WO2011133677A1 - Suppression des changements chimiques dans une batterie au plomb/acide pour améliorer sa durée de vie - Google Patents

Suppression des changements chimiques dans une batterie au plomb/acide pour améliorer sa durée de vie Download PDF

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Publication number
WO2011133677A1
WO2011133677A1 PCT/US2011/033263 US2011033263W WO2011133677A1 WO 2011133677 A1 WO2011133677 A1 WO 2011133677A1 US 2011033263 W US2011033263 W US 2011033263W WO 2011133677 A1 WO2011133677 A1 WO 2011133677A1
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WO
WIPO (PCT)
Prior art keywords
battery
battery separator
separator
lead
vanillin
Prior art date
Application number
PCT/US2011/033263
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English (en)
Inventor
Robert R. Waterhouse
Chi Thuong-Le La
Richard W. Pekala
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Amtek Research International, Llc
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Publication date
Application filed by Amtek Research International, Llc filed Critical Amtek Research International, Llc
Publication of WO2011133677A1 publication Critical patent/WO2011133677A1/fr

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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H01M50/437—Glass
    • 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
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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

  • This disclosure relates to battery separators for use in a lead-acid battery and, in particular, to a battery separator in which, throughout its porous structure, a benzaldehyde derivative is dispersed as a hydrogen-evolution inhibitor to improve the cycle life of a deep cycle battery.
  • the recombinant cell and the flooded cell are two different types of commercially available lead acid battery designs. Both types include adjacent positive and negative electrodes that are separated from each other by a porous battery separator.
  • the porous separator prevents the adjacent electrodes from coming into physical contact and provides space for an electrolyte to reside.
  • Such separators are formed of materials that are sufficiently porous to permit the electrolyte to reside in the pores of the separator material, thereby permitting ionic current flow between adjacent positive and negative plates.
  • the recombinant battery also referred to as a valve regulated lead-acid (“VRLA”) battery, typically includes an absorptive glass mat (AGM) separator composed, in whole or in part, of microglass fibers.
  • AGM absorptive glass mat
  • AGM separators provide high porosity and uniform electrolyte distribution with a certain fraction of the pores left open to facilitate the transport of oxygen from the positive electrode, where the oxygen is produced during charging, to the negative electrode, where the oxygen is recombined with hydrogen ions to produce water.
  • AGM separators also exhibit low puncture resistance, which can be disadvantageous to the operation of the VRLA battery in certain applications, such as high vibration environments.
  • flooded cell battery separators typically include porous derivatives of cellulose, polyvinyl chloride, organic rubber, and polyolefins. More specifically, microporous polyethylene separators are commonly used because of their ultrafine pore size, which inhibits dendritic growth while providing low electrical resistance, good oxidation resistance, and excellent flexibility.
  • polyethylene separator is something of a misnomer because these microporous separators require large amounts of precipitated silica to be sufficiently acid wettable.
  • the volume fraction of precipitated silica and its distribution in the separator generally control its electrical properties, while the volume fraction and orientation of polyethylene in the separator generally control its mechanical properties.
  • precipitated silica is typically combined with a polyolefin, a process oil, and various minor ingredients to form a separator mixture that is extruded at an elevated temperature through a slot die to form an oil-filled sheet.
  • the oil-filled sheet is calendered to its desired thickness and profile, and the majority of the process oil is extracted.
  • the sheet is dried to form a microporous polyolefin separator and is slit into an appropriate width for a specific battery design.
  • the separator is fed to a machine that forms "envelopes" by cutting the separator material and sealing its edges such that an electrode can be inserted to form an electrode package.
  • the electrode packages are stacked such that the separator acts as a physical spacer and an electronic insulator between positive and negative electrodes.
  • An electrolyte is then introduced into the assembled battery to facilitate ionic conduction within the battery.
  • the primary purposes of the polyolefin contained in the separator are to (1 ) provide mechanical integrity to the polymer matrix so that the separator can be enveloped at high speeds and (2) to prevent grid wire puncture during battery assembly or operation.
  • the hydrophobic polyolefin preferably has a molecular weight that provides sufficient molecular chain entanglement to form a microporous web with high puncture resistance.
  • the primary purpose of the hydrophilic silica is to increase the acid wettability of the separator web, thereby lowering the electrical resistivity of the separator. In the absence of silica, the sulfuric acid would not wet the hydrophobic web and ion transport would not occur, resulting in an inoperative battery.
  • Controlled chemical reactions between active chemicals produce the desired conversion of chemical energy into electrical energy occurring in a lead-acid battery.
  • the desired chemical reactions on which battery operation depends are also accompanied by adverse chemical side-reactions that consume or impede the reactions of some of the active chemicals.
  • Decomposition of water and changes in the volume and composition of the electrolyte are undesirable effects of adverse chemical side-reactions occurring in lead-acid battery operation.
  • One chemical side- reaction, hydrogen gas evolution is greatly increased by the presence of antimony (Sb) in the grids of the positive battery electrode plates.
  • Antimony from the grid of the positive electrode dissolves slowly into the acid electrolyte. Once in solution, the antimony diffuses throughout the electrolyte, where some of the antimony
  • the antimony becomes reduced and deposits onto the negative electrode.
  • the deposited antimony has a lower overpotential for hydrogen evolution (i.e., hydrogen is more easily evolved from it) than that of the lead electrode. This results in an increase in hydrogen evolution during charging of the battery, a reduction in charging efficiency, and an increase in the rate of water loss from the battery. Suppression of hydrogen gas evolution would, therefore, prolong the nominal operational
  • a battery separator includes dispersed throughout its porous structure a benzaldehyde derivative as a hydrogen-evolution inhibitor to improve the cycle life of a lead-acid battery containing the battery separator.
  • the disclosed battery separator is particularly useful in a deep cycle battery installed in an electric vehicle, such as a golf car or a floor scrubber.
  • Preferred embodiments of the disclosed battery separator are based on a microporous polyethylene separator material that includes a microporous polyolefin web exhibiting high-strength mechanical and low electrical resistance properties.
  • the microporous polyolefin web has dispersed throughout its porous structure vanillin (4- hydroxy 3-methoxybenzaldehyde) compound as a preferred derivative of benzaldehyde that interacts with antimony present in the battery electrode plates to suppress hydrogen gas evolution.
  • vanillin (4- hydroxy 3-methoxybenzaldehyde) compound
  • the presence of vanillin dispersed throughout the porous structure exhibits strong antimony- suppression behavior and thereby maintains hydrogen evolution inhibitor properties during handling and manipulation of the battery separator.
  • Other compounds exhibiting strong antimony-suppression behavior include ortho-anisaldehyde
  • An alternative preferred embodiment of the disclosed battery separator is based on an AGM battery separator material also having a porous structure through which a benzaldehyde hydrogen gas evolution inhibitor of the above-described type is dispersed.
  • Fig. 1 is a bar graph showing antimony selectivity ratios for different sets of battery separators.
  • Figs. 2, 3, and 4 are graphs showing voltammetry scan results for microporous polyethylene battery separators dip-coated in solutions of vanillin in acetone.
  • Fig. 5 is a graph showing voltammetry scan results for a microporous polyethylene battery separator treated in solution of vanillin in trichloroethylene (TCE).
  • Fig. 6 is a graph showing voltammetry scan results for a microporous polyethylene battery separator treated in solution of vanillin in water.
  • Fig. 7 is a graph showing voltammetry scan results for a commercial deep discharge separator.
  • Fig. 8 is a graph showing voltammetry scan results for an absorptive glass mat (AGM) battery separator treated in solution of vanillin in acetone.
  • AGM absorptive glass mat
  • Fig. 9 is a diagram of a lead-acid cell, illustrating the position and function of the disclosed battery separator.
  • First preferred embodiments of the disclosed battery separator are based on a RhinoHide® microporous polyethylene battery separator material, which is manufactured by Entek International LLC, Riverside, Oregon.
  • a benzaldehyde hydrogen gas evolution inhibitor is dispersed throughout the porous structure of the RhinoHide® separator.
  • Vanillin is a preferred derivative of benzaldehyde because it is soluble in water and readily available. Distribution of vanillin throughout the porous structure of the RhinoHide® separator makes it more durable when compared to a vanillin surface coating, which would crystallize on the separator surface and fall off with handling.
  • the vanillin compound interacts with the antimony present at the surface of the negative electrodes of the battery to inhibit hydrogen gas evolution.
  • Vanillin exhibits significant antimony selectivity, which is defined for a given cathode voltage, as a ratio of relative change in the hydrogen evolution current to relative change in lead (Pb) discharge capacity. A higher selectivity ratio indicates better hydrogen evolution inhibition.
  • the vanillin compound is applied to the RhinoHide® separator by dip coating sheets of the RhinoHide® separator material in a 1 %-3% aqueous vanillin solution heated to 50°C-75°C. Dip coating the separator material in the heated solution achieves wetting of the pore structure and good dispersion of vanillin throughout the porous structure of the RhinoHide® separator.
  • Use of the disclosed vanillin-treated RhinoHide® separator in a deep cycle lead-acid battery installed in an electric vehicle increases the number of charge-to-discharge cycles
  • a first set of samples of separator material was dip-coated in solutions of vanillin in acetone at 0.24% and 2.4% concentrations. Batteries made with these separators demonstrated good performance compared to a Daramic, Inc., HD separator, which functioned as a control.
  • a second set of samples of separator material included separators treated with vanillin using three different solvents:
  • the Antimony Suppression Test performed to carry out this study uses Linear Scanning Voltammetry (LSV) to examine the hydrogen evolving behavior of the negative lead electrode in the presence of antimony together with a candidate antimony control additive (ACA).
  • LSV Linear Scanning Voltammetry
  • ACA candidate antimony control additive
  • the leachates were prepared by adding 100 ml of 1 .210 s.g., pre- electrolyzed sulfuric acid to the following separator materials and cooking them for 4 days at 70°C:
  • the Antimony Suppression Test was performed using a three-electrode cell apparatus. After three cathodic cycles between -700 mV and -1700 mV to condition the electrode, a blank LSV scan was run. The electrode was held at a fixed potential of -1200 mV for 15 minutes, then swept from -1200 mV to -700 mV at 5 mV/sec. Following the blank scan, 1 .0 ml of 0.1 % Sb 3+ ion in HN0 3 acidified solution was added to the electrolyte, resulting in a concentration of 8.2 ppm, and the LSV scan was repeated.
  • the voltammetry scans produced for each test are shown in Figs. 2-7.
  • the selectivity ratio for each test was determined from the relative change in hydrogen evolution current at -1200 mv divided by the relative change in Pb discharge capacity, which is expressed as:
  • Fig. 2 presents the Antimony Selectivity Test results for a separator treated with 2.4% vanillin in acetone in the first set. The curves show that suppression of the antimony behavior is significant.
  • Fig. 3 presents the Antimony Selectivity Test results for a separator treated with 0.24% vanillin in acetone in the first set. The curves show that suppression of the antimony behavior is small but significant.
  • Fig. 4 presents the Antimony Selectivity Test results for a separator treated with 2.4% vanillin in acetone in the second set. The curves show that suppression of the antimony behavior is significant.
  • Fig. 5 presents the Antimony Selectivity Test results for a separator treated with 2.5% vanillin in TCE in the second set. The curves show that suppression of the antimony behavior is significant.
  • Fig. 6 presents the Antimony Selectivity Test results for a separator treated with 3.0% vanillin in water in the second set. The curves show that suppression of the antimony behavior is significant.
  • Fig. 7 presents the Antimony Selectivity Test results for a Daramic HD separator, which is a commercial separator for deep discharge batteries. The curves show that suppression of the antimony behavior is significant.
  • the separator described above is delivered in roll form to lead-acid battery manufacturers where the separator is fashioned into "envelopes.” An electrode can then be inserted into a separator to form an electrode package. The electrode packages are stacked so that the separator acts as a physical spacer and as an electrical insulator between positive and negative electrodes.
  • a second preferred embodiment of the disclosed battery separator is based on an absorptive glass mat (AGM) battery separator material, such as that manufactured by Hollingsworth and Vose, East Walpole, MA.
  • a benzaldehyde hydrogen gas evolution inhibitor is dispersed throughout the porous structure of the AGM separator.
  • Vanillin is a preferred derivative of benzaldehyde because it is soluble in water and readily available. Distribution of vanillin throughout the porous structure of the AGM separator makes it more durable when compared to a vanillin surface coating, which would crystallize on the separator surface and fall off with handling.
  • a sheet of AGM separator with a basis weight of 225 grams per square meter, was cut into a piece measuring 28 cm x 38 cm.
  • a 1 % solution by weight of vanillin (Alfa Aesar, 99%) in acetone (Chem Products, reagent grade) was prepared. This solution was poured over the AGM sheet in a glass pan until the sheet was covered. The saturated sheet was lifted out of the solution and placed in another glass pan and allowed to dry at ambient conditions for two hours, followed by oven drying for 20 minutes at 70°C. The uptake of vanillin solution by the AGM sheet was approximately 130 ml.
  • Fig. 9 is a diagram of a lead-acid cell 100, which includes two electrodes 102, each with one end dipped in an electrolytic fluid or gel 104, typically sulfuric acid, and each with the other end connected by a wire 106 to an external electric circuit 108.
  • Each electrode 102 separately undergoes one-half of an electrochemical oxidation-reduction reaction to either produce or consume free electric charge.
  • a lead anode 1 10, or negative electrode is oxidized in a reaction that supplies electrons 1 12.
  • a lead oxide cathode 1 14, or positive electrode is reduced in a reaction that consumes electrons.
  • a main requirement is that electrodes 102 be kept separate from each other so that electron transfer is forced to occur through wire 106 in external electric circuit 108.
  • a separator 1 16 is therefore used to divide cell 100 into a left compartment 1 18a and a right compartment 1 18b. Separator 1 16 prevents electrodes 102 from coming into physical contact with each other and short-circuiting cell 100. Separator 1 16 permits electrolyte 104 to reside in the pores of the separator material and thereby facilitates diffusion of ions 120 between left compartment 1 18a and right compartment 118b. If separator 1 16 is insufficiently porous, ionic current flow through electrolyte 104 is hindered and the electrochemical reaction may be hindered or ultimately arrested.
  • Battery separator 1 16 based on microporous polyethylene material of the first preferred embodiments or on AGM material of the second preferred embodiment and through the porous structure of which a benzaldehyde hydrogen gas evolution inhibitor is dispersed, improves the cycle life of lead-acid battery 100.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Cell Separators (AREA)

Abstract

Un séparateur de batterie (116) inclut, dispersé partout dans sa structure poreuse, un dérivé de benzaldéhyde comme inhibiteur de dégagement d'hydrogène pour améliorer la durée de vie d'une batterie au plomb/acide (100) contenant le séparateur de batterie. Le séparateur de batterie divulgué est en particulier utile dans une batterie à décharge poussée installée dans un véhicule électrique, comme une voiture de golf ou un appareil à nettoyer les sols. Les modes de réalisation préférés du séparateur de batterie divulgué sont basés sur un matériau de séparateur microporeux de polyéthylène ou sur une pâte vitreuse absorbante (AGM) ayant une structure poreuse à travers laquelle l'inhibiteur de dégagement d'hydrogène est dispersé. Le composé de vanilline (4-hydroxy-3-méthoxybenzaldéhyde) est un dérivé préféré de benzaldéhyde qui interagit avec l'antimoine présent dans les plaques d'électrode de batterie pour supprimer le dégagement du gaz d'hydrogène. La vanilline dispersée partout dans la structure poreuse montre un fort comportement suppresseur d'antimoine et de cette façon maintient les propriétés d'inhibiteur de dégagement d'hydrogène durant le maniement et la manipulation du séparateur de batterie.
PCT/US2011/033263 2010-04-23 2011-04-20 Suppression des changements chimiques dans une batterie au plomb/acide pour améliorer sa durée de vie WO2011133677A1 (fr)

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US61/327,512 2010-04-23

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015103314A3 (fr) * 2013-12-31 2015-11-12 Energy Power Systems LLC Procédé et appareil permettant d'améliorer la prise de charge d'accumulateurs au plomb
WO2015176016A1 (fr) * 2014-05-15 2015-11-19 Amtek Research International Llc Électrolytes de gel réticulés de façon covalente
CN105355821A (zh) * 2015-08-10 2016-02-24 达拉米克有限责任公司 性能改进的电池串
US9595360B2 (en) 2012-01-13 2017-03-14 Energy Power Systems LLC Metallic alloys having amorphous, nano-crystalline, or microcrystalline structure
CN112038573A (zh) * 2020-08-19 2020-12-04 江苏塔菲尔新能源科技股份有限公司 极片及其制备方法、电芯及电池
CN112038644A (zh) * 2020-08-24 2020-12-04 江苏塔菲尔新能源科技股份有限公司 一种功能涂层、电极极片以及电化学装置
US11211612B2 (en) 2014-06-17 2021-12-28 Owens Corning Intellectual Capital, Llc Water loss reducing pasting mats for lead-acid batteries
US11380962B2 (en) 2014-06-17 2022-07-05 Owens Corning Intellectual Capital, Llc Anti-sulphation pasting mats for lead-acid batteries

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US6576373B1 (en) * 2000-01-26 2003-06-10 Matsushita Electric Industrial Co., Ltd. Non-aqueous electrochemical apparatus and electrolyte thereof

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BOHNSTEDT ET AL.: "Antimony poisoning in lead-acid batteries.", JOURNAL OF POWER SOURCES, vol. 19, no. ISS.4, April 1987 (1987-04-01), pages 307 - 314, Retrieved from the Internet <URL:http://www.sciencedirect.com/science/article/pii/0378775387870064> [retrieved on 20110614] *
DIETZ ET AL.: "Influence of substituted benzaldehydes and their derivatives as inhibitors for hydrogen evolution in lead/acid batteries.", JOURNAL OF POWER SOURCES, vol. 53, no. ISS.2, February 1995 (1995-02-01), pages 359 - 365, Retrieved from the Internet <URL:http://www.sciencedirect.com/science/article/pii/037877539402001J> [retrieved on 20110614] *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9595360B2 (en) 2012-01-13 2017-03-14 Energy Power Systems LLC Metallic alloys having amorphous, nano-crystalline, or microcrystalline structure
WO2015103314A3 (fr) * 2013-12-31 2015-11-12 Energy Power Systems LLC Procédé et appareil permettant d'améliorer la prise de charge d'accumulateurs au plomb
CN106575775B (zh) * 2014-05-15 2021-05-18 安特克研发国际公司 共价交联凝胶电解质
CN106575775A (zh) * 2014-05-15 2017-04-19 安特克研发国际公司 共价交联凝胶电解质
US10199692B2 (en) 2014-05-15 2019-02-05 Amtek Research International Llc Covalently cross-linked gel electrolytes
WO2015176016A1 (fr) * 2014-05-15 2015-11-19 Amtek Research International Llc Électrolytes de gel réticulés de façon covalente
US11211612B2 (en) 2014-06-17 2021-12-28 Owens Corning Intellectual Capital, Llc Water loss reducing pasting mats for lead-acid batteries
US11380962B2 (en) 2014-06-17 2022-07-05 Owens Corning Intellectual Capital, Llc Anti-sulphation pasting mats for lead-acid batteries
US12119497B2 (en) 2014-06-17 2024-10-15 Owens Corning Intellectual Capital, Llc Water loss reducing pasting mats for lead-acid batteries
WO2017027535A1 (fr) * 2015-08-10 2017-02-16 Daramic, Llc Séparateurs, batteries et chaînes de batteries améliorés ayant des performances améliorées, et procédés associés
CN105355821A (zh) * 2015-08-10 2016-02-24 达拉米克有限责任公司 性能改进的电池串
US12113178B2 (en) 2015-08-10 2024-10-08 Daramic, Llc Separators, batteries, battery strings with improved performance, and related methods
CN112038573A (zh) * 2020-08-19 2020-12-04 江苏塔菲尔新能源科技股份有限公司 极片及其制备方法、电芯及电池
CN112038644A (zh) * 2020-08-24 2020-12-04 江苏塔菲尔新能源科技股份有限公司 一种功能涂层、电极极片以及电化学装置

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