality of discrete carbon nanotubes comprise a plurality of open ended tubes. 9. The composition of embodiment 1 wherein the discrete carbon nanotubes comprise a plurality of open ended tubes.
  • Example 1 Construction of a Lead-Acid Battery Implementing the Disclosed Process
  • a lead-acid battery is constructed over a series of steps, two of which are modified in the present disclosure. Specifically, the mixing process (1) is modified to include a plurality of discrete carbon nanotubes and the formation process (5) is modified to elicit construction of the intended corrosion layer on at least one anode or at least one cathode of a lead-acid battery. This corrosion layer is in at least partial contact with lead oxide paste and the lead or lead-alloy grid.
  • Paste Mixing Lead- Acid Battery construction begins with the mixing of active materials which typically comprise Leady Oxide (defined as a mixture of 60-85 % PbO and 15-40% Pb formed through the incomplete aid oxidation of pure Pb ingots by either heated ball-milling or a Barton Pot furnace), reinforcing fibers, water, acid, and, in the case of the negative active mass, a quotient of Expander (a mixture of lignin sulfonate, barium sulfate, and carbon). Additional additives are in existence, but this list details the most basic lead-acid battery paste mixture.
  • active materials typically comprise Leady Oxide (defined as a mixture of 60-85 % PbO and 15-40% Pb formed through the incomplete aid oxidation of pure Pb ingots by either heated ball-milling or a Barton Pot furnace), reinforcing fibers, water, acid, and, in the case of the negative active mass, a quotient of Expander (a mixture of lignin
  • the dry ingredients are added to a planetary or double-planetary mixer, for example, mixed for a short period, combined with water, mixed again, and introduced to a quantity of acid over an extended period to control temperature increases as the chemical reactions take place.
  • a plurality of discrete carbon nanotubes is introduced into the leady oxide paste as a fluid suspension of no less than 0.3 percent solids towards an in-paste concentration of about 0.01 to about 0.10 weight percent with respect to the mass of leady oxide in the paste alongside the water.
  • Some manufacturers change the order of addition to adapt to their equipment or climate, but the discrete carbon nanotubes are always added alongside the water addition and always before the acid addition.
  • Final paste density, moisture analysis, and/or Humboldt penetration are typically used as quality controls to determine adequate paste consistency.
  • the addition of discrete carbon nanotubes to the paste does not change the density appreciably but will change the rheology of the mixture which impacts, in some cases, the feel of the mixture and enhances its workability.
  • Gridding/Plate Production Once the paste mixture has successfully reached its Quality Control benchmarks, the material is applied to to a lead or lead-alloy grid either manually or mechanically to produce a paste-coated grid. These grids adopt various designs depending on application and system of manufacture. Grids can be produced from molten lead alloy through various means comprising “book molding”, “con-casting”, “con-rolling”, “punching”, and “expanding; details of which are commonly understood by those familiar with the art (Pavlov, Garche). The process disclosed is applicable to the list comprising these grid designs. After the paste material is applied to the grid, it is often passed through a flash drying oven which dries the outer layer of the plate and makes it easier to handle in subsequent steps. The flash drying oven is usually held at temperatures over 75 °C but residence time is less than a few minutes.
  • the paste-applied, flash-dried grids (aka “the plate”) are then loaded into a second, specialized oven which is designed to nurture the growth of specific crystal types inside the plate; a process known as curing.
  • the plate By storing these grids in high- humidity ovens, water can move in and out of the plate as crystal morphologies take shape on the soon-to-be-active materials and corrosion processes continue on the residual, free lead (Pb°) in the material, and the grid itself.
  • the environment is held at >70% humidity and ⁇ 75 °C.
  • Curing conditions vary by manufacturer and application, but the process disclosed requires only a successful cure measured by analysis of the finished plate components comprising free Pb° content ⁇ 7.5% and tribasic-lead sulfate (3PbO PbSCri ⁇ O, or “3BS”) or tetrabasic-lead sulfate (4PbO PbSCri, or “4BS”) or combinations thereof >20%, more optimally ⁇ 5% Pb° and >30% 3BS or 4BS or combinations there of, and more optimally ⁇ 2% Pb°, and >35% 3BS or 4BS or combinations thereof.
  • a drying step is employed to drive off any remaining water from the plates. In this step, humidity is held ⁇ 15% and temperature is held >75 °C.
  • process quality control targets comprise a plate moisture level ⁇ 2%.
  • additives could be added to the acid including NaS04 or MgS04, gelation agents, or polymers.
  • Two posts, protruding from the battery at the ends of the series circuit, will be the physical attachment point for the battery rectifier (charger) and the end use application (ex. car electrical system)
  • Formation A specifically modified formation is critical for the process disclosed. Formation is the term used to describe the battery’s first charge which acts to bring the battery materials from their inactive cured/dried state into their active forms, specifically by reducing Pb0/3BS/4BS/lBS/PbS04/PbC03 minerals to Pb° on the anode/negative plate and oxidizing Pb0/3BS/4BS/lBS/PbS04/PbC03 minerals to PbC on the cathode/positive plate.
  • There are many protocols which have been utilized in the field including constant current charging, pulsed charging when current is intermittently delivered to the battery, constant temperature charging when current is defined by the input required to keep a battery at a certain temperature, and other more unique profiles.
  • the battery’s formation must be modified so that the desired corrosion layer may form.
  • the battery is charged using a net quantity of charge of about 1.5*C2O to about 4*C2o Amphour, where C20 is the amount of charge the battery was designed to maximally discharge over 20 h in units of Amp hour. This prevents over forming which negatively affects the discrete carbon nanotube-developed positive plate structure through a series of undesired processes comprising intense gas bubble development within the plate, excess heat generation in the battery, higher water loss leading to increased acid concentrations, and a litany of other events.
  • the battery is charged using a net quantity of charge of about 2.0*C2o and 3.5*C2o Ah, and still more optimally between about 2.1*C2o and 3.0*C2O Ah.
  • the rate at which the current is delivered is also important since the battery, in its early charging, handles high currents poorly and this can lead to paste shedding, undesired crystal morphologies in the plate and, from a more fiscal point of view, inefficient use of the rectifier energy which increases overall cost of manufacture.
  • a final type of first charging is known as Tank Formation where NAM and PAM plates are formed outside of the case in a large, acid filled vat prior to strapping, tabbing, posting, and cell assembly.
  • the tank formation tactic is particularly popular with Valve- Regulated Lead-Acid batteries and very large-format flooded batteries where water loss incurred during the formation process is not replaceable and therefor held within very tight specifications or plate thickness or weight lead to decreased formation efficiencies that are mitigated by out-of-case formation, respectively.
  • the formulae disclosed prior for charge input and charge rate break down since there is no intended C20 available for a tank of battery plates.
  • the battery plates are charged using a net quantity of charge in units of Amp hour equal to about 200*(IPRAM * X) to about 950*(mpAM * X), more optimally about 250*(IPRAM *X) to about 500*(IPRAM * X), and still more optimally about 260*(IPRAM * X) to about 350*(IPRAM * X), where I ⁇ RAM is the total mass of positive active material in kilograms to be formed in the bath including only the active material weight and excluding grid weight of all plates in the bath, and X is the solids percentage of mpAM which corrects the formula for any moisture still contained in the plate.
  • X can be calculated using moisture analyzing devices such as a Torball ATS60, or by simply measuring the weight of the plate before and after extensive drying; either method will return a solids percentage.
  • PAM and NAM plates should be balanced such that the active material weight, not including the weight of the grids themselves, is within the ratio of P/N of about 1.05 to 1.30, more optimally 1.07 to 1.25, as is understood to those familiar with the art.
  • the Tank Formation process should occur over a period of 15-25 h for most applications.
  • the discrete carbon nanotubes are considered a sacrificial agent responsible for the structural rearrangement and reinforcement of the active material in the cured/dried state which, when combined with a specific formation procedure, act to generate the desired corrosion layer.
  • Example 2 Process-Induced Corrosion Layer Improvements Provide Enhanced Cyclability at 50 °C
  • Preparation of Material Positive paste mixtures were prepared by mixing 680 kg of leady oxide with -0.2% standard polypropylene fiber for a period of 2 mins followed by a volume of battery-grade water. Discrete carbon nanotubes were added to the mixture by substituting a part of the standard, control quantity of battery -grade water with a volume of discrete carbon nanotube suspension such that the final concentration of the discrete carbon nanotubes relative to the weight of leady oxide was 0.1%. These components were mixed for an additional 2 mins and then 1.4 spgr acid was slowly added to the paste over the course of 5 mins. After the mixing period was complete, density was confirmed to be -4 g/mL. Pb-Sb Grids were pasted with material using standard equipment and then cured in a high humidity oven for 32-48h at 45-50 °C prior to a 24h drying step at 90 °C and low humidity.
  • Preparation of Material 1000 g of leady oxide (20% Free Pb) was mixed with 2 g of Kanecaron fiber and mixed for 1 min. 69.5 mL of battery-grade water and 33.3 mL of a discrete carbon nanotube suspension were added such that the final concentration of the nanomaterial attenuator was 0.1% with respect to the weight of the leady oxide and the material was mixed again for 1 min. Over the course of 5 mins, 113 g of 1.4 spgr acid was added to the mixture to start the reactions. After the mixing procedure, the density of the resultant paste was 4.25+/-0.05 g/mL, by pycnometer (density cup).
  • Example 4 Process-Attenuated Corrosion Layer Is Created During Formation and Endures
  • Lead- Acid battery pastes were manufactured with a standard SLI mix of leady oxide, water, and 1.4 spgr acid. Solids were mixed first for 3 mins, followed by a 5 min water or water plus attenuator suspension addition, and then the acid was added over the course of 12 mins as the mixture was agitated. Discrete carbon nanotube suspension was added such that the final concentration of solids was 0.1% with respect to leady oxide. This mixture produced a paste with density of 4.2 g/mL. Finished paste was then used to produce full plates using Pb-Ca alloy grids. These plates were cured and dried by standard conditions (high humidity /low heat for 32h, low humidity /high head for 16h).
  • Example 5 Process-Developed Corrosion Layer Is Thinner, Monophasic, and Sharply Transitioning
  • Formation included a total of over 4.2*C2O Ah (within our disclosed process limits) administered at charge rates between 0.25- 0.44*C2O (within our disclosed process limits). These are within the required ranges for formation of the nanomaterial-attenuated corrosion layer.

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  • Electrochemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
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Abstract

La présente invention, dans divers modes de réalisation, décrit un procédé de commande d'une couche de corrosion dans un accumulateur au plomb, comprenant au moins une anode et au moins une cathode, la grille d'anode et la grille de cathode au moins partiellement en contact avec des mélanges respectifs de pâte d'oxyde de plomb, ce qui confère une durée de vie améliorée dans des environnements à forte intensité de corrosion.
PCT/US2020/043679 2019-08-19 2020-07-27 Procédé de commande d'une couche de corrosion Ceased WO2021034455A1 (fr)

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CN117737735A (zh) * 2023-12-12 2024-03-22 江苏理士电池有限公司 一种铅酸蓄电池板栅腐蚀剂配方及其制备方法
PL444716A1 (pl) * 2023-04-30 2024-11-04 Innbat Spółka Z Ograniczoną Odpowiedzialnością Sposób wytwarzania masy czynnej płyty dodatniej i ujemnej akumulatora ołowiowo-kwasowego, masy czynne wytworzone tym sposobem, oraz akumulator ołowiowo-kwasowy wykorzystujący te masy czynne
PL448970A1 (pl) * 2024-06-25 2025-08-04 Politechnika Poznańska Masa aktywna elektrod akumulatora kwasowo-ołowiowego
PL449582A1 (pl) * 2024-08-23 2026-03-02 Politechnika Poznańska Zastosowanie materiału węglowego pozyskanego w procesie karbonizacji wełny owczej pranej, jako dodatku do materiału elektrodowego akumulatora kwasowo-ołowiowego

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL444716A1 (pl) * 2023-04-30 2024-11-04 Innbat Spółka Z Ograniczoną Odpowiedzialnością Sposób wytwarzania masy czynnej płyty dodatniej i ujemnej akumulatora ołowiowo-kwasowego, masy czynne wytworzone tym sposobem, oraz akumulator ołowiowo-kwasowy wykorzystujący te masy czynne
CN117737735A (zh) * 2023-12-12 2024-03-22 江苏理士电池有限公司 一种铅酸蓄电池板栅腐蚀剂配方及其制备方法
CN117737735B (zh) * 2023-12-12 2024-10-25 江苏理士电池有限公司 一种铅酸蓄电池板栅腐蚀剂配方及其制备方法
PL448970A1 (pl) * 2024-06-25 2025-08-04 Politechnika Poznańska Masa aktywna elektrod akumulatora kwasowo-ołowiowego
PL449582A1 (pl) * 2024-08-23 2026-03-02 Politechnika Poznańska Zastosowanie materiału węglowego pozyskanego w procesie karbonizacji wełny owczej pranej, jako dodatku do materiału elektrodowego akumulatora kwasowo-ołowiowego

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