WO2021046373A1 - Additifs d'électrolyte pour batteries au plomb-acide - Google Patents

Additifs d'électrolyte pour batteries au plomb-acide Download PDF

Info

Publication number
WO2021046373A1
WO2021046373A1 PCT/US2020/049440 US2020049440W WO2021046373A1 WO 2021046373 A1 WO2021046373 A1 WO 2021046373A1 US 2020049440 W US2020049440 W US 2020049440W WO 2021046373 A1 WO2021046373 A1 WO 2021046373A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrolyte
lead
stpp
positive
acid battery
Prior art date
Application number
PCT/US2020/049440
Other languages
English (en)
Inventor
Maria Borisova Matrakova
Plamen Milchev NIKOLOV
Albena Krasimirova ALEKSANDROVA-NIKOLOVA
Original Assignee
Cabot Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cabot Corporation filed Critical Cabot Corporation
Publication of WO2021046373A1 publication Critical patent/WO2021046373A1/fr

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
    • H01M10/08—Selection of materials as electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • H01M2300/0011—Sulfuric acid-based
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates generally to batteries. Specifically, the present disclosure relates to electrolyte additives for lead acid batteries.
  • the lead-acid battery is an electrochemical storage battery generally comprising a positive plate, a negative plate, and an electrolyte comprising aqueous sulfuric acid.
  • the plates are held in a parallel orientation and electrically isolated by porous separators to allow free movement of charged ions between the two plates.
  • the positive battery plates contain a current collector (i.e., a metal plate or grid) that can be covered with a layer of positive active material (also called positive active mass) that is electrically conductive and can include lead dioxide (PbCk).
  • the negative battery plates contain a current collector that can be covered with a negative active material (also called negative active mass), which is typically lead (Pb) metal.
  • Example l is a lead acid battery comprising: a positive electrode; a negative electrode; and an electrolyte in contact with the positive electrode and the negative electrode, the electrolyte comprising greater than 0.1% polyphosphate by weight .
  • Example 2 includes the subject matter of Example 1, comprising sodium tripolyphosphate or sodium hexametaphosphate or both.
  • Example 3 includes the subject matter of Example 2, wherein the electrolyte comprises from 0.3 to 1.8 wt. % of sodium tripolyphosphate or sodium hexametaphosphate.
  • Example 4 includes the subject matter of any of Examples 1-3, wherein the positive electrode is comprised of at least one of lead, lead-antimony alloy, and lead-calcium-tin alloy.
  • Example 5 includes the subject matter of any of Examples 1-4, wherein the negative electrode is comprised of lead or lead-calcium alloy.
  • Example 6 includes the subject matter of any of Examples 1-5, comprising a positive paste at least partially covering the positive electrode, the positive paste comprising lead dioxide, sulfuric acid, and water.
  • Example 7 includes the subject matter of any of Examples 1-6, comprising a negative paste at least partially covering the negative electrode, the negative paste including lead dioxide, carbon black, lignosulphonate and barium sulfate.
  • Example 8 includes the subject matter of Example 7, wherein the carbon black exhibits a Brunauer-Emmett-Teller (BET) surface area ranging from about 1300 m 2 /g to about 1550 m 2 /g.
  • BET Brunauer-Emmett-Teller
  • Example 9 includes the subject matter of Example 7, wherein the negative paste comprises between 0.25 and 0.75% (w/w) carbon black.
  • Example 10 includes the subject matter of any of Examples 1-9, wherein the tripolyphosphate is less than 1.5% by weight of the electrolyte.
  • Example 11 includes the subject matter of any of Examples 1-10 wherein the positive and negative electrodes are formed in an electrolyte comprising the polyphosphate.
  • Example 12 includes the subject matter of any of Examples 1-10 wherein the polyphosphate is added to the battery after the positive and negative electrodes are formed.
  • Example 13 is an electrolyte composition for a lead-acid cell, the composition comprising sulfuric acid and at least 0.1% polyphosphate by weight.
  • Example 14 includes the subject matter of Example 13, wherein the composition comprises at least 0.3% sodium tripolyphosphate by weight.
  • Example 15 includes the subject matter of either of Examples 13 or 14, wherein sodium tripolyphosphate comprises between 0.6% and 1.8% weight to volume of the composition.
  • Example 16 includes the subject matter of any of Examples 13-15 wherein the polyphosphate is selected from tripolyphosphate and hexametaphosphate.
  • Example 18 includes the subject matter of Example 17 wherein a negative plate of the cell comprises carbon black.
  • Example 19 includes the subject matter of either of Examples 17 and 18 wherein the ratio is greater than 1 :5 for a freshly formed plate or greater than 1 :30 for a cycled plate.
  • Example 20 includes the subject matter of any of Examples 17-19 wherein the positive plate is formed in electrolyte comprising a polyphosphate selected from tripolyphosphate and hexametaphosphate.
  • Example 21 includes the subject matter of any of Examples 17-19 wherein the cell is cycled using an electrolyte comprising a polyphosphate selected from tripolyphosphate and hexametaphosphate.
  • Example 22 includes the subject matter of any of Examples 17-21 including an electrolyte comprising sodium tripolyphosphate or sodium hexametaphosphate or both.
  • FIGS. 1 A and IB are schematic illustrations of a lead-acid battery, in an embodiment of the present disclosure.
  • FIG. 2A is a schematic illustration of sodium tripolyphosphate (STPP) used as an additive in lead-acid battery electrolyte, in an embodiment of the present disclosure.
  • STPP sodium tripolyphosphate
  • FIG. 2B is a schematic illustration of sodium hexametaphosphate (SHMP) used as an additive in lead-acid battery electrolyte, in an embodiment of the present disclosure.
  • SHMP sodium hexametaphosphate
  • FIG. 3 is cross-sectional view (taken perpendicular to a plane of the collector plates) of an example lead-acid 2 Volt (V) cell construction that includes an electrolyte with added STPP, in an embodiment of the present disclosure.
  • V lead-acid 2 Volt
  • FIG. 4A shows current versus voltage experimental results for both an oxidation and a reduction reaction for a pure lead electrode versus a Hg/Hg2S04 reference electrode for a cell that includes 1.2 wt. % STPP in 4.5 M H2SO4 electrolyte compared to a cell with 4.5 M H2SO4 electrolyte (i.e., lacking STPP), in an embodiment.
  • FIG. 4B shows discharge capacity experimental values as a function of the number of charge/discharge cycles for a pure lead electrode versus a Hg/Hg2S04 reference electrode for a cell that includes 1.2 wt. % STPP in 4.5 M H2SO4 electrolyte compared to a cell with 4.5 M H2SO4 electrolyte (i.e., lacking STPP), in an embodiment.
  • FIG. 4C shows current versus voltage experimental results for both an oxidation and a reduction reaction for a lead antimony alloy electrode versus a Hg/Hg2S04 reference electrode for a cell that includes 1.2 wt. % STPP in 4.5 M H2SO4 electrolyte compared to a cell with H2SO4 electrolyte (i.e., lacking STPP), in an embodiment.
  • FIG. 4D shows discharge capacity experimental values as a function of the number of charge/discharge cycles for a lead antimony electrode versus a Hg/Hg2S04 reference electrode for a cell that includes 1.2 wt. % STPP in 4.5 M H2SO4 electrolyte compared to a cell with 4.5 M H2SO4 electrolyte (i.e., lacking STPP), in an embodiment.
  • FIG. 4E shows current versus voltage experimental results for both an oxidation and a reduction reaction for a lead calcium alloy electrode versus a Hg/Hg2S04 reference electrode for a cell that includes 1.2 wt. % STPP in 4.5 M H2SO4 electrolyte compared to a cell with 4.5 M H2SO4 electrolyte (i.e., lacking STPP), in an embodiment.
  • FIG. 4F shows discharge capacity experimental values as a function of the number of charge/discharge cycles for a lead calcium electrode versus a Hg/Hg2S04 reference electrode for a cell that includes 1.2 wt. % STPP in 4.5 M H2SO4 electrolyte compared to a cell with 4.5 M H2SO4 electrolyte (i.e., lacking STPP), in an embodiment.
  • FIG. 5A illustrates discharge capacities (as a percentage of rated capacity) for 2pPbSb/3nPbCa cells that do not include STPP added to the electrolyte (“Blank”) and identically configured cells that do include 1.2 wt. % STPP, in an embodiment.
  • FIG. 5B illustrates discharge capacities (as a percentage of rated capacity) for 2pPbCa/3nPbCa cells that do not include STPP added to the electrolyte (“Blank”) and identically configured cells that variously include 0.6 wt. %, 1.2 wt. % and 1.8 wt. % added to the electrolyte, in embodiments.
  • FIG. 6A illustrates discharge capacities (as a percentage of rated capacity) for 3pPbSb/2nPbCa cells with 0 wt. % STPP (“Blank”) and 0.6 wt. %, 1.2 wt. % and 1.8 wt. % added to the electrolyte, in embodiments.
  • FIG. 6B illustrates discharge capacities (as a percentage of rated capacity) for 3pPbCa/2nPbCa cells with 0 wt. % STPP (“Blank”) and 0.6 wt. %, 1.2 wt. % and 1.8 wt. % added to the electrolyte, in embodiments.
  • FIG. 7A illustrates cycle life experimental results for 2p/3n cell configurations with one of PbSb or PbCa positive grids at various concentrations of STPP added to electrolyte, in embodiments.
  • FIG. 7B illustrates cycle life experimental results for 3p/2n cell configurations with one of PbSb or PbCa positive grids, at various concentrations of STPP added to electrolyte, in embodiments.
  • FIG. 8 illustrates water loss test results for a cell that includes 1.2 wt. % STPP added to the electrolyte compared to water loss test results for a reference cell that does not include STPP added to the electrolyte, in an embodiment.
  • FIG. 9 is a bar graph illustrating the initial battery capacities for several embodiments of STPP doped electrolyte.
  • FIG. 10 is a bar graph illustrating initial capacities for several embodiments of polyphosphate doped electrolyte.
  • FIG. 11 provides graphic data showing depth of discharge cycling results for different embodiments.
  • FIG. 12 provides graphic data showing depth of discharge cycling results for additional embodiments.
  • FIG. 13 provides graphic data showing depth of discharge cycling results for additional embodiments.
  • FIG. 14 provides graphic data showing depth of discharge cycling results for additional embodiments.
  • FIGS. 15A-15E provide tabular data showing the results of charge acceptance tests for various embodiments of a 2p/3n electrode configuration.
  • FIGS. 16A-16F are bar graphs showing the specific surface area of positive and negative plates in different embodiments.
  • FIGS. 17A-17J provide tabular data regarding surface area, pore area, pore volume and pore radius in various embodiments of positive and negative active masses.
  • FIG. 18A is a graphical plot showing XRD peak intensity for both freshly formed and cycled embodiments.
  • FIGS. 18B-18D provide tabular data for XRD peak intensities illustrating relative quantities of a-PbCk and b-PbCb in the positive active mass for different embodiments of doped electrolyte.
  • FIG. 19A is a photomicrograph of the positive active mass after cycling in different embodiments of doped electrolyte.
  • FIG. 19B is a photomicrograph of the negative active mass after cycling in different embodiments of doped electrolyte.
  • FIG. 20 is a table depicting data directed to ion chromatography results for characterizing different embodiments of STPP.
  • FIGS. 1A and IB Schematic illustrations of example configurations of lead-acid batteries are shown in FIGS. 1A and IB.
  • an example lead-acid battery 100 is shown in FIG. 1 A.
  • the lead-acid battery 100 includes a first electrode 102, a second electrode 104, and an electrolyte 106.
  • Electrodes 102, 104 are typically plates (or grids) held in a parallel orientation and electrically isolated by a porous separator that allows the movement of ions.
  • Example configurations include 2 positive/3 negative (2p/3n) or 3 positive/2 negative (3p/2n) plate configurations.
  • the first electrode 102 is a positive battery plate that includes a current collector (e.g., a metal plate or metal grid) that is covered with a layer of positive electrically conductive active material.
  • a current collector e.g., a metal plate or metal grid
  • Example materials that can be used to form the positive current collector include, but are not limited to, alloys of lead (Pb) and antimony (Sb), or alloys of lead, calcium, and tin.
  • Example materials that can coat the positive current collector include (but are not limited to) PbCE, PbO, water, and EbSCri (sulfuric acid) on one or more surfaces.
  • the second electrode 104 is a negative battery plate that includes a current collector (e.g., a metal plate or metal grid) that is covered with a negative, electrically conducive active material (such as lead metal (Pb)) on one or more surfaces.
  • a current collector e.g., a metal plate or metal grid
  • a negative, electrically conducive active material such as lead metal (Pb)
  • Example materials that can be used to form the negative current collector include, but are not limited to, lead (Pb), alloys of lead (Pb) and antimony (Sb), or alloys of Pb, calcium (Ca), and tin (Sn).
  • Negative plates of lead-acid batteries can be produced by applying a paste including lead oxide powder and sulfuric acid to electrically conductive lead alloy structures, known as grids. After the plates have been cured and dried, the plates can be assembled into a battery and charged to convert the lead oxide into metallic lead (Pb). In some cases, an “expander mixture” is added to the paste to improve the performance of the negative plate.
  • the expander mixture may include, for example, barium sulfates as a nucleating agent for lead sulfate produced when the plate is discharged, carbon black particles to increase the electrical conductivity of the active material in the discharged state, and a lignosulfonate or other organic material to increase surface area of the active material and to assist in stabilizing the physical structure of the active material.
  • barium sulfates as a nucleating agent for lead sulfate produced when the plate is discharged
  • carbon black particles to increase the electrical conductivity of the active material in the discharged state
  • a lignosulfonate or other organic material to increase surface area of the active material and to assist in stabilizing the physical structure of the active material.
  • FIG. IB Another example lead-acid battery 120 is shown in FIG. IB.
  • the example lead-acid battery 120 is a 12 Volt (V) battery that includes 6 cells. Each cell is rated at 2 V and includes a plurality (e.g., from 6 to 8) of positive plates and a corresponding plurality of negative plates (and associated negative and positive masses). The positive and negative plates are placed in an alternating fashion and are electrically insulated from one another by a separator material, as described above in the context of FIG. 1 A.
  • V Volt
  • Example applications that could benefit from improved lead-battery technology include, for example, micro-hybrid cars with start-stop and regenerative braking functions, as well as in stationary energy storage systems (ESS) charged by renewable energy sources (e.g., wind, solar).
  • ESS stationary energy storage systems
  • lead-acid energy capacity can decline over time as the battery is repeatedly charged and discharged. This effect is sometimes noticed when the battery experiences frequent partial state of charge cycling conditions. This decline in capacity can be attributed to any of a number of causes.
  • electrical contact between the Pb02 particles of the positive active mass and the corresponding positive grid can degrade with time.
  • a layer of PbS04 crystals can form on the surface of the electrodes.
  • Formation of PbSCri crystals can electrically isolate some of the active mass from an underlying plate or grid.
  • the positive grid can form an oxide layer on the grid, which can electrically isolate the corresponding active mass from the grid. Corrosion can degrade the structure of the positive grid, also increasing its resistance and decreasing its electrical connection with the overlying positive active mass.
  • carbon black particles e.g., high surface area carbon particles
  • the presence of carbon black particles in the negative active mass while thought to beneficially form a conductive network within the lead sulfate matrix of a discharged negative plate, can also contribute to high gassing related to hydrogen and oxygen evolution at one or both of the positive and negative plates.
  • Evolution of these gasses can occur at a voltage above the water decomposition voltage within a lead-acid battery, thus activating the oxygen evolution reaction or “OER.”
  • the evolution of these gasses can lead to increased electrolyte concentrations away from desired values and/or lead to accelerated sulfation of one or both of the negative and positive active masses.
  • lead-acid batteries described herein include a polyphosphate salt.
  • the polyphosphate described herein can include 2, 3, 4, 5 or more phosphates covalently bound together.
  • the polyphosphate salts are typically sodium salts but it is understood that other cations can be substituted.
  • Example polyphosphate salts include sodium tripolyphosphate (STPP) and sodium hexametaphosphate (SHMP). STPP, the anion of which can be expressed as [P3O10] 5' or SHMP can be added directly to an electrolyte of a lead-acid battery.
  • Inclusion of a polyphosphate salt in an electrolyte of a lead-acid battery can increase battery capacity (e.g., the number of hours of discharge at a given discharge current and voltage) and/or cycle life (i.e., the number of cycles of discharging and charging that a battery can undergo before failing).
  • battery capacity e.g., the number of hours of discharge at a given discharge current and voltage
  • cycle life i.e., the number of cycles of discharging and charging that a battery can undergo before failing.
  • FIG. 2A an example depiction of the structure of STPP is illustrated in FIG. 2A (along with example counter ions) and the structure of SHMP is provided in FIG. 2B. It will be appreciated that other additives, such as surfactants, can be included in the battery electrolyte.
  • FIG. 3 An example embodiment of a lead-acid 2 Volt (V) cell 300 of the present disclosure is shown in FIG. 3.
  • the example lead-acid cell 300 includes an outer case 304, positive electrode assemblies 308, negative electrode assemblies 312, porous separators 316, and an electrolyte solution that includes STPP 320. It will be appreciated that some elements of the lead-acid cell 300 known to those of skill in the art have been omitted from FIG. 3 for clarity of depiction and convenience of explanation.
  • the example cell 300 (one or more of which can be used with other components to produce a battery) includes 2 positive electrode assemblies 308 and 3 negative electrode assemblies 312 (2p/3n). It will be appreciated that any of a number of other configurations are possible, including but not limited to, 3 positive electrode assemblies 308 and 2 negative electrode assemblies 312 (3p/2n).
  • the outer case 304 is simply a shell within which the various other components of the lead-acid battery can be contained.
  • the outer case 304 is sometimes referred to simply as a “battery container.”
  • the outer case 304 can be made from a polymer material and can be formed into any shape convenient for the housing of other components.
  • the positive electrode assembly 308 can be fabricated from a positive collector 324 that is optionally coated with a conductive paste (or “positive active mass”) 328.
  • the positive collector 324 include a plate or a grid formed from alloys of antimony (Sb) and lead (Pb) and/or lead, calcium (Ca), and tin (Sn), among other alloys.
  • the positive active mass 328 can be formed from lead oxide, water, and sulfuric acid, in some examples.
  • the negative electrode assembly 312 can be fabricated from a negative collector 332 that is optionally coated with a conductive paste (or “negative active mass”) 336.
  • the negative collector 332 can be either a plate or a grid formed from alloys of lead and calcium, among other alloys.
  • the negative active mass 336 can be formed from example materials that include (but are not limited to) PbO, carbon black (such as 0.5 weight % PBX ® 51 carbon black produced by CABOT CORPORATION of Boston, Massachusetts and having a BET nitrogen surface area of from 1300-1550 m 2 /g as tested according to ASTM D6556), 0.8 weight % BaS04, and 0.2 weight % VANISPERSE A (produced by BORREGAARD LIGNOTECH of Sarpsborg, Norway).
  • carbon blacks used may have a BET nitrogen surface area of from 500 to 2500 m 2 /g, from 1000 to 2000 m 2 /g, or from 1200 to 1700 m 2 /g.
  • Examples of carbon, in addition to carbon black, that can be used to formulate the negative active mass include, but are not limited to, graphite, graphenes, activated carbons, carbon nanotubes having surface areas in the range of 20 m 2 /g to 2000 m 2 /g.
  • Example loadings of carbon (in any form or allotrope) in the active mass can be from 0.01 wt. % to 5 wt. % of the mass of PbO used in the negative mass.
  • Other example loadings of carbon (relative to the mass of PbO) can be from 0.3 wt% to 3 wt. % or from 0.5 wt. % to 1.5 wt. %.
  • the separator 316 can be a sheet of material that is porous to ionic transfer between negative 312 and positive 308 electrodes but that is an electrical insulator that prevents direct electrical contact (i.e., shorting) between the negative 312 and positive 308 electrodes.
  • Example materials that can be used for the separator 316 include polyethylene-based fabrics (e.g., for use in flooded lead-acid batteries), adsorptive glass matt material (AGM) (e.g., for used in AGM lead-acid batteries), or silica-based separators (e.g., for use in gel lead-acid batteries).
  • the electrolyte (320) which can include an additive such as STPP, is used to fill (or “flood”) the various electrode assemblies 308, 312, porous separators 316, and intervening spaces within the outer case 304.
  • the electrolyte with STPP 320 can include water and sulfuric acid (H2SO4) in addition to the additive.
  • STPP described above, is an inorganic anionic phosphate salt.
  • the counter-ion to the anionic salt is sodium (Na + ), but other cationic counter-ions, such as one or more of potassium, lithium, magnesium and calcium, are possible.
  • Other electrolyte solvents, other than sulfuric acid can also be used in combination with STPP to form the electrolyte with STPP 320.
  • polyphosphate salts when disposed in the electrolyte 320, can be adsorbed onto one or both of the positive collector 324 and negative collector 332 surfaces.
  • the additive can bond to metal cations, which can in turn inhibit corrosion reactions that would otherwise degrade the surface of (and electrical contact with) the collector plates 324, 332.
  • the additive can slow the anodic oxidation of PbSCri to PbCE and the cathodic reduction of PbCh to PbSCri.
  • a polyphosphate salt can shift the overpotential of oxygen (O2) to higher voltages.
  • O2 overpotential of oxygen
  • the effect of this shift is to increase a voltage needed for oxygen to be evolved from components of an electrolyte (e.g., water) in the lead-acid battery. Because the voltage is increased, the oxygen evolution reaction is less likely to occur.
  • this shift can cause the OER to occur under a narrower set of operating conditions. This can delay, reduce, and/or prevent the undesirable evolution of oxygen from the positive active mass and/or hydrogen from the negative active mass in the battery, thus reducing gassing and water loss and improving battery performance.
  • the additive such as STPP or SHMP, can be added to the electrolyte 320 in any effective concentration including the following concentrations: from 0.2 weight (wt.) % to 5 wt. %; from 0. 2 wt. % to 0.6 wt. %; from 0.2 wt. % to 1.0 wt. %; from 0.2 to 1.2%, from 0.2 to 1.4%; from 0.2 to 1.6%, from 0.5 wt. % to 1.5 wt. %; from 1.5 wt. % to 2 wt.
  • concentrations from 0.2 weight (wt.) % to 5 wt. %; from 0. 2 wt. % to 0.6 wt. %; from 0.2 wt. % to 1.0 wt. %; from 0.2 to 1.2%, from 0.2 to 1.4%; from 0.2 to 1.6%, from 0.5 wt. % to 1.5 wt. %; from 1.5 wt. % to 2
  • the density of electrolyte solution of sulfuric acid in water can be at any effective level and may be within any of the following ranges: from 0.01 g/cm 3 to 1.84 g/cm 3 from 1.0 g/cm 3 to 1.4 g/cm 3 or from 1.05 g/cm 3 to 1.36 g/cm 3 .
  • Experiment set 1 The following experiments present various procedures and formulations used with lead-acid batteries (e.g., configured like the example battery 300) using an electrolyte that also contains an additive, as described above. Details of the lead-acid battery construction, the component formulation tested, and the corresponding test results follow.
  • Each of these additives was tested at 0.3%, 0.6%, 0.9%, 1.2% and 1.4% by weight. Each additive at each concentration was also tested in a “formed” system and a “refilled” system. A formed system is when electrodes are formed in the presence of the electrolyte containing the additive. A refilled system is when electrodes are formed without the additive present and then the additive electrolyte is added afterwards, prior to testing.
  • FIGS. 4A-4F show cyclic voltammetry experimental results for a lead-acid battery that includes an electrolyte composed of 4.5 Molar (M) sulfuric acid both with and without 1.2 wt. % STPP A (natural STPP) for various positive collector alloy compositions.
  • a mercury (Hg)/mercury sulfate (HgiSCri) reference electrode was used as a reference electrode to test the performance of the various cells.
  • the composition of the working electrodes was formed according to the composition noted in each figure. Namely, FIGS. 4 A and 4B included a pure lead (99.99% Pb) positive electrode; FIGS. 4C and 4D included a PbSb (1.8 wt.
  • FIGS. 4E and 4F included a PbCaSn (0.06 wt. % Ca and 1.25 wt. % Sn) positive electrode.
  • the smooth model electrode geometrical area that was exposed to the electrolyte was 0.4 cm 2 .
  • a Pb (99.99 wt. %) electrode having an exposed area of 2.5 cm 2 was used as a counter-electrode.
  • the test electrodes were subjected to cyclic voltammetry measurements in the PbSCri/PCh potential range from 0.7V to 1.5V (vs. Hg/Hg2S04) at a scan rate of 10 milli Volts (mV)/s for 600 cycles in sulfuric acid solution having a density of 1.28 g/cm 3 .
  • Negative active mass for the experiments described below was prepared in 1 kilogram (kg) batches.
  • PbO (1 kg) was added into a paste mixing container and mixed for 1 min, followed by the addition of sodium lignosulfonate (Vanisperse A, 2 g for 0.2 wt. %) and barium sulfate (8 g for 0.8 wt.%).
  • Carbon black (PBX ® 51 carbon black, 5 g for 0.5 wt.% loading vs. PbO) pre-wetted with 12 g water, was then added to the mixer and mixed for 3 min, followed by the addition of water (140 mL) and additional mixing for 10 min. Finally, sulfuric acid (80 mL,
  • Positive electrode paste was made according to the same procedure but without carbon black or other additives and with a composition corresponding to the positive electrode.
  • Electrodes were hand-pasted with 22 g wet paste on a 5.5 x 5 cm 2 on Pb-1 8Sb or Pb- 0.06Ca-1.25Sn alloy grids. Electrodes were cured in a humidity-controlled oven. The curing protocol was the same for positive and negative plates: 72 h at 35°C, 95% relative humidity (RH), followed by 24 h at 60°C, 10% RH. The negative active mass weight after curing was typically 20 g per plate.
  • Cells were assembled by torch welding three positive plates and two negative plates together or by welding two positive plates and three negative plates together. The cell configurations are denoted as 3p/2n or 2p/3n, respectively.
  • Electrode and separator stacks were inserted in polymethylmethacrylate cases and compressed with Nylon mesh shims. Case lids were screwed on with 2 mm diameter vent openings. Completed cells were 2V single cells, with nominal capacity of 4.0 and 4.7 Ah for 2p/3n and 3p/2n cell configuration, respectively. Formation was performed in a container with 1.255 g/cm 3 sulfuric acid (typically 85 mL). The formation algorithm comprises multiple current steps with total duration of 65h and total capacity of 26.76 Ah. The electrolyte density target after formation was 1.28 g/ cm 3 .
  • Cycle-life testing of the cells with 17.5% depth of discharge was performed by fully charging the cells at 2.5V for 24h, then discharging at 0.2Cn for 2.5h to reach 50% state-of- charge.
  • the cycling consists of charging the cells with 0.35Cn for 40 minutes (with upper voltage limit of 2.4V) and discharging them with 0.35Cn for 30 minutes (with lower voltage limit of 1.66V). Cycles are repeated continuously until the lower voltage limit is reached.
  • “Formed” cells differ in that the electrodes are formed, not refilled, in the presence of the doped electrolyte.
  • Control cells (without surfactant electrolyte additives) were also assembled and named “blank” in the figures.
  • Initial capacity tests and continuous cycling tests at continuous 17.5% depth of discharge (DoD) cycling test were performed, the latter of which measured performance changes in start-stop partial discharge conditions. Results for samples with 1.2 wt. % STPP are shown in FIGS. 4A-4F.
  • Performance of cells with “blank” electrolyte (i.e., without additive) is consistent with expected performance. Experimental data shown in FIGS.
  • FIGS. 4B, 4D and 4F present the discharge capacity values (amount of cathodic electricity) for pure Pb, PbSb alloy, and PbCa alloy electrodes for cells with 1.2 wt. % STPP in 4.5 M H2SO4 compared to cells with the same electrode composition but without any STPP (4.5 M H2SO4 electrolyte).
  • the discharge capacity is calculated by integration of the surface area of the cathodic peak corresponding to the reduction of PbCk to PbS04, for the different experimental electrodes. As can be seen, the PbSb electrode exhibits the highest capacity when compared to the Pb and PbCa alloy electrodes.
  • FIGS. 5A, 5B, 6A, 6B and 7 illustrate various electrochemical experimental results.
  • the samples described below were 2p/3n lead-acid batteries configured to have a voltage of 2.0V and a capacity of 4 Amp hours (Ah).
  • These “flooded” cells were prepared as described above in the context of FIGS. 4A-4F and which variously include STPP concentrations of 0.6 wt. % STPP, 1.2 wt. % STPP and 1.8 wt. % STPP.
  • Positive collectors were formed from PbSb or PbCaSn alloy grids (as indicated in the figures).
  • FIG. 5A illustrates discharge capacities for 2pPbSb/3nPbCa cells. More specifically, FIG. 5A shows the first three initial C20 discharge capacities of the cells as percentage of actual measured capacity versus the rated nominal Cn capacity for the cell configuration. “Blank” test results are control cells that differ from other tested cells only in their lack of STPP in the electrolyte. The results indicate that cells that include 1.2 wt. % STPP added to electrolyte reduce the 1st C20 capacity value. During the next two capacity tests, the C20 capacities increase and all cells meet the capacity requirements and have higher initial capacities than the rated values (100%).
  • FIG. 5B illustrates the first three initial C20 discharge capacities as a percentage of rated capacity cells with electrode compositions identical to those described in FIG. 5A except for differing concentrations of STPP added to the electrolytes.
  • “Blank” results correspond to control samples lacking STPP added to the electrolyte.
  • the other experimental results depicted in FIG. 5B were prepared with 0.6 wt. %, 1.2 wt. % and 1.8 wt. % added to the electrolyte. At all tested additive concentrations, the initial C20 capacity decreases compared to the blank cell, however all C20 capacities are still higher than Cn nominal capacity.
  • FIGS. 6A and 6B show results similar to those shown in FIG.
  • FIG. 6A illustrates the first three initial C20 discharge capacities as a percentage of rated capacity cells for 3p/2n cells and specifically 3pPbSb/2nPbCa cells with 0 wt. % STPP (“Blank”) and 0.6 wt. %, 1.2 wt. % and 1.8 wt. % STPP added to the electrolyte.
  • FIG. 6B illustrates the first three initial C20 discharge capacities as a percentage of rated capacity cells for 3p/2n cells and specifically 3pPbCa/2nPbCa cells with 0 wt. % STPP (“Blank”) and 0.6 wt. %, 1.2 wt. % and 1.8 wt. % STPP added to the electrolyte.
  • cells with STPP electrolyte additive exhibit initial C20 capacity higher by at least 15-20% than the Cn nominal capacity value.
  • FIGS. 7 A and 7B show cycle life experimental results for two different cell configurations and for two different positive electrode compositions.
  • FIG. 7 A illustrates experimental results for 2p/3n cells that have either PbSb positive electrodes or PbCa positive electrodes.
  • the 2p/3n PbSb cells with STPP added to the electrolyte exhibit more than two times longer cycle life as compared to that of the blank electrolyte cell (lacking added STPP in the electrolyte). This is the case for all concentrations of STPP.
  • 0.6 wt. % and 1.2 wt. % concentrations of STPP in electrolyte for PbCa positive electrodes have longer cycle life that the blank electrolyte cell.
  • FIG. 7B illustrates water loss test results for a 3pPbCa/ 2PbCa (and carbon) cell.
  • the control (blank) cell filled with the same electrolyte described above in other experimental examples. That is 4.5 M H2SO4 without STPP added.
  • the tested cell included this electrolyte with 1.2 wt. % STPP added.
  • the electrodes were prepared as follows:
  • the cells were flooded (liquid electrolyte) cells with polyethylene separators and grids made of lead/calcium/tin alloy (PbCaSn). Two configurations were used. The first was 2 positive and 3 negative electrodes with nominal capacity of 4.0 Ah. The second was 3 positive and 2 negative electrodes with nominal capacity of 4.6 Ah.
  • the paste for the negative electrodes was comprised of 0.5 wt % carbon black (PBX-51), 0.2 wt % sodium lignosulfonate (Vanisperse A), 0.8 wt % BaSCri, 1000 g PbO, 130 mL water and 80 mL of 1.40 sg sulfuric acid.
  • the paste for the positive electrode was comprised of 1000 g PbO, 120 mL water and 75 mL of 1.40 sg sulfuric acid.
  • the electrodes were formed in the presence of the additive being tested.
  • the electrodes were formed without the additive present and then the cells were refilled with electrolyte including the additive being evaluated. Additional procedures were the same as for Experiment Set 1.
  • STPP sodium hexametaphosphate
  • A The first form of STPP (A) is a natural product meaning that it is mined and not synthesized.
  • STPP B
  • B The second form of STPP (B) is another natural product purchased from Amazon.com (Pure Organic Ingredients).
  • STPP C
  • the SHMP was purchased from Minerals Water Ltd, UK.
  • FIG. 9 provides a bar graph showing results for STPP A in a formed configuration.
  • the blank electrolyte performed slightly better than the test samples and exhibited initial capacities at 1, 2 and 3 cycles that were above the 100 % nominal target (at least 110 % after three cycles) that represents a threshold for these cells. Since the blank electrolyte performed the best, it is surprising that the STPP A at concentrations of 0.6% and 1.2% outperformed the samples at 0.1% and 0.3 % of STPP A.
  • FIG. 10 provides a bar graph showing the results for STPP A, B, C and SHMP. The blank performed slightly better than most of the test samples, however all test samples were above the 100% nominal threshold for these cells. Sample STPP B at 0.6% had the least amount of initial capacity loss through cycles two and three.
  • the x-axis indicates the number of discharges cycles and the y-axis indicates the output voltage at the end of discharge.
  • Each test was run on two identical cells, cell A and cell B, which are plotted together in the same graph.
  • the cycle threshold, as shown in the Blank plot in FIG. 11 is that the cell obtain 1,000 cycles before dropping below 1.66 V.
  • FIG. 11 provides results from a system using a formed configuration with electrolyte containing STPP A at different concentrations shown in different graphs. Except for cell A at 0.1% STPP, all concentrations were able to maintain adequate voltage at greater than 1,000 discharge cycles.
  • FIG. 12 provides results from a system using a refilled configuration and with the same electrolyte and STPP A as the tests from FIG. 11. These plots indicate that at concentrations of 0.6%, 0.9%, 1.2% and 1.4% the STPP provided for an increased number of discharge cycles when compared to the blank of the same electrode configuration.
  • FIG. 13 provides test results from a system using the refilled configuration and includes results for STPP B and STPP C. Note that all concentrations of both forms of STPP met the 1,000 cycle threshold but that the STPP C (synthetic) sample extended the number of cycles out to 2,000, 3,000 and 4,000 cycles.
  • FIG. 14 shows results from the same test as FIG. 13 (refilled cell) except using SHMP instead of STPP. Results show greater than 1,000 cycles for 0.6% and greater than 3,000 cycles for greater than 1.2% SHMP.
  • FIGS. 15A-15E provide tabular data showing the results of these charge acceptance tests for a 2p/3n electrode configuration. Each figure is labeled with the percent of discharge that was used. As illustrated in the tables, from 50 to 90% DoD, the cells using the test samples of STPP and SHMP took consistently higher charging current from 5 seconds up to 600 seconds. It is notable that the sample containing 1.2% of STPP C provide the best results across all time intervals.
  • SSA specific surface area
  • BET Brunauer, Emmett and Teller
  • FIGS. 16A-16F provide bar graphs illustrating the SSA of various additive compositions under cycled and freshly formed conditions.
  • FIGS. 16A and 16B show the SSA change for the positive and negative plates, respectively, for a sample containing STPP A at the concentrations shown in the graphs. This is a refilled configuration where the plate is formed and the electrolyte containing the additive is added after formation, and then the cell is cycled. In this test the cell was cycled. As can be seen, the beneficial effect of the STPP A on positive active mass SSA increases with increasing concentration of STPP from 0.6% to 0.9% and to 1.2%.
  • the blank shows an SSA of about 3 m 2 /g while the samples containing STPP A indicate a surface area of about 10 m 2 /g or greater. This is about a doubling of the SSA compared to the freshly formed plates and about three times the SSA of the cycled blank plates.
  • FIGS. 16C and 16D illustrate the results from a test similar to that of FIGS. 16A and 16B except that STPP C was used instead of STPP A. Results show that at 0.6% STPP C there is an increase in SSA for the positive plate compared to the blank but a drop off in SSA compared to the blank for the negative plate. From these results it is believed that the positive effect achieved from the use of polyphosphate salts such as STPP is due to the change it has on the positive plate rather than the negative plate as is generally the case with flooded cell additives.
  • FIGS. 16E and 16F provide results using the same test procedure as 16C and 16D except that SHMP was evaluated in place of the STPP.
  • Results show an SSA of about 3X the area of the blank in the positive plate and about 2/3 the SSA of the blank for the negative plate. This reinforces the theory that it is the effect on the positive plate that accounts for the improved performance of the cells containing a polyphosphate additive.
  • FIGS. 17A through 17J provide surface area and porosity data for the positive active mass (PAM) and the negative active mass (NAM) with various configurations and additive packages.
  • Surface area was analyzed by BET, and mercury intrusion porosimetry was used to measure pore area, pore volume and pore radius.
  • Different cell configurations were tested including a formed electrode system (additive included before formation) and a refilled electrode system (additive added to electrolyte after active mass formation). Measurements were taken before and after cycling of the electrodes. Additives were tested at 0.1%, 0.3%, 0.6% and 1.2% in the electrolyte. In both pre and post cycling, the PAM showed an increase in surface area and pore area compared to the blank.
  • FIGS. 17A and 17B provide data in tabular form of a system with PAM and NAM formed in the electrolyte comprising STPP A. Both new and cycled plates were tested.
  • FIGS. 17C and 17D provide the same data for a test that used a refilled configuration where the additive was added after formation of the electrodes.
  • FIGS. 17E and 17F provide data for STPP B in a refilled cell configuration.
  • FIGS. 17G and 17H provide tabular data for STPP C in a refilled cell configuration.
  • FIGS. 171 and 17J provide tabular data for SHMP in a refilled cell configuration.
  • a-PbCk alpha form of lead dioxide
  • XRD x-ray diffraction
  • FIG. 18A provides a plot showing the intensity of the alpha and beta lead dioxide peaks (XRD) in the positive active mass for cycled (>1,000) and fresh plates at different levels of STPP A. The plates were formed in the STPP doped electrolyte. The graph illustrates that as the concentration of STPP increases, the amount of alpha lead dioxide increases while the amount of beta lead dioxide decreases.
  • FIG. 18B is a table providing XRD intensities that indicate the relative amounts of a- Pb02 and b ⁇ 02 in both freshly formed and cycled active masses.
  • the active masses were formed in the presence of STPP A.
  • all of the additive concentrations in both the fresh and the cycled samples resulted in greater amounts of a-PbCk and a reduction in b-PbCb.
  • the concentration of STPP A increases the amount of a-PbCk also increases for both freshly formed and cycled positive active masses.
  • the peak intensity for a-PbCk was at least 2X the peak intensity for the blank and in some cases at least 3X the peak intensity of the blank.
  • the a-PbCk peak intensity was up to 3X (1.2% STPP) the value for the blank.
  • the b-PbCb intensities were reduced by more than 20%, more than 30% and more than 40% when compared to the blank under the same conditions.
  • FIG. 18C is a table providing data for tests similar to those completed for FIG. 18B except that only cycled active masses from the refilled cells with electrolyte including the additives STPP A, STPP B, STPP C and SHMP were tested. All of the additives at each concentration raised the amount of a-PbCk present in the active mass and in some cases by two or three times. The relative amount of b-PbCb was reduced for each of the additives as well and in some cases was reduced by greater than 20%, greater than 30%, greater than 40% or greater than 50%. It is of interest that the greatest changes were effected using STPP A while the lowest change was realized for STPP B. Together with the results from FIG. 18B, these data indicate that the improvement in cycling seen in cells that include these additives may be the result of an increase in a-PbCk realized as a result of the use of the polyphosphate additives in the electrolyte.
  • the presence of a-PbCk in the active mass is believed to be important for building the PAM structural skeleton to provide mechanical support.
  • This skeleton is formed in the corrosion layer of the PAM, so build-up and maintenance of a-PbCk in the corrosion layer is important to produce batteries with high capacities and long life cycles.
  • the corrosion layer is the portion of the PAM that is in direct contact with the grid.
  • the PAM corrosion layer can include 15%, 20% or 30% more a-PbCk than in a PAM that has not been produced or cycled in doped electrolyte.
  • the table in FIG. 18D illustrates how the presence of STPP A in the electrolyte can promote the formation and maintenance of a-PbCk in the corrosion layer.
  • FIGS. 19A and 19B are SEM micrographs showing the morphology of the crystals in a cycled PAM and cycled NAM, respectively. The cell was refilled with doped electrolyte after formation.
  • both the STPP C and the SHMP produced smaller PbCE crystal sizes, meaning that the surface area is greater and thus improving performance.
  • Pb crystals were larger with the doped electrolyte than in the blank sample, however, in contrast to the blank, the micrographs also show an absence of PbSCri crystals in the STPP and SHMP test samples. The absence of PbSCri crystals is indicative of improved performance.
  • STPP A, B natural (STPP A, B) and synthetic (STPP C) STPP
  • solutions of STPP A and STPP C were analyzed by ion chromatography to determine the actual composition and purity of each sample.
  • the samples were tested after dissolving in water and also after dissolving in 37 wt% sulfuric acid, to replicate the conditions in the battery electrolyte.
  • the solutions were shaken to dissolve, allowed to settle for an hour and then serially diluted to reach a concentration of about 2 ppm.
  • the IC was operated isocraticly under the following conditions:
  • Instrument Metrohm 930 Compact IC
  • FIG. 20 provides quantitative data regarding the STPP (measured), metaphosphate, pyrophosphate, ortho-phosphate, sulfate and chloride content in water prepared samples and sulfuric acid prepared samples.
  • the actual STPP content measured was significantly greater in the STPP C sample than in the STPP B natural sample.
  • sulfuric acid much of the phosphate content in both the natural and synthetic samples was converted to pyrophosphate and orthophosphate.
  • a greater amount of STPP remained in the synthetic sample, meaning that, for a given mass of dopant, the synthetic sample likely provides a greater amount of STPP to a battery electrolyte than does the natural STPP.
  • the synthetic STPP may be preferred to the natural STPP because high levels of chloride can have a negative impact on cycle life.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne une composition d'électrolyte pour batteries au plomb-acide qui améliore les performances de la batterie. Le polyphosphate, et plus spécifiquement le tripolyphosphate de sodium (STPP), peut être ajouté à un électrolyte au plomb-acide. Ce dopant augmente le nombre d'heures de décharge à un courant et une tension de décharge donnés et/ou le nombre de cycles de décharge et de charge qu'une batterie peut subir avant d'être défaillante.
PCT/US2020/049440 2019-09-06 2020-09-04 Additifs d'électrolyte pour batteries au plomb-acide WO2021046373A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201962896760P 2019-09-06 2019-09-06
US62/896,760 2019-09-06

Publications (1)

Publication Number Publication Date
WO2021046373A1 true WO2021046373A1 (fr) 2021-03-11

Family

ID=72644878

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2020/049440 WO2021046373A1 (fr) 2019-09-06 2020-09-04 Additifs d'électrolyte pour batteries au plomb-acide

Country Status (1)

Country Link
WO (1) WO2021046373A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115360423A (zh) * 2022-09-20 2022-11-18 济南大学 一种改善金属二次电池电性能的方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4555458A (en) * 1982-02-15 1985-11-26 Compagnie Europeenne D'accumulateurs, S.A. Electrolyte for a lead acid accumulator, and an accumulator using said electrolyte
CN102738519A (zh) * 2012-06-25 2012-10-17 天能集团江苏科技有限公司 超级电池的电解液
US20150357643A1 (en) * 2014-06-10 2015-12-10 Cabot Corporation Electrode compositions comprising carbon additives
CN107732251A (zh) * 2017-10-10 2018-02-23 吉林省凯禹电化学储能技术发展有限公司 一种铅炭电池正极板栅的防腐修饰涂层的可控制备方法
US20180205083A1 (en) * 2015-07-17 2018-07-19 Cabot Corporation Oxidized carbon blacks and applications for lead acid batteries
CN110380137A (zh) * 2019-06-10 2019-10-25 吉林大学 一种铅酸电池电解液添加剂及其制备方法
CN110797509A (zh) * 2019-09-25 2020-02-14 双登集团股份有限公司 一种改善铅酸蓄电池负极板硫酸盐化的组分

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4555458A (en) * 1982-02-15 1985-11-26 Compagnie Europeenne D'accumulateurs, S.A. Electrolyte for a lead acid accumulator, and an accumulator using said electrolyte
CN102738519A (zh) * 2012-06-25 2012-10-17 天能集团江苏科技有限公司 超级电池的电解液
US20150357643A1 (en) * 2014-06-10 2015-12-10 Cabot Corporation Electrode compositions comprising carbon additives
US20180205083A1 (en) * 2015-07-17 2018-07-19 Cabot Corporation Oxidized carbon blacks and applications for lead acid batteries
CN107732251A (zh) * 2017-10-10 2018-02-23 吉林省凯禹电化学储能技术发展有限公司 一种铅炭电池正极板栅的防腐修饰涂层的可控制备方法
CN110380137A (zh) * 2019-06-10 2019-10-25 吉林大学 一种铅酸电池电解液添加剂及其制备方法
CN110797509A (zh) * 2019-09-25 2020-02-14 双登集团股份有限公司 一种改善铅酸蓄电池负极板硫酸盐化的组分

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHADI HOSSEINI ET AL: "Sodium hexa meta phosphate impact as electrolyte additive on electrochemical behavior of lead-acid battery", JOURNAL OF ENERGY STORAGE, vol. 17, 1 June 2018 (2018-06-01), pages 170 - 180, XP055750460, ISSN: 2352-152X, DOI: 10.1016/j.est.2017.11.015 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115360423A (zh) * 2022-09-20 2022-11-18 济南大学 一种改善金属二次电池电性能的方法

Similar Documents

Publication Publication Date Title
US9263745B2 (en) Rechargeable electrochemical battery cell
Wu et al. The electrochemical performance improvement of LiMn2O4/Zn based on zinc foil as the current collector and thiourea as an electrolyte additive
US9728775B2 (en) Composite anode structure for aqueous electrolyte energy storage and device containing same
EP3196964B1 (fr) Additif graphite avancé pour améliorer le cycle de vie des décharges profondes des batteries plomb-acide
Jiang et al. Extending the cycle life of Na 3 V 2 (PO 4) 3 cathodes in sodium-ion batteries through interdigitated carbon scaffolding
Saravanan et al. An in situ generated carbon as integrated conductive additive for hierarchical negative plate of lead-acid battery
Park et al. Bismuth oxide as an excellent anode additive for inhibiting dendrite formation in zinc-air secondary batteries
Lu et al. Rechargeable hybrid aqueous batteries using silica nanoparticle doped aqueous electrolytes
Enos et al. Understanding function and performance of carbon additives in lead-acid batteries
CA3051078A1 (fr) Dispositifs de stockage d'energie contenant des additifs a base de carbone et leurs procedes de production
KR20110017850A (ko) 나트륨 이온계 수성 전해질 전기화학 2차 에너지 저장 장치
EP3635805B1 (fr) Batterie plomb-acide
KR20140070525A (ko) 애노드 제한 전기화학 셀들로 구성된 고전압 배터리
Qiu et al. Porous hydrated ammonium vanadate as a novel cathode for aqueous rechargeable Zn-ion batteries
Chen et al. Electrochemical performance of electrospun LiFePO4/C submicrofibers composite cathode material for lithium ion batteries
WO2021046373A1 (fr) Additifs d'électrolyte pour batteries au plomb-acide
US10355316B2 (en) High performance lead acid battery with advanced electrolyte system
Park et al. Influence of the electrode materials on the electrochemical performance of room temperature Li-SO2 rechargeable battery
Rogulski et al. Cathode modification in the Leclanché cell
Pavlov et al. Lead-carbon electrode with inhibitor of PbSO4 recrystallization in lead-acid batteries operating on HRPSoC duty
KR20160126580A (ko) 축전지 전해액 조성물 및 그 제조방법
Vujković Comparison of lithium and sodium intercalation materials
Sarawutanukul et al. Influence of Electrode Density on the Microstructural NCA Positive Electrode for Scalable 18650 Li-Ion Batteries
JP2014107115A (ja) ナトリウム二次電池
De Marco Influence of lead (II) carbonate films of non-antimonial grids on the deep discharge cycling behaviour of maintenance-free lead/acid batteries

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20780402

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20780402

Country of ref document: EP

Kind code of ref document: A1