WO2017027037A1 - Séparateurs améliorés pour des batteries planes - Google Patents

Séparateurs améliorés pour des batteries planes Download PDF

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Publication number
WO2017027037A1
WO2017027037A1 PCT/US2015/045060 US2015045060W WO2017027037A1 WO 2017027037 A1 WO2017027037 A1 WO 2017027037A1 US 2015045060 W US2015045060 W US 2015045060W WO 2017027037 A1 WO2017027037 A1 WO 2017027037A1
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WO
WIPO (PCT)
Prior art keywords
batteries
flat plate
separators
separator
battery
Prior art date
Application number
PCT/US2015/045060
Other languages
English (en)
Inventor
Surendra Kumar Mittal
Naveen Prabhu SHANMUGAM
J. Kevin Whear
Eric H. Miller
Original Assignee
Daramic, Llc
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 Daramic, Llc filed Critical Daramic, Llc
Priority to PCT/US2015/045060 priority Critical patent/WO2017027037A1/fr
Priority to CN202110936305.3A priority patent/CN113644381A/zh
Priority to PCT/US2016/046668 priority patent/WO2017027765A1/fr
Priority to US15/235,197 priority patent/US10693118B2/en
Priority to CN201680058696.0A priority patent/CN108352481B/zh
Publication of WO2017027037A1 publication Critical patent/WO2017027037A1/fr
Priority to US16/886,805 priority patent/US11705582B2/en

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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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/12—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • 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
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • H01M50/466—U-shaped, bag-shaped or folded
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present disclosure or invention is directed to novel or improved separators, battery separators, flat plate separators, batteries, cells, and/or methods of manufacture and/or use of such separators, battery separators, flat plate separators, cells, and/or batteries.
  • the present disclosure or invention is directed to novel or improved lead acid battery separators for flat plate cycling batteries, flat plate deep cycling batteries, flat plate inverter batteries, flat plate UPS batteries, flat plate home UPS batteries, flat plate long cycle life batteries, deep cycle stationary, traction, inverter, or fork lift batteries, flooded batteries, UPS, ESS, BESS, flat plate cells, and/or improved methods of making and/or using such improved separators, cells, batteries, systems, and/or the like.
  • the present disclosure or invention is directed to an improved separator for flat plate stationary batteries and/or improved methods of using such batteries having such improved separators.
  • disclosed herein are methods, systems and battery separators for enhancing battery life, reducing water loss, and/or improving uniformity in at least flat plate stationary batteries.
  • VLA battery One type of lead acid flooded or VLA battery is known as a flat plate deep cycle battery (or more simply, a flat plate battery). These batteries are often employed in high-temperature and partial charge applications, such as found in inverters, photo voltaic systems, and the like. When used for deep cycling applications, flat plate stationary batteries tend to remain under charged or in a partial state of charge.
  • the battery's efficiency and/or charge time diminish over the life of the battery.
  • the battery plates deteriorate due to sulphation (or sulfation), and the battery life ends prematurely.
  • the typical float charging voltage for instance, about 13.8V to 14.4V
  • flat plate deep cycle batteries do not fully recover after a deep discharge.
  • simply increasing the float charging voltage is not a general solution, because higher voltages accelerate the corrosion of the grid and may reduce cycle life.
  • the key requirements include better re-chargeability, improved backup time as well as lower water loss to reduce maintenance needs.
  • improvement of one criteria can be
  • the present disclosure or invention may address the above issues or needs and/or may provide novel or improved
  • the present disclosure or invention is directed to novel or improved separators, battery separators, flat plate separators, batteries, cells, and/or methods of manufacture and/or use of such separators, battery separators, flat plate separators, cells, and/or batteries.
  • the present disclosure or invention is directed to novel or improved lead acid battery separators for flat plate cycling batteries, flat plate deep cycling batteries, flat plate inverter batteries, flat plate UPS batteries, flat plate home UPS batteries, flat plate long cycle life batteries, deep cycle stationary, traction, inverter, or fork lift batteries, flooded batteries, UPS, ESS, BESS, fork truck, pallet jack, golf car, or scissor lift batteries, flat plate cells, and/or improved methods of making and/or using such improved separators, cells, batteries, systems, and/or the like.
  • the present disclosure or invention is directed to an improved separator for flat plate stationary batteries and/or improved methods of using such batteries having such improved separators.
  • the present disclosure or invention is directed to an improved separator for flat plate batteries wherein the separator includes performance enhancing additives or coatings, hybrid envelopes, cross rib shapes or profiles, and/or the like.
  • the separators preferably include or contain performance enhancing additives, hybrid envelope shapes, and/or ribbed surfaces.
  • a separator in the shape of a hybrid envelope is provided.
  • the separator can be a porous membrane, for instance a porous polyolefin such as polyethylene.
  • the hybrid envelope can contain one or more openings or slits along the bottom edge. Preferably, the openings are not disposed in a corner of the envelope.
  • a plurality of ribs may be disposed upon the inner face of the envelope.
  • a plurality of ribs may be disposed upon the outer face of the envelope in a direction different than the ribs upon the inner face (cross ribs).
  • the ribs of the inner and outer faces may be substantially perpendicular to each other.
  • the ribs of the outer face (the negative face) may be mini-ribs or mini-cross ribs (smaller and more closely spaced than the positive or inner face ribs).
  • the separator may contain a surfactant additive along with other additives or agents, residual oil, and fillers.
  • Figure 1 photographically depict the difference between a separator shaped into a hybrid envelope (Fig. 1A) with slits or openings and a separator in a more
  • Figure 2A, 2B and 2C depict the discharge (as a percentage of initial discharge) over the course of 168 cycles (discharging at 43A to 10.5 V, charging at 13.9 V for 10 hour) for a flat plate inverter battery having a conventional separator (lowest trace), a ribbed separator having an additive and in the shape of a conventional envelope (middle trace) and a ribbed separator having an additive and in the shape of a hybrid envelope (top trace).
  • Figure 3A, 3B and 3C depict the discharge (as a percentage of initial discharge) over the course of 168 cycles (discharging at 43A to 10.5 V, charging at 13.9 V for 10 hour) for a flat plate inverter battery having a conventional separator (bottom trace) and a ribbed separator having an additive and in the shape of a hybrid envelope (top trace).
  • Figure 4A, 4B and 4C depict the comparative recharge over the course of 168 cycles (discharging at 43A to 10.5 V, charging at 13.9 V for 10 hour) for a flat plate inverter battery having a conventional separator (bottom trace) and a ribbed separator having an additive and in the shape of a hybrid envelope (top trace).
  • Figure 5A, 5B and 5C depict the comparative specific gravity over the course of 50 cycles (discharging at 43A to 10.5 V, charging at 13.9 V for 10 hour) for a flat plate inverter battery having a conventional separator (bottom trace) and a ribbed separator having an additive and in the shape of a hybrid envelope (top trace).
  • Figure 6A, 6B and 6C depict the comparative recharge profile (discharging at 43A to 10.5 V, charging at 13.9 V for 10 hour) for a flat plate inverter battery having a conventional separator and a ribbed separator having an additive and in the shape of a hybrid envelope.
  • Figure 8A, 8B and 8C depict the comparative recharge input data in Ah during inverter battery cycling tests for a flat plate inverter battery having a conventional separator (bottom trace) and a ribbed separator having an additive and in the shape of a hybrid envelope (top trace).
  • Figure 9A, 9B and 9C depict the comparative specific gravity during inverter battery cycling tests for a flat plate inverter battery having a conventional separator (bottom trace) and a ribbed separator having an additive and in the shape of a hybrid envelope (top trace).
  • Figure 10 depicts the comparative water loss for a flat plate inverter battery having a conventional separator and a ribbed separator having an additive and in the shape of a hybrid envelope.
  • Figures 11 A, 11 B, 11C, 11 D, 11 E, and 11 F depict the comparative water loss for a flat plate inverter battery having a conventional separator (top trace) and a ribbed separator having an additive and in the shape of a hybrid envelope (bottom trace).
  • the inventive separator is preferably a porous membrane (such as a
  • microporous membrane having pores less than about 1 micron, mesoporous, or a macroporous membrane having pores greater than about 1 micron) made of natural or synthetic materials, such as polyolefin, polyethylene, polypropylene, phenolic resin, PVC, rubber, synthetic wood pulp (SWP), glass fibers, cellulosic fibers, or combinations thereof, more preferably a microporous membrane made from thermoplastic polymers.
  • the preferred microporous membranes may have pore diameters of about 0.1 micron (100 nanometers) and porosities of about 60%.
  • the thermoplastic polymers may, in principle, include all acid-resistant thermoplastic materials suitable for use in lead acid batteries.
  • the preferred thermoplastic polymers include polyvinyls and polyolefins.
  • the polyvinyls include, for example, polyvinyl chloride (PVC).
  • the polyolefins include, for example, polyethylene, ultrahigh molecular weight polyethylene (UHMWPE), and polypropylene.
  • One preferred embodiment may include a mixture of filler (for example, silica) and UHMWPE.
  • the preferred separator may be made by mixing, in an extruder, about 30% by weight silica with about 10% by weight UHMWPE, and about 60% processing oil.
  • the mixture may also include minor amounts of other additives or agents as is common in the separator arts (such as wetting agents, colorants, antistatic additives, and/or the like) and is extruded into the shape of a flat sheet.
  • Suitable surfactants include surfactants such as salts of alkyi sulfates; alkylarylsulfonate salts; alkylphenol-alkylene oxide addition products; soaps; alkyl-naphthalene-sulfonate salts; dialkyl esters of sulfo-succinate salts; quaternary amines; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.
  • surfactants such as salts of alkyi sulfates; alkylarylsulfonate salts; alkylphenol-alkylene oxide addition products; soaps; alkyl-naphthalene-sulfonate salts; dialkyl esters of sulfo-succinate salts; quaternary amines; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.
  • the additive can be a non-ionic surfactant such as polyol fatty acid esters, polyethoxylated esters, polyethoxylated alcohols, alkyi polysaccharides such as alkyi polyglycosides and blends thereof, amine ethoxylates, sorbitan fatty acid ester ethoxylates, organosilicone based surfactants, ethylene vinyl acetate terpolymers, ethoxylated alkyi aryl phosphate esters and sucrose esters of fatty acids.
  • a non-ionic surfactant such as polyol fatty acid esters, polyethoxylated esters, polyethoxylated alcohols, alkyi polysaccharides such as alkyi polyglycosides and blends thereof, amine ethoxylates, sorbitan fatty acid ester ethoxylates, organosilicone based surfactants, ethylene vinyl acetate terpolymers,
  • the battery separators can be provided in various ways with the additive, agents, fillers, or additives.
  • the additives can for example be applied to the separator when it is finished (i.e. after the extraction) and/or added to the mixture used to produce the separator.
  • the additive or a solution of the additive is applied to the surface of the separator.
  • This variant is suitable in particular for the application of non-thermostable additives and additives which are soluble in the solvent used for the subsequent extraction.
  • Particularly suitable as solvents for the additives according to the invention are low-molecular-weight alcohols, such as methanol and ethanol, as well as mixtures of these alcohols with water.
  • the application can take place on the side facing the negative electrode, the side facing the positive electrode or on both sides of the separator.
  • the additive can be present at a density of at least 0.5 g/m 2 , 1.0 g/m 2 , 1.5 g/m 2 , 2.0 g/m 2 , 2.5 g/m 2 , 3.0 g/m 2 , 3.5 g/m 2 , 4.0 g/m 2 , 4.5 g/m 2 , 5.0 g/m 2 , 5.5 g/m 2 , 6.0 g/m 2 , 6.5 g/m 2 , 7.0 g/m 2 , 7.5 g/m 2 , 8.0 g/m 2 , 8.5 g/m 2 , 9.0 g/m 2 , 9.5 g/m 2 or 10.0 g/m 2 .
  • the additive can be present on the separator at a density between 0.5-10 g/m 2 , 1.0-10.0 g/m 2 , 1.5-10.0 g/m 2 , 2.0-10.0 g/m 2 , 2.5-10.0 g/m 2 , 3.0-10.0 g/m 2 , 3.5- 0.0 g/m 2 , 4.0-10.0 g/m 2 , 4.5-10.0 g/m 2 , 5.0-10.0 g/m 2 , 5.5-10.0 g/m 2 , 6.0-10.0 g/m 2 , 6.5-10.0 g/m 2 , 7.0-10.0 g/m 2 , 7.5-10.0 g/m 2 , 5.0-10.5 g/m 2 , 5.0-1 .0 g/m 2 , 5.0-12.0 g/m 2 , or 5.0-15.0 g/m 2 .
  • the application may also take place by dipping the battery separator in the additive or a solution of the additive and subsequently optionally removing the solvent, e.g. by drying. In this way the application of the additive can be combined for example with the extraction often applied during separator production.
  • Another preferred option is to mix the additive or additives into the mixture of thermoplastic polymer and optionally fillers and other additives which is used to produce the battery separators.
  • the additive-containing homogeneous mixture is then formed into a web-shaped material.
  • a battery separator with ribs can have transverse cross-ribs on the opposite face of the separator as the longitudinal ribs.
  • the ribbed separator can have a transverse rib height of at least 0.005 mm, 0.01 mm, 0.025 mm, 0.05 mm, 0.075 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, or 1.0 mm.
  • the ribbed separator can have a transverse rib height between 0.005-1.0 mm, 0.01-0.5 mm, 0.025-0.5 mm, 0.05- 0.5 mm, 0.075-0.5 mm, 0.1-0.5 mm, 0.2-0.4 mm, 0.3-0.5 mm, or 0.4-0.5 mm.
  • the ribbed separator can have longitudinal rib height of at least 0.005 mm, 0.01 mm, 0.025 mm, 0.05 mm, 0.075 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, or 1.5 mm.
  • the ribbed separator can have a transverse rib height between 0.005-1.5 mm, 0.01-1.0 mm, 0.025-1.0 mm, 0.05-1.0 mm, 0.075-1.0 mm, 0.1-1.0 mm, 0.2-1.0 mm, 0.3-1.0 mm, 0.4-1.0 mm, 0.5-1.0 mm, 0.4-0.8 mm or 0.4-0.6 mm.
  • the ribbed separator can have a sheet (substrate) thickness of at least 0.005 mm, 0.01 mm, 0.025 mm, 0.05 mm, 0.075 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, or 1.0 mm.
  • the ribbed separator can have a sheet (substrate) thickness between 0.005- 1.0 mm, 0.01-1.0 mm, 0.025-1.0 mm, 0.05-1.0 mm, 0.075-1.0 mm, 0.1-1.0 mm, 0.2-1.0 mm, 0.3-1.0 mm, 0.4-1.0 mm, 0.4-0.9 mm, 0.4-0.8 mm, 0.5-0.8 mm or 0.6-0.8 mm.
  • the ribbed separator can have overall thickness (positive rib + backweb + negative rib) of at least 0.05 mm, 0.1 mm, 0.25 mm, 0.5 mm, 0.75 mm, 1.0 mm, 1.5 mm, 2.0 mm, 2.5 mm, 3.0 mm, 3.5 mm, 4.0 mm, 4.5 mm, 5.0 mm, or 6.0 mm.
  • the ribbed separator can have a transverse rib height between 0.05-5.0 mm, 0.1-5.0 mm, 0.2-5.0 mm, 0.5-5.0 mm, 1.0-5.0 mm, or 1.0- 4.0 mm.
  • the ribbed separator can have the following:
  • Transverse Rib Height preferably between about 0.02 to 0.45 mm, and most preferably between about 0.075 to 0.3 mm.
  • the separator is made up of an ultrahigh molecular weight polyethylene (UHMWPE) mixed with a processing oil plus additive and precipitated silica.
  • UHMWPE ultrahigh molecular weight polyethylene
  • the separator is made up of an ultrahigh molecular weight polyethylene (UHMWPE) mixed with a processing oil and precipitated silica.
  • the additive can then be applied to the separator via one or more of the techniques described above.
  • the negative cross ribs are rounded mini-ribs and preferably have a 2 to 6 mil radius and a 10 to 50 mil rib spacing.
  • the separator is made of a microporous
  • thermoplastic material which is provided with longitudinal positive ribs and transverse negative ribs with the height of at least a majority of the longitudinal ribs being greater than that of the transverse ribs, and the longitudinal and transverse ribs being solid ribs which are formed integrally from the plastic, characterized in that the transverse ribs extend across substantially the entire back width of the separator.
  • the separator back web or sheet thickness may be approximately 0.10 to 0.50 mm
  • the height of the longitudinal ribs may be 0.3 to 2.0 mm and the height of the transverse ribs may be 0.1 to 0.7 mm
  • the longitudinal rigidity with 00 mm width may be approximately 5 mJ and the transverse rigidity may be approximately 2.5 mJ
  • the total thickness of the separator may be less than 3.5 mm, preferably less than 2.5 mm.
  • the separators can be be processed to form hybrid envelopes.
  • the hybrid envelope can be formed by forming one or more slits or openings before, during or after, folding the separator sheet in half and bonding edges of the separator sheet together so as to form an envelope.
  • the sides are bonded together using welds or mechanical seals to form seams that bring one side of the separator sheet into contact with another side of the separator sheet.
  • Welds can be accomplished, for instance, using heat or ultrasonic processes. This process results in an envelope shape having a bottom folded edge and two lateral edges.
  • Separators can be made from polyethylene and can contain V-shaped mini-ribs extending in the transverse or horizontal direction. These ribs are believed to facilitate release of generated gases in the electrolyte by creating channels by which the gas can escape.
  • Openings can be created in a bottom or lateral edge of the envelope using conventional means.
  • the hybrid envelop can have one or more slits or openings.
  • the length of the openings can at least 1/50 th , 1/25 th , 1/20 th , 1/15 th ., 1/10 th , 1/8 th , 1/5 th , 1/4 th , or 1/3 rd the length of the entire edge.
  • the length of the openings can be 1/50 th to 1/3 rd , 1/25 th to 1/3 rd , 1/20 th to 1/3 rd , 1/20 th to 1/4 th , 1 /15 th to 1/4 th , 1/15 th to 1/5 th or 1/10 th to 1/5 th the length of the entire edge.
  • the hybrid envelope can have 1-5, 1-4, 2-4, 2-3 or 2 openings, which may or may not be equally disposed along the length of the bottom edge.
  • a hybrid envelope according to the present invention is depicted in Figiire 1A. It is preferred that no opening is in the comer of the envelope. Without wishing to be bound by theory, it is believe the openings permit enhanced electrolyte flow between electrodes, while still catching debris released from plate.
  • Range 250 - 500 micron; preferably between 300 - 400 micron
  • separators are also designed to bring other benefits.
  • the separators have the negative cross rib design to maximize bending stiffness and ensure highest productivity.
  • both separators have superior puncture and oxidation resistance when compared to standard PE separators. Combined with the lowest separator resistance, battery manufacturers are likely to find improved and sustained electrical performance in their batteries with these new separators.
  • the preferred products have a micro-porous structure and can be fabricated into pockets or sleeves, which give added protection against side and bottom shorts.
  • inverter batteries meet the consumer's need. In such cases, the lead acid battery has filled the need well and will continue to do so.
  • the inverter batteries may be discharged for up to 8 to 16 hours a day and may only receive an occasional charge. In service these inverter batteries may never get fully recharged and may ultimately fail simply due to under charging. These batteries are often returned to the dealer during the warranty period, receive a vigorous recharge and continue on in serviceable life. With this challenging situation in mind, any actions that can improve the charge acceptance or capacity of the battery will provide longer serviceable life.
  • separators that were negative wrapped sleeves, standard design positive rib profile and 0.6 mm glass-mat. This is a basic configuration currently being used for inverter batteries.
  • separators with the cross or horizontal rib profile, facing the negative plate.
  • the microporous polymer layer is preferably made of a polyolefin, such as polypropylene, ethylene-butene copolymer, and preferably polyethylene, more preferably high molecular weight polyethylene, i.e. polyethylene having a molecular weight of at least 600,000, even more preferably ultra high molecular weight polyethylene, i.e.
  • a polyolefin such as polypropylene, ethylene-butene copolymer
  • polyethylene more preferably high molecular weight polyethylene, i.e. polyethylene having a molecular weight of at least 600,000, even more preferably ultra high molecular weight polyethylene, i.e.
  • polyethylene having a molecular weight of at least 1 ,000,000, in particular more than 4,000,000, and most preferably 5,000,000 to 8,000,000 (measured by viscosimetry and calculated by Margolie's equation), a standard load melt index of substantially 0 (measured as specified in ASTM D 1238 (Condition E) using a standard load of 2,160 g) and a viscosity number of not less than 600 ml/g, preferably not less than 1 ,000 ml/g, more preferably not less than 2,000 ml/g, and most preferably not less than 3,000 ml/g (determined in a solution of 0.02 g of polyolefin in 100 g of decalin at 130° C).
  • the separator is made up of an ultrahigh molecular weight polyethylene (UHMWPE) mixed with a processing oil and precipitated silica.
  • UHMWPE ultrahigh molecular weight polyethylene
  • the separator is made up of an ultrahigh molecular weight polyethylene (UHMWPE) mixed with a processing oil, additive and precipitated silica.
  • the microporous polymer layer preferably comprises a homogeneous mixture of 8 to 100 vol. % of polyolefin, 0 to 40 vol. % of a plasticizer and 0 to 92 vol. % of inert filler material.
  • the preferred filler is dry, finely divided silica.
  • the preferred plasticizer is petroleum oil. Since the plasticizer is the component which is easiest to remove from the polymer-filler-plasticizer composition, it is useful in imparting porosity to the battery separator.
  • the microporous polymer layer has an average pore size of less than 1 pm in diameter. Preferably more than 50% of the pores are 0.5 pm or less in diameter. It is especially preferred that at least 90% of the pores have a diameter of less than 0.5 pm.
  • the microporous polymer layer preferably has an average pore size within the range of 0.05 to 0.5 pm, preferably 0.1 to 0.2 pm.
  • the thickness of the microporous polymer layer is preferably greater than 0.1 mm and less than or equal to 0.6 mm.
  • the thickness of the microporous polymer layer is within the range of 0.25 to 0.45 mm and most preferably is about 0.3 mm.
  • the microporous polyolefin may be provided with one or more additives.
  • One such additive that may be present in the polyolefin is a surfactant.
  • Suitable surfactants include surfactants such as salts of alkyl sulfates; alkylarylsulfonate salts; alkylphenol- alkylene oxide addition products; soaps; alkyl-naphthalene-sulfonate salts; dialkyi esters of sulfo-succinate salts; quaternary amines; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyi phosphate esters.
  • the additive can be a non-ionic surfactant such as polyol fatty acid esters, polyethoxylated esters,
  • polyethoxylated fatty alcohols alkyl polysaccharides such as alkyl polyglycosides and blends thereof, amine ethoxylates, sorbitan fatty acid ester ethoxylates, organosilicone based surfactants, ethylene vinyl acetate terpolymers, ethoxylated aikyl aryl phosphate esters and sucrose esters of fatty acids.
  • the additive can be represented by a compound of Formula (I)
  • R is a non-aromatic hydrocarbon radical with 10 to 4200 carbon atoms, preferably 13 to 4200, which can be interrupted by oxygen atoms,
  • R is H,— (CH 2 ) k COOM x+ i /x or— (CH 2 ) k — S0 3 M x+ i x, preferably H, where k is 1 or 2,
  • M is an alkali metal or alkaline-earth metal ion, H + or NH + , where not all the
  • n O or l
  • m is 0 or an integer from 10 to 1400 and
  • the ratio of oxygen atoms to carbon atoms in the compound according to Formula (I) being in the range from 1 :1.5 to 1 :30 and m and n not being able to simultaneously be 0. However, preferably only one of the variables n and m is different from 0.
  • non-aromatic hydrocarbon radicals radicals which contain no aromatic groups or which themselves represent one.
  • the hydrocarbon radicals can be interrupted by oxygen atoms, i.e. contain one or more ether groups.
  • R is preferably a straight-chain or branched aliphatic hydrocarbon radical which can be interrupted by oxygen atoms. Saturated, uncross-linked hydrocarbon radicals are quite particularly preferred. Surprisingly it was found that through the use of the compounds of Formula (I) for the production of battery separators, they can be effectively protected against oxidative destruction.
  • Battery separators are preferred which contain a compound according to
  • R is a hydrocarbon radical with 10 to 180, preferably 12 to 75 and quite particularly preferably 14 to 40 carbon atoms, which can be interrupted by 1 to 60, preferably 1 to 20 and quite particularly preferably 1 to 8 oxygen atoms, particularly preferably a hydrocarbon radical of formula R 2 — [(OC 2 H 4 ) p (OC 3 H 6 ) q ]— , in which
  • R 2 is an alkyl radical with 10 to 30 carbon atoms, preferably 12 to 25, particularly preferably 14 to 20 carbon atoms,
  • o P is an integer from 0 to 30, preferably 0 to 10, particularly preferably 0 to 4 and o q is an integer from 0 to 30, preferably 0 to 10, particularly preferably 0 to 4, o compounds being particularly preferred in which the sum of p and q is 0 to 10, in particular 0 to 4,
  • R 2 [(OC2H 4 ) p (OC 3 H 6 ) q ]— is to be understood as also including those compounds in which the sequence of the groups in square brackets differs from that shown.
  • compounds are suitable in which the radical in brackets is formed by alternating (OC 2 H 4 ) and (OC 3 H 6 ) groups.
  • Additives in which R 2 is a straight-chain or branched alkyl radical with 10 to 20, preferably 14 to 18 carbon atoms have proved to be particularly advantageous.
  • OC 2 H 4 preferably stands for OCH 2 CH 2 , OC 3 H 6 for OCH(CH 3 )CH 2 and/or OCH 2 CH(CH 3 ).
  • primary alcohols being particularly preferred
  • the fatty alcohol alkoxyiates are for example accessible through reaction of the corresponding alcohols with ethylene oxide or propylene oxide.
  • additives which contain a compound according to Formula (I), in which
  • R is an alkane radical with 20 to 4200, preferably 50 to 750 and quite particularly preferably 80 to 225 carbon atoms,
  • M is an alkali metal or alkaline-earth metal ion, H + or NH 4 + , in particular an alkali metal ion such as Li + , Na + and K + or H + , where not all the variables M
  • m is an integer from 10 to 1400 and
  • polyacrylic acids polymethacrylic acids and acrylic acid-methacrylic acid copolymers, whose acid groups are at least partly, i.e. preferably 40%, particularly preferably 80%, neutralized.
  • the percentage refers to the number of acid groups.
  • poly(meth)acrylic acids which are present entirely in the salt form.
  • poly(meth)acrylic acids are meant polyacrylic acids, polymethacrylic acids and acrylic acid-methacrylic acid copolymers.
  • Poly(meth)acrylic acids are preferred and in particular polyacrylic acids with an average molar mass M w of 1 ,000 to 100,000 g/mol, particularly preferably 1 ,000 to 15,000 g/mol and quite particularly preferably 1 ,000 to 4,000 g/mol.
  • the molecular weight of the poly(meth)acrylic acid polymers and copolymers is ascertained by measuring the viscosity of a 1% aqueous solution, neutralized with sodium hydroxide solution, of the polymer (Fikentscher's constant).
  • copolymers of (meth)acrylic acid in particular copolymers which, besides (meth)acrylic acid contain ethylene, maleic acid, methyl acrylate, ethyl acrylate, butyl acrylate and/or ethylhexyl acrylate as comonomer.
  • Copolymers are preferred which contain at least 40 wt.-%, preferably at least 80 wt.-% (meth)acrylic acid monomer, the percentages being based on the acid form of the monomers or polymers.
  • alkali metal and alkaline- earth metal hydroxides such as potassium hydroxide and in particular sodium hydroxide are particularly suitable.
  • the microporous polyolefin can be provided in various ways with the additive or additives.
  • the additives can for example be applied to the polyolefin when it is finished (i.e. after the extraction) or added to the mixture used to produce the polyolefin.
  • the additive or a solution of the additive is applied to the surface of the polyolefin.
  • This variant is suitable in particular for the application of non-thermostable additives and additives which are soluble in the solvent used for the subsequent extraction.
  • Particularly suitable as solvents for the additives according to the invention are low-molecular-weight alcohols, such as methanol and ethanol, as well as mixtures of these alcohols with water.
  • the application can take place on the side facing the negative electrode, the side facing the positive electrode or on both sides of the separator.
  • the additive can be present at a density of at least 0.5 g/m 2 , 1.0 g/m 2 , 1.5 g/m 2 , 2.0 g/m 2 , 2.5 g/m 2 , 3.0 g/m 2 , 3.5 g/m 2 , 4.0 g/m 2 , 4.5 g/m 2 , 5.0 g/m 2 , 5.5 g/m 2 , 6.0 g/m 2 , 6.5 g/m 2 , 7.0 g/m 2 , 7.5 g/m 2 , 8.0 g/m 2 , 8.5 g/m 2 , 9.0 g/m 2 , 9.5 g/m 2 or 10.0 g/m 2 .
  • the additive can be present on the separator at a density between 0.5-10 g/m 2 , 1.0-10.0 g/m 2 , 1.5-10.0 g/m 2 , 2.0-10.0 g/m 2 , 2.5-10.0 g/m 2 , 3.0-10.0 g/m 2 , 3.5-10.0 g/m 2 , 4.0-10.0 g/m 2 , 4.5-10.0 g/m 2 , 5.0-10.0 g/m 2 , 5.5-10.0 g/m 2 , 6.0-10.0 g/m 2 , 6.5-10.0 g/m 2 , 7.0-10.0 g/m 2 , 7.5-10.0 g/m 2 , 5.0-10.5 g/m 2 , 5.0-11.0 g/m 2 , 5.0-12.0 g/m 2 , or 5.0-15.0 g/m 2 .
  • the application may also take place by dipping the polyolefin in the additive or a solution of the additive and subsequently optionally removing the solvent, e.g. by drying. In this way the application of the additive can be combined for example with the extraction often applied during polyolefin production.
  • the microporous polyolefin separator layer (either having the performance enhancing additive or not) comprises a plurality of acid filling channels or a network of acid filling channels. These acid filling channels are imparted to this microporous polyolefin layer by adding ribs to the layer and/or embossing the layer. When ribs are added to the layer, such ribs may be added to one side or both sides of the polyolefin layer. In some embodiments where ribs are added to both sides, one side may include negative cross-ribs. In some embodiments, the negative cross-ribs may be at an angle relative to the machine direction or transverse direction of the layer.
  • a pattern of ribs may be added to the layer, and such a pattern may include embattlements, serrations, interrupted ribs, and/or the like.
  • the various patterns of ribs and/or embossed regions include patterns that allow battery acid into the separator, quickly, while simultaneously allowing air to escape out of the separator.
  • the acid filling channels or air flow channels
  • the separator may be a PE separator and can be a leaf or sheet, a U fold, a sleeve, or a pocket or envelope, preferably a hybrid envelope.
  • batteries are best suitable for high ambient temperature and partial state of charge usage, they are used in various applications like domestic inverters, off grid solar photo voltaic system, home lighting systems, alarm systems, signaling equipments and remote telecom units.
  • a cycle life of over 500 - 600 cycles under deep discharge conditions A cycle life of over 500 - 600 cycles under deep discharge conditions.
  • the separators of the present invention are particularly useful for flat plate cycling batteries.
  • the separators of the present invention effectively enhance the battery re-chargeability and the backup time.
  • the separators of the present invention contributes to the reduction of water loss in the battery, lowering the maintenance needs in service. It is expected that batteries having the separators of the present invention will be useful in various applications, such as golf carts, Such batteries will be useful in inverters, golf carts, as well as solar and traction application.
  • the control battery had the following characteristics: a conventional envelop polyethylene separator of 72V profile, back web: 350, OT: 1.25 mm, with 0.9 mm wet glass mat - negative wrap.
  • the experimental batteries had the following characteristics: a hybrid envelope polyethylene separator of 72X profile, back web: 400 inclusive of the X rib (300+ 00), OT: 1.5 mm, with 1.1 mm wet glass mat (2 layers, 0.8 mm and 0.3 mm) - negative wrap. Some of the experimental batteries further contained the V coating surfactant additive described above. The comparative performance of the batteries are depicted in Figures 2-11.
  • the present disclosure or invention is directed to novel or improved separators, battery separators, flat plate separators, batteries, cells, and/or methods of manufacture and/or use of such separators, battery separators, flat plate separators, cells, and/or batteries.
  • the present disclosure or invention is directed to novel or improved lead acid battery separators for flat plate cycling batteries, flat plate deep cycling batteries, flat plate inverter batteries, flat plate UPS batteries, flat plate home UPS batteries, flat plate long cycle life batteries, deep cycle stationary, traction, inverter, or fork lift batteries, flooded batteries, UPS, ESS, BESS, flat plate cells, and/or improved methods of making and/or using such improved separators, cells, batteries, systems, and/or the like.
  • the present disclosure or invention is directed to an improved separator for flat plate stationary batteries and/or improved methods of using such batteries having such improved separators.
  • disclosed herein are methods, systems and battery separators for enhancing battery life, reducing water loss, and/or improving uniformity in at least flat plate stationary batteries.
  • the present disclosure or invention is directed to an improved separator for flat plate batteries wherein the separator includes performance enhancing additives or coatings, hybrid envelopes, cross rib shapes or profiles, and/or the like.
  • the separators can contain performance enhancing additives, novel hybrid envelope shapes, and/or ribbed surfaces.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Cell Separators (AREA)

Abstract

La présente invention concerne des séparateurs nouveaux ou améliorés, des séparateurs de batterie, des séparateurs plans, des batteries, des cellules et/ou des procédés de fabrication et/ou d'utilisation de séparateurs, de séparateurs de batterie, de séparateurs plans, de cellules et/ou de batteries de ce genre. Selon au moins certains modes de réalisation, la présente divulgation ou invention a trait à des séparateurs nouveaux ou améliorés de batteries au plomb pour des batteries planes à décharge, des batteries planes à décharge poussée, des batteries planes de convertisseur, des batteries planes d'onduleur, des batteries planes d'onduleur domestique, des batteries planes de longue durée, des batteries stationnaires à décharge poussée de traction, d'inverseur ou d'élévateur à fourches, des batteries immergées, des onduleurs, des ESS, des BESS, des cellules planes et/ou des procédés améliorés pour fabriquer et/ou utiliser des séparateurs, des cellules, des batteries, des systèmes améliorés etc. de ce genre. Selon au moins certains modes de réalisation, la présente divulgation ou invention a trait à un séparateur amélioré pour des batteries stationnaires planes et/ou à des procédés améliorés d'utilisation de telles batteries ayant de tels séparateurs améliorés. La présente invention concerne en outre des procédés, des systèmes et des séparateurs de batterie pour prolonger la durée de vie des batteries, pour réduire la perte d'eau et/ou pour améliorer l'uniformité dans au moins des batteries stationnaires planes. Selon au moins des modes de réalisation particuliers, la présente divulgation ou invention a trait à un séparateur amélioré pour des batteries planes, lequel séparateur présente des additifs ou des revêtements, des enveloppes hybrides, des formes de nervures transversales ou des profilés, etc. améliorant les performances.
PCT/US2015/045060 2015-08-13 2015-08-13 Séparateurs améliorés pour des batteries planes WO2017027037A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
PCT/US2015/045060 WO2017027037A1 (fr) 2015-08-13 2015-08-13 Séparateurs améliorés pour des batteries planes
CN202110936305.3A CN113644381A (zh) 2015-08-13 2016-08-12 改进的平板电池隔板、改进的电池和相关方法
PCT/US2016/046668 WO2017027765A1 (fr) 2015-08-13 2016-08-12 Séparateurs améliorés pour des batteries planes, batteries améliorées, et procédés associés
US15/235,197 US10693118B2 (en) 2015-08-13 2016-08-12 Separators for flat plate batteries, improved batteries, and related methods
CN201680058696.0A CN108352481B (zh) 2015-08-13 2016-08-12 改进的平板电池隔板、改进的电池和相关方法
US16/886,805 US11705582B2 (en) 2015-08-13 2020-05-29 Separators for flat plate batteries, improved batteries, and related methods

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CN108352481A (zh) 2018-07-31

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