WO2021122202A1 - Matériau composite ignifuge - Google Patents

Matériau composite ignifuge Download PDF

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Publication number
WO2021122202A1
WO2021122202A1 PCT/EP2020/085223 EP2020085223W WO2021122202A1 WO 2021122202 A1 WO2021122202 A1 WO 2021122202A1 EP 2020085223 W EP2020085223 W EP 2020085223W WO 2021122202 A1 WO2021122202 A1 WO 2021122202A1
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WIPO (PCT)
Prior art keywords
substrate
composite material
nonwoven
salt
porous substrate
Prior art date
Application number
PCT/EP2020/085223
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English (en)
Inventor
Han-Seong Kim
Hyun-Cheol Lee
Lawrence Alan Hough
Gary Woodward
Craig DOSSITER
Pascal Metivier
Original Assignee
Rhodia Operations
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Publication date
Application filed by Rhodia Operations filed Critical Rhodia Operations
Publication of WO2021122202A1 publication Critical patent/WO2021122202A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D06M15/43—Amino-aldehyde resins modified by phosphorus compounds
    • D06M15/431—Amino-aldehyde resins modified by phosphorus compounds by phosphines or phosphine oxides; by oxides or salts of the phosphonium radical
    • 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
    • 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
    • H01M50/429—Natural polymers
    • H01M50/4295—Natural cotton, cellulose or wood
    • 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
    • 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 invention relates to a process for manufacturing a composite material, comprising the steps of a) spraying an aqueous solution of a tetrakis(hydroxyorgano) phosphonium (THP) salt, an organic nitrogen compound and optionally an aliphatic amine having at least one alkyl group having at least 12 carbon atoms onto a i) porous substrate; b) drying the substrate; c) curing the substrate with ammonia; d) oxidizing the substrate; e) treating the substrate with a metalbi sulfite salt; and f) washing the substrate with excessive water and also to a composite material produced by the process, wherein said step a) is implemented at a speed of 3.0 ml/sec or less of the aqeuous solution, preferably 2.0 ml/sec or less of the aqeuous solution.
  • THP tetrakis(hydroxyorgano) phosphonium
  • the present invention also relates to a composite material comprising a i) porous substrate and a ii) reaction product of a THP salt, an organic nitrogen compound, and optionally an aliphatic amine having at least one alkyl group having at least 12 carbon atoms, wherein the ii) reaction product is impregnated into the pores of the i) porous substrate; to an electrochemical device comprising the composite material as a separator, and to the use of the composite material as a separator in an electrochemical device, in particular a Li-ion secondary battery, a lead-acid battery or a supercapacitor for improving safety performance.
  • Li-ion batteries have retained a dominant position in the market of rechargeable energy storage devices due to their many benefits comprising light-weight, reasonable energy density, and good cycle life. Nevertheless, current Li-ion batteries still suffer from poor safety and relatively low energy density with respect to the required energy density for high power applications, such as electrical vehicles (EVs), hybrid electrical vehicles (HEVs), grid energy storage, etc.
  • An electrolyte is a substance which produces an electrically conducting solution when it is dissolved in a polar solvent. The dissolved electrolyte splits into cations and anions, which disperse through the solvent in a uniform manner.
  • Such a solution is electrically neutral, but if an electrical potential is applied, the cations in the solution move to the electrode having abundant electrons, whereas the anions move to the electrode having a deficit of electrons. That is, the movement of cations and anions in opposite directions results in an electrical current.
  • a separator in an electrochemical device, in particular, in secondary batteries, is necessary to keep the two electrodes apart to prevent electrical short circuits, while permitting the transport of ionic charge carriers which are needed to close the circuit during the passage of current in an electrochemical cell.
  • Separators are critical components in batteries with liquid electrolyte because their structure and properties considerably affect the battery performance, including energy/power densities, cycle life, and safety.
  • a separator generally consists of a polymeric membrane forming a microporous layer. The separator must be (electro)chemically stable with regard to the electrolyte and electrode materials, and also mechanically strong enough to withstand the high tension during the process of battery assembly.
  • the battery must be able to shut down when overheating occurs, so as to avoid thermal runaway, which may cause dimensional shrinkage or even melting of the separator, eventually resulting in the physical contact of the electrodes.
  • inorganic composite membranes have been investigated for this purpose, and are widely used as separators for electrochemical devices including secondary batteries, in particular Li-ion batteries.
  • porous inorganic composite membranes are disclosed in many prior art documents, including US 2002/197413A (Teijin Limited).
  • inorganic composite separators are usually not mechanically strong enough to withstand stress applied during cell assembly, even though they offer excellent wettability of electrolytes and good thermal stability.
  • Such a conventional process for the flame-retardant treatments which have been used only for textiles and garments for several decades, usually requires padding and mangling steps for effective impregnation of the chemicals into the textiles, i.e., passing the target substrate through an aqueous bath containing a solution of the flame-retardant agent and any other additives, and subsequently through rollers.
  • existing methods to apply an aqueous solution of a THP salt and an organic nitrogen compound onto textiles are typically continuous processes, where the textiles need to be dipped into the aqueous solution and subsequently the excess water needs to be removed by either roller or mangle.
  • said process is not appropriate to be used in manufacturing a battery separator with a purpose to impart better safety performance thereto without a sacrifice in other properties, and hence the state of the art has been inactive in the field of batteries over a long period prior to the present invention, even though during that time an urgent need for the improvement of safety in batteries has demonstrably and continuously existed.
  • the reaction product from the aqueous solution of a THP salt, an organic nitrogen compound, and optionally an aliphatic amine having at least one alkyl group having at least 12 carbon atoms can be effectively impregnated into the pores of the i) porous substrate.
  • the reaction product is a water- insoluble cross-linked polymer, which becomes mechanically fixed across the pores of the i) porous substrate, and the resulting composite material is suitable to be used as a separator in an electrochemical device having good safety performance and flexibility as well as good cycle performance.
  • a first object of the present invention is to provide a process for manufacturing a composite material comprising the steps of a) spraying an aqueous solution of a tetrakis(hydroxyorgano) phosphonium (THP) salt, an organic nitrogen compound and optionally an aliphatic amine having at least one alkyl group having at least 12 carbon atoms onto a i) porous substrate; b) drying the substrate; c) curing the substrate with ammonia; d) oxidizing the substrate; e) treating the substrate with a metalbi sulfite salt; and f) washing the substrate with excessive water, wherein said step a) is implemented at a speed of 3.0 ml/sec or less of the aqeuous solution, preferably 2.0 ml/sec or less of the aqeuous solution.
  • THP tetrakis(hydroxyorgano) phosphonium
  • a second object of the present invention is to provide a composite material produced by the process according to the present invention.
  • a third object of the present invention is to provide a composite material comprising a i) porous substrate and a ii) reaction product of a THP salt, an organic nitrogen compound, and optionally an aliphatic amine having at least one alkyl group having at least 12 carbon atoms, wherein the ii) reaction product is impregnated into the pores of the i) porous substrate.
  • a fourth object of the present invention is to provide an electrochemical device comprising the composite materials as described above as a separator.
  • Another object of the present invention is the use of the composite material as described above as a separator in an electrochemical device, in particular, a Li-ion secondary battery, a lead-acid battery, or a supercapacitor for improving safety performance.
  • Figure 1 is SEM images of the surface of a separator according to the present invention (A) and of the surface of separator made of the original nonwoven cellulose (B).
  • Figure 2 is cross-section SEM images of the separator according to the present invention (C) and of the surface of separator made of the original nonwoven cellulose (D).
  • alkyl groups include saturated hydrocarbons having one or more carbon atoms, including straight-chain alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclic alkyl groups (or "cycloalkyl” or “alicyclic” or “carbocyclic” groups), such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, branched-chain alkyl groups, such as isopropyl, tert-butyl, sec-butyl, and isobutyl, and alkyl- substituted alkyl groups, such as alkyl-substituted cycloalkyl groups and cycloalkyl-substituted alkyl groups.
  • aliphatic group includes organic moieties characterized by straight or branched-chains, typically having between 1 and 18 carbon atoms. In complex structures, the chains may be branched, bridged, or cross-linked. Aliphatic groups include alkyl groups, alkenyl groups, and alkynyl groups.
  • Ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
  • a temperature range of about 120°C to about 150°C should be interpreted to include not only the explicitly recited limits of about 120°C to about 150°C, but also to include sub-ranges, such as 125°C to 145°C, 130°C to 150°C, and so forth, as well as individual amounts, including fractional amounts, within the specified ranges, such as 122.2°C, 140.6°C, and 141.3°C, for example.
  • the amount of a component in a composition is indicated as the ratio between the weight of the component and the total weight of the composition multiplied by 100 (i.e., % by weight or wt%).
  • separatator it is hereby intended to denote a monolayer or multilayer polymeric or inorganic material, which electrically and physically separates the electrodes of opposite polarities in an electrochemical cell and is permeable to ions flowing between them.
  • porous substrate By the term “porous substrate”, it is hereby intended to denote a substrate containing pores of finite dimensions, which is electrically and chemically inert.
  • the substrate has typically a porosity advantageously of at least 5%, preferably of at least 10%, more preferably of at least 20% or at least 40% and advantageously of at most 90%, preferably of at most 80%, e.g. measured via Gurley number as described in method ISO 5636-5.
  • electrochemical cell By the term “electrochemical cell”, it is hereby intended to denote an electrochemical device/assembly comprising a positive electrode, a negative electrode and a liquid electrolyte, wherein a monolayer or multilayer separator is adhered to at least one surface of one of the said electrodes.
  • suitable electrochemical devices include, notably, secondary batteries, especially, alkaline or an alkaline-earth secondary batteries such as lithium ion batteries, lead-acid batteries, and capacitors, especially lithium ion- based capacitors and electric double-layer capacitors (supercapacitors).
  • the present invention provides a process for manufacturing a composite material comprising the steps of a) spraying an aqueous solution of a THP salt, an organic nitrogen compound and optionally an aliphatic amine having at least one alkyl group having at least 12 carbon atoms onto a i) porous substrate; b) drying the substrate; c) curing the substrate with ammonia; d) oxidizing the substrate; e) treating the substrate with a metalbi sulfite salt; and f) washing the substrate with excessive water, wherein said step a) is implemented at a speed of 3.0 ml/sec or less of the aqeuous solution, preferably 2.0 ml/sec or less of the aqeuous solution.
  • the step a) of spraying is implemented onto the porous substrate suspended by a support frame in a horizontal direction.
  • the step a) is carried out with less tension as much as possible so that the substrate can withstand stress once being sprayed.
  • the porous substrate remains soaked within the aqueous solution for at least 3 secons, preferably for at least 5 seconds before the step b) of drying.
  • the i) porous substrate can be made with any porous substrate commonly used for a separator in an electrochemical device, comprising at least one material selected from the group consisting of cellulose, polyester such as polyethylene terephthalate and polybutylene terephthalate, polyphenylene sulphide, polyacetal, polyamide, polycarbonate, polyimide, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, polyethylene naphthalene, polyethylene oxide, polyacrylonitrile, polyolefin such as polyethylene and polypropylene, or mixtures thereof.
  • polyester such as polyethylene terephthalate and polybutylene terephthalate
  • polyphenylene sulphide polyacetal
  • polyamide polycarbonate
  • polyimide polyether sulfone
  • polyphenylene oxide polyphenylene sulfide
  • polyethylene naphthalene polyethylene oxide
  • polyacrylonitrile polyolefin such as polyethylene and polyprop
  • the i) porous substrate is a nonwoven material, which comprises cellulosic nonwoven and optionally non-cellulosic nonwoven.
  • the non-cellulosic nonwoven is selected from the group consisting of polyester nonwoven, polyamide nonwoven, acrylic nonwoven, aramid nonwoven and polybenzimidazole nonwoven, preferably polyester nonwoven.
  • the nonwoven is a blend of cellulose and polyester.
  • the nonwoven is a blend of 50 wt% of cellulose and 50 wt% of polyester.
  • the porous substrate is a nonwoven material consisting of cellulose only.
  • nonwoven is intended to denote a planar structure obtainable by randomly interlocking or bonding mechanically, thermally or chemically one or more sets of polymer materials, leading to a structure with numerous pores.
  • cellulose By the term “cellulose”, it is hereby intended to denote a component of the cell walls of plants.
  • Examples of celluloe include cotton, rayon, linen, hemp and cellulose acetate, while the most common example is cotton.
  • the THP salt according to the present invention is preferably a tetrakis(hydroxyalkyl) phosphonium salt, for example tetrakis(hydroxymethyl) phosphonium chloride (THPC) or tetrakis(hydroxymethyl) phosphonium sulphate (THPS).
  • THPC tetrakis(hydroxymethyl) phosphonium chloride
  • THPS tetrakis(hydroxymethyl) phosphonium sulphate
  • the organic nitrogen compound according to the present invention is a compound containing nitrogen which may form a condensate with a THP salt. Without wishing to be bound by any particular theory, it is believed that the adjustment of the pH of THP salt to about 6.0 may render the salt more reactive towards the organic nitrogen compound.
  • the organic nitrogen compound is an amide, for example urea or thiourea.
  • aliphatic amine examples include, but not limited to, a primary amine, a secondary amine, a quaternary ammonium salt, an ethoxylated amine, an ethoxylated diamine, an amide oxide, an alkylamino-substituted carboxylic acid, an amide, an ethoxylated amide, an amido-imidazoline, a siolxane, and a silane derivative.
  • the aliphatic amine having at least one alkyl group having at least 12 carbon atoms is an amine, it may, for example, consist essentially of n- dodecylamine, n-octadecylamine, n-hexadecylamine, n-eicosylamine, or mixtures thereof.
  • the substrate is dried.
  • the step of b) drying is performed at a temperature of between 1°C and 200°C, preferably between 20°C and 100°C. Care should be taken not to dry the material too quickly as migration of the chemical may occur.
  • the substrate is dried to a moisture content of 20% or less, preferably between 1% and 15%, and more preferably between 5% and 10%.
  • the moisture content can be measured from the increase in weight of the substrate and the weight of chemicals applied thereto by spraying.
  • the substrate is cured with ammonia, usually gaseous ammonia, so as to produce a water-insoluble cross- linked polymer, corresponding to the reaction product from the aqueous solution of a THP salt, an organic nitrogen compound and optionally an aliphatic amine having at least one alkyl group having at least 12 carbon atoms, which is mechanically fixed across the pores of the i) porous substrate.
  • ammonia usually gaseous ammonia
  • an oxidation corresponding to the step d) is carried out using an oxidant, for instance, a peroxy compound such as aqueous hydrogen peroxide solution and sodium perborate solution, so as to convert the trivalent phosphorus to its stable form of pentavalent phosphorus, followed by a treatment with a base, such as sodium carbonate for neutralization.
  • an oxidant for instance, a peroxy compound such as aqueous hydrogen peroxide solution and sodium perborate solution
  • a base such as sodium carbonate for neutralization
  • the oxidation may be performed with a gas containing molecular oxygen, preferably air.
  • the substrate is treated with a metabi sulfite salt, preferably sodium metabi sulfite to reduce the amount of formaldehyde present in the final product, which is then washed with excessive water and dried.
  • a metabi sulfite salt preferably sodium metabi sulfite to reduce the amount of formaldehyde present in the final product, which is then washed with excessive water and dried.
  • Softened water is chosen for the final wash of the process in an attempt to minimize the number of metal ions that may be left on the final product.
  • a second object of the present invention is to provide a composite material produced by the process according to the present invention.
  • a third object of the present invention is to provide a composite material comprising a i) porous substrate; and a ii) reaction product of a THP salt, an organic nitrogen compound, and optionally an aliphatic amine having at least one alkyl group having at least 12 carbon atoms, wherein the ii) reaction product is impregnated into the pores of the i) porous substrate.
  • the ii) reaction product is a water-insoluble cross- linked polymer, which becomes mechanically fixed across the pores of the i) porous substrate.
  • the composite material according to the present invention exhibits good thermal resistivity and flexibility, while maintaining good cycle performance, suitable to be used as a separator in an electrochemical cell.
  • a separator in an electrochemical cell must have sufficient pore density to hold the liquid electrolyte which enables ions to move between two electrodes.
  • excessive porosity also can hinder the ability of the pores to close, which is vital to allow the separator to shut down an overheated battery.
  • the pore size of a separator is a key factor in an electrochemical cell. Undersize pore will decrease the transmission rate of a metal ion, e.g., Li ion. A relatively large pore size is necessary for low ionic resistance, which can result in good charge/discharge acceptance, particularly at high C-rate. On the other side, however, in order to suppress the internal short circuits of batteries, separators should have relatively small pore size and sufficiently narrow distribution of pore sizes. Accordingly, it’s very important to have optimal pore size, which is thin enough and at the same time is not detrimental in view of internal short circuits.
  • the average pore size of polyolefin-based membrances is between 0.02 pm and 0.2 pm, preferably between 0.03 pm and 0.1 pm. In addition, the average pore size of nonwoven membranes is between 1 pm and 10 pm.
  • the composite material according to the present invention has the average pore size of between 0.1 pm and 1 pm, preferably between 0.2 pm and 0.8 pm, and more preferably between 0.4 pm and 0.6 pm.
  • Porosity can be measured using liquid or gas absorption methods according to the ASTM D-2873.
  • a separator for Li-ion battery provides a porosity of 40%.
  • the composite material according to the present invention has porosity of between 10% and 90%, preferably between 30% and 80% and more preferably between 40% and 80%.
  • the pores should be uniformly distributed while also having a tortuous structure, which enables uniform distribution of current throughout the separator, while suppressing the growth of Li dendrites on the anode.
  • the distribution and structure of pores can be analyzed using a capillary flow porometer or a scanning electron microscope (SEM).
  • a separator in an electrochemical cell should be thin to facilitate the energy density of the battery. Its thickness should be defined in consideration of mechanical strength and safety performance. The thickness should be also uniform to support many charging cycles.
  • the thickness of the composite material according to the present invention is from 3 to 100 pm, preferably from 5 to 50 pm, and more preferably from 8 to 40 pm.
  • Determination of the thickness can be performed by any suitable method.
  • the thickness is preferably determined according to ISO 4593 standard procedure.
  • a fourth object of the present invention is an electrochemical device comprising the composite materials as described above as a separator.
  • Another object of the present invention is the use of the composite material as described above as a separator in an electrochemical device, in particular a Li- ion secondary battery, a lead-acid battery or a supercapacitor for improving safety performance.
  • the electrolyte composition was prepared by mixing the different compounds using a magnetic stirrer. All required components were added to one bottle and mixed while stirring until a transparent solution was obtained.
  • Li salt LiPF 6 (lithium hexafluorophosphate); 1 mol.L 1
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • VC vinylene carbonate
  • PS 1,3-propane sultone
  • a substrate of original nonwoven cellulose (NW; thickness: 35 pm; TF4035 available from Nippon Kodoshi Corp.) was suspended from a frame (dimension : 600 mm x 150 mm) under slight tension.
  • a 20% w/w solution of PerformTM LF (an aqueous condensate solution of a THPS salt and urea; available from Solvay Solutions UK) was prepared with distilled water.
  • PerformTM LF solution was sprayed onto the horizontally-oriented NW until being saturated at a speed of about 2.0 ml/sec. Wet NW was left within PerformTM LF solution for 5 seconds and was found to have poor wet strength at this stage. Wet NW was then dried in an oven and left in ambient humidity after drying to re-gain moisture.
  • CE1 and CE2 were prepared in the same manner as El, respectively, except that different separator was used. That is, polyethylene (PE; thickness : 20 pm; porosity : about 40%; available from Toray Tonen Specialty Separator Godo Kaisha) was used for CE1 and original NW (thickness : 30 pm) without the treatment as El was used for CE2.
  • PE polyethylene
  • the liquid electrolyte as prepared was injected into the dry cells by pipette.
  • the amount of liquid electrolyte composition injected into each cell was 100 pi.
  • the dry cells were kept in a vacuum container for wetting of the liquid electrolyte to the electrode components. After releasing the vacuum, the cells were kept as such for 1 minute for better wetting. After wetting, the cells were sealed by vacuum sealing machine and the cells were kept in the laboratory additionally for 1 day at room temperature.
  • the surface and cross-section morphologies of the composite separators were characterized by SEM images.
  • the separator of CE2 with original nonwoven cellulose showed many open pores on the surface, whereas the separator of El according to the present invention showed smaller pores in comparison with CE2 ( Figure 1).
  • the cross section of CE2 was circular, while the cross section of El clearly showed the difference, i.e., the polymeric layer around the cellulose fiber.
  • the initial discharge capacity of the test cells with CE1 and CE2 was respectively 30.7 mAh and 30.9 mAh, while the initial discharge capacity of the test cell with El was 25.9 mAh, about 13.7 % lower than the discharge capacity as designed (30 mAh). However, the discharge capacity was recovered during first 30 cycles with 0.5C and first 50 cycles with 1.0C.
  • Li-ion cells possess a high energy density and are used to store and supply energy to diverse applications. Incidents relating to the overheating or thermal runaway of the cells may cause severe damage, through fire or explosion. Accordingly, thermal studies of Li-ion cells are very important for ensuring the safety and reliability of cells. This study is to evaluate the thermal behavior of Li-ion cells under adiabatic conditions. The thermal runaway of a Li- ion cell is dominated by the exothermic reaction between the electrolyte and electrode materials. Thermal runaway occurs when the exothermic reactions go out of control so that the self-heating rate of the cell increases to the point that it begins to generate more heat than what can be dissipated.
  • the thermal exposure tests were implemented by using GL800 (a data logger, available from Graphtec Corporation) in an explosion proof chamber under the following conditions: - heating up to 200°C with a heating rate of 5°C/min; and
  • the onset temperatures of thermal runaway (a.k.a. thermal resistivity temperatures) of CE1, CE2 and El were 162 °C, 175 °C, and 187 °C, respectively.
  • the thermal resistivity temperature of El was higher than those of CE1 and CE2, which means that El according to the present invention increases the safety performance in terms of thermal resistivity temperatures in comparison with CE1 and CE2.
  • a separator made of the composite material according to the present invention exhibits comparable or superior thermal resistivity performance while maintaining good cycling performance.

Abstract

La présente invention se rapporte à un procédé de fabrication d'un matériau composite, consistant a) à pulvériser une solution aqueuse d'un sel de tétrakis(hydroxyorgano) phosphonium (THP), d'un composé azoté organique et facultativement d'une amine aliphatique ayant au moins un groupe alkyle ayant au moins 12 atomes de carbone sur i) un substrat poreux ; b) à sécher le substrat ; c) à durcir le substrat avec de l'ammoniac ; d) à oxyder le substrat ; e) à traiter le substrat avec un sel de métalbisulfite ; et f) à laver le substrat avec de l'eau en abondance, ladite étape a) étant mise en œuvre à une vitesse de 3,0 ml/sec ou moins de la solution aqueuse, de préférence 2,0 ml/sec ou moins de la solution aqueuse et l'invention se rapporte également à un matériau composite produit par le procédé. La présente invention se rapporte également à un matériau composite comprenant i) un substrat poreux et ii) un produit de réaction d'un sel THP, d'un composé d'azote organique et facultativement d'une amine aliphatique ayant au moins un groupe alkyle ayant au moins 12 atomes de carbone, ii) le produit de réaction étant imprégné dans les pores i) du substrat poreux ; à un dispositif électrochimique comprenant le matériau composite en tant que séparateur, et à l'utilisation du matériau composite comme séparateur dans un dispositif électrochimique, en particulier une batterie secondaire au lithium-ion, une batterie au plomb-acide ou un supercondensateur pour améliorer les performances de sécurité.
PCT/EP2020/085223 2019-12-16 2020-12-09 Matériau composite ignifuge WO2021122202A1 (fr)

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EP19216479 2019-12-16
EP19216479.6 2019-12-16

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3101278A (en) * 1960-11-21 1963-08-20 Hooker Chemical Corp Flame proofing of cellulosic materials
CA715627A (en) * 1965-08-10 M. Wagner George Polymerization inhibited methylol-phosphorus flame-retardant compositions
US4156747A (en) * 1972-04-17 1979-05-29 Hooker Chemicals & Plastics Corp. Process for flame retarding cellulosics
GB2040299B (en) 1979-01-26 1983-04-27 Albright & Wilson Polymeric phosphonium flameproofing agents
EP0294234A2 (fr) 1987-06-05 1988-12-07 Albright & Wilson Limited Traitement de textile
EP0451665A1 (fr) * 1990-04-12 1991-10-16 Albright & Wilson Limited Traitement de tissus
EP0709518A1 (fr) 1994-10-25 1996-05-01 Albright & Wilson Limited Traitement ignifuge et adoucissant de matériaux textiles
US20020197413A1 (en) 1999-03-07 2002-12-26 Takahiro Daido Process for production of composite porous film
WO2013092842A2 (fr) * 2011-12-23 2013-06-27 Rhodia Operations Traitement de matière textile

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA715627A (en) * 1965-08-10 M. Wagner George Polymerization inhibited methylol-phosphorus flame-retardant compositions
US3101278A (en) * 1960-11-21 1963-08-20 Hooker Chemical Corp Flame proofing of cellulosic materials
US4156747A (en) * 1972-04-17 1979-05-29 Hooker Chemicals & Plastics Corp. Process for flame retarding cellulosics
GB2040299B (en) 1979-01-26 1983-04-27 Albright & Wilson Polymeric phosphonium flameproofing agents
EP0294234A2 (fr) 1987-06-05 1988-12-07 Albright & Wilson Limited Traitement de textile
EP0451665A1 (fr) * 1990-04-12 1991-10-16 Albright & Wilson Limited Traitement de tissus
EP0709518A1 (fr) 1994-10-25 1996-05-01 Albright & Wilson Limited Traitement ignifuge et adoucissant de matériaux textiles
US20020197413A1 (en) 1999-03-07 2002-12-26 Takahiro Daido Process for production of composite porous film
WO2013092842A2 (fr) * 2011-12-23 2013-06-27 Rhodia Operations Traitement de matière textile

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