WO2025129574A1 - 一种双层锂离子筛纤维材料及其制备方法和应用 - Google Patents

一种双层锂离子筛纤维材料及其制备方法和应用 Download PDF

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Publication number
WO2025129574A1
WO2025129574A1 PCT/CN2023/140705 CN2023140705W WO2025129574A1 WO 2025129574 A1 WO2025129574 A1 WO 2025129574A1 CN 2023140705 W CN2023140705 W CN 2023140705W WO 2025129574 A1 WO2025129574 A1 WO 2025129574A1
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Prior art keywords
ion sieve
layer
double
fiber material
lithium ion
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PCT/CN2023/140705
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English (en)
French (fr)
Inventor
谢英豪
余海军
王涛
李爱霞
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Application filed by Hunan Brunp Recycling Technology Co Ltd, Guangdong Brunp Recycling Technology Co Ltd filed Critical Hunan Brunp Recycling Technology Co Ltd
Priority to CN202380012565.9A priority Critical patent/CN118159422B/zh
Priority to PCT/CN2023/140705 priority patent/WO2025129574A1/zh
Publication of WO2025129574A1 publication Critical patent/WO2025129574A1/zh
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/02—Layered products comprising a layer of synthetic resin in the form of fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic Table
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/22—Polymers or copolymers of halogenated mono-olefins
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides

Definitions

  • the present disclosure relates to the field of lithium resource technology, and in particular to a double-layer lithium ion sieve fiber material and a preparation method and application thereof.
  • Ion sieve is an important adsorbent commonly used for lithium extraction from salt lakes, but ion sieve is generally a powder raw material, which has the problems of poor fluidity and difficult recycling. In this regard, it is generally solved by granulation or film casting. The ion sieve after granulation is used to fill the column, which is easier to recycle. However, the adsorption performance of the ion sieve after granulation and film casting is generally lower than that of the powder ion sieve.
  • the purpose of the present disclosure is to provide a double-layer lithium ion sieve fiber material and a preparation method and application thereof.
  • the core layer includes a flexible carrier and a manganese ion sieve dispersed in the flexible carrier, the flexible carrier is composed of soft polyvinyl chloride and hydrophilic polyethersulfone, and a plurality of first holes are constructed on the flexible carrier;
  • the thickness ratio of the core layer to the cladding layer is 1:(1-3).
  • the specific surface area of the core layer is 5 m 2 /g-12 m 2 /g.
  • the specific surface area of the coating layer is 5 m 2 /g-12 m 2 /g.
  • the mass ratio of the manganese ion sieve, the soft polyvinyl chloride and the hydrophilic polyether sulfone is (25-40): (70-100): (25-50).
  • the titanium ion sieve, the poly(p-phenylene terephthalamide) and the poly(hexadiamine adipamide) The mass ratio of diamine is (25-40):(45-80):(25-50).
  • the mass ratio of the titanium ion sieve, the poly(p-phenylene terephthalamide), the poly(hexamethylene adipamide), the coating layer solvent and the sodium carbonate is (25-40):(45-80):(25-50):(140-250):(15-30).
  • the spinning includes dry spinning, wet spinning or electrospinning.
  • the coating layer solvent includes methanesulfonic acid and isocresol
  • the method for preparing the coating layer spinning solution includes: first mixing the methanesulfonic acid and the poly(p-phenylene terephthalamide), heating to 70°C-85°C, and stirring for 5h-6h to obtain a poly(p-phenylene terephthalamide) solution; then mixing the isocresol with the poly(hexamethylene adipamide), heating to 70°C-85°C, and stirring for 5h-6h to obtain a poly(hexamethylene adipamide) solution; mixing the poly(p-phenylene terephthalamide) solution and the poly(hexamethylene adipamide) solution, stirring evenly, cooling to room temperature, and then adding the sodium carbonate, stirring evenly, and then adding the titanium ion sieve, stirring evenly to obtain the coating layer spinning solution.
  • the present disclosure provides the use of a double-layer lithium ion sieve fiber material as described in any of the aforementioned embodiments or a double-layer lithium ion sieve fiber material prepared by the preparation method of the double-layer lithium ion sieve fiber material as described in any of the aforementioned embodiments as an adsorbent in lithium extraction from salt lake brine.
  • the salt lake brine includes at least one of original brine and old brine.
  • the double-layer lithium ion sieve fiber material places the manganese ion sieve that is more easily dissolved in the core layer of the fiber material, and the coating layer fiber material forms a protective layer for the manganese ion sieve, reducing the direct contact between the acid and the manganese ion sieve, inhibiting the corrosion of the acid to the manganese ion sieve, thereby reducing the dissolution of the manganese ion sieve and ensuring the circulation performance of the fiber material.
  • the precipitation of carbon dioxide further increases the porosity of the fiber material, so that the lithium ion sieve exposes more adsorption sites, improving the lithium
  • the prepared double-layer lithium ion sieve fiber material can be widely used in lithium extraction from brine.
  • the present disclosure provides a double-layer lithium ion sieve fiber material, which includes a core layer and a coating layer, and the thickness ratio of the core layer to the coating layer is 1: (1-3).
  • the core layer includes a flexible carrier and a manganese ion sieve dispersed in the flexible carrier, the flexible carrier is composed of soft polyvinyl chloride and hydrophilic polyethersulfone, a plurality of first holes are constructed on the flexible carrier, and the specific surface area of the core layer is 5m2 /g- 12m2 /g.
  • the coating layer includes a rigid carrier and a titanium ion sieve dispersed in the rigid carrier, the rigid carrier is composed of poly(p-phenylene terephthalamide) and poly(hexamethylene adipamide), a plurality of second holes are constructed on the flexible carrier, and the specific surface area of the coating layer is 5m2 /g- 12m2 /g.
  • the raw materials of the core layer include the following components in parts by weight: 25-40 parts of manganese ion sieve, 70-100 parts of soft polyvinyl chloride, 25-50 parts of hydrophilic polyether sulfone, 135-235 parts of core layer solvent and 15-30 parts of sodium bicarbonate;
  • the raw materials of the coating layer include the following components in parts by weight: 25-40 parts of titanium ion sieve, 45-80 parts of poly(p-phenylene terephthalamide), 25-50 parts of poly(hexamethylene adipamide), 140-250 parts of coating layer solvent and 15-30 parts of sodium carbonate.
  • Manganese ion sieves have a high affinity for lithium ions and good adsorption performance for lithium ions. However, during the adsorption and desorption of lithium ions, especially in the desorption stage, manganese dissolution is serious, which will cause certain water pollution during actual application. Titanium ion sieves have less dissolution, and titanium ion sieves are basically the ion sieves with the least water pollution.
  • the manganese ion sieve is arranged in the core layer and the titanium ion sieve is arranged in the coating layer. Since the dissolution loss rate of the titanium ion sieve is relatively small, it can fully contact with the brine to adsorb lithium ions, and the fiber strength of the coating layer is relatively large and not easy to break, and it can well resist water pressure and better maintain the structural integrity of the fiber material; the manganese ion sieve is placed in the core layer, and the fiber material of the coating layer can form protection for the manganese ion sieve of the core layer, reducing the direct contact of the manganese ion sieve with the acid during desorption, inhibiting the corrosion of the acid to the manganese ion sieve, and reducing the dissolution loss of the manganese ion sieve. At the same time, the hydrophilicity of the core layer material is relatively large, which can improve the inward permeability of the brine, improve the wettability of the core layer material, and increase the
  • the molecular chain of poly(p-phenylene terephthalamide) in the coating fiber material is rigid and has good strength. High tensile strength and toughness; polyhexamethylene adipamide has high mechanical strength, high rigidity and high tensile strength.
  • the present invention uses poly(p-phenylene terephthalamide) and poly(hexamethylene adipamide) as the skeleton material of the coating layer fiber, and the obtained coating layer material has high mechanical strength, which plays a supporting role for the material, and at the same time can make the material have appropriate flexibility, the material is not easy to break, can resist water pressure well, better maintain the structural integrity of the fiber material, and improve the service life of the fiber material.
  • the density of soft polyvinyl chloride is 1.2g/cm 3 -1.3g/cm 3 , and the yield strength is 15MPa-25MPa. It has good softness and high elongation at break, making the material rigid on the outside and soft on the inside, not easy to break and having good strength.
  • the core material is modified by adding hydrophilic polyethersulfone, which can improve the hydrophilicity of the core fiber material, improve the permeability and wettability of the core fiber material, and ensure the lithium ion adsorption effect of the core material.
  • Sodium carbonate is a pore-forming agent for the fiber material of the coating layer
  • sodium bicarbonate is a pore-forming agent for the fiber material of the core layer.
  • the fiber material is placed in an acid solution for immersion.
  • Sodium carbonate and sodium bicarbonate will react chemically with the acid solution to produce carbon dioxide.
  • the precipitation of carbon dioxide will cause the material to form many pores, thereby increasing the porosity of the fiber material.
  • the core layer fiber material is coated with the fiber material of the coating layer. During acid immersion, the acid first contacts the fiber material of the coating layer and reacts with the sodium carbonate thereon to produce carbon dioxide.
  • the acid After the acid passes through the fiber material of the coating layer, it enters the fiber material of the core layer and reacts with the sodium bicarbonate on the fiber of the core layer to produce carbon dioxide.
  • the reaction of sodium bicarbonate with acid is more intense than that of sodium carbonate with acid.
  • the core layer fiber ensures that the core layer fiber material produces more bubbles through a more intense reaction.
  • the bubbles produced in the core layer precipitate from the inside to the outside, further promoting the coating layer material to produce more pores.
  • pores are formed by reacting sodium carbonate and sodium bicarbonate with acid, which can significantly increase the specific surface area of the core layer and the coating layer, thereby having a more excellent adsorption effect.
  • the core layer comprises the following components in parts by weight: 28-38 parts of manganese ion sieve, 80-90 parts of soft polyvinyl chloride, 30-45 parts of hydrophilic polyether sulfone, 155-210 parts of core layer solvent and 20-28 parts of sodium bicarbonate;
  • the coating layer comprises the following components in parts by weight: 28-38 parts of titanium ion sieve, 50-75 parts of poly(p-phenylene terephthalamide), 30-45 parts of poly(hexamethylene adipamide), 160-220 parts of coating layer solvent and 18-28 parts of sodium carbonate.
  • the weight of the manganese ion sieve can be, for example, 28 parts, 30 parts, 32 parts, 35 parts, 36 parts or 38 parts, or any range between two of them;
  • the weight of the soft polyvinyl chloride can be, for example, 80 parts, 82 parts, 85 parts, 87 parts, 88 parts, 90 parts, or any range between two of them;
  • the weight of the hydrophilic polyether sulfone can be, for example, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts or 45 parts, or any range between two of them.
  • the weight of the core layer solvent can be, for example, any one of 155 parts, 165 parts, 175 parts, 185 parts, 195 parts, 200 parts, 205 parts or 210 parts, or a range between any two of them;
  • the weight of the sodium bicarbonate can be, for example, any one of 20 parts, 22 parts, 25 parts, 26 parts, 27 parts or 28 parts, or a range between any two of them;
  • the weight of the titanium ion sieve can be, for example, any one of 28 parts, 30 parts, 32 parts, 35 parts, 36 parts or 38 parts.
  • the weight portion of poly(p-phenylene terephthalamide) can be, for example, any one of 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, or any range between two of them;
  • the weight portion of poly(hexamethylene adipamide) can be, for example, any one of 30 parts, 34 parts, 38 parts, 42 parts, or 45 parts, or any range between two of them;
  • the weight portion of the coating layer solvent can be, for example, any one of 160 parts to 220 parts, or any range between two of them;
  • the weight portion of sodium carbonate can be, for example, any one of 18 parts to 28 parts, or any range between two of them.
  • the core layer solvent can be used as long as it can dissolve the components of the core layer.
  • the coating layer solvent can be used as long as it can dissolve the components of the coating layer.
  • the core layer solvent includes at least one of dimethylformamide and N-methylpyrrolidone.
  • the core layer solvent includes dimethylformamide and N-methylpyrrolidone in a mass ratio of (75-135): (60-100).
  • the core layer solvent includes dimethylformamide and N-methylpyrrolidone in a mass ratio of (85-120): (70-90).
  • the coating layer solvent includes at least one of methanesulfonic acid and meta-cresol.
  • the coating layer solvent includes methanesulfonic acid and meta-cresol in a mass ratio of (90-150): (50-100).
  • the coating layer solvent includes methanesulfonic acid and meta-cresol in a mass ratio of (100-130): (60-90).
  • the double-layer lithium ion sieve fiber material is a fiber membrane or a fiber line.
  • its diameter is 0.5 ⁇ m to 100 ⁇ m, for example, nanometer level (500 to 1000 nm) or micrometer level (1 to 100 ⁇ m).
  • This embodiment is basically the same as embodiment 1, except that the formula of the double-layer lithium ion sieve fiber material is different, as follows:
  • a double-layer lithium ion sieve fiber material comprises a core layer and a coating layer, wherein the core layer comprises the following components in parts by weight: 30 parts of manganese ion sieve, 85 parts of soft polyvinyl chloride, 35 parts of hydrophilic polyether sulfone, 110 parts of dimethylformamide, 80 parts of N-methylpyrrolidone, and 27 parts of sodium bicarbonate; and the coating layer comprises the following components in parts by weight: 30 parts of titanium ion sieve, 65 parts of poly(p-phenylene terephthalamide), 35 parts of poly(hexamethylene adipamide), 120 parts of methanesulfonic acid, 80 parts of meta-cresol, and 25 parts of sodium carbonate.
  • the core layer comprises the following components in parts by weight: 30 parts of manganese ion sieve, 85 parts of soft polyvinyl chloride, 35 parts of hydrophilic polyether sulfone, 110 parts of dimethylformamide, 80 parts of N-methylpyrrolidone
  • Preparation of core layer spinning solution Mix the formulated amounts of dimethylformamide and N-methylpyrrolidone, then add the formulated amounts of soft polyvinyl chloride and hydrophilic polyethersulfone, raise the temperature to 70°C, stir for 7 hours, cool to room temperature, then add the formulated amount of sodium bicarbonate, stir evenly, then add the formulated amount of manganese ion sieve, stir evenly, to obtain the core layer spinning solution.
  • the core layer spinning solution is placed in a core layer spinning solution storage tank, the coating layer spinning solution is placed in a coating layer spinning solution storage tank, the core layer spinning solution storage tank is connected to the inner tube of the nozzle, the coating layer spinning solution storage tank is connected to the outer tube of the nozzle, the coaxial electrospinning equipment is started, the core layer spinning solution and the coating layer spinning solution are sprayed out from the spray port at the same time, and a double-layer fiber material is formed on the receiving device, and the material is in a film shape; during the coaxial electrospinning process, the ambient temperature is set to 20 ⁇ 5°C, the ambient humidity is less than 30%, the spinning voltage is 15kv, the coating layer melt spinning solution propulsion flow rate is 0.28mL/h, and the core layer spinning solution propulsion flow rate is 0.18mL/h.
  • Drying Drying the double-layer fiber material after acid leaching.
  • Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the core layer spinning solution and the coating layer spinning solution of Example 1 are blended to form a blended solution, and the blended solution is prepared by an electrospinning process, but the electrospinning process is not coaxial electrospinning, but conventional electrospinning.
  • the ambient temperature is set to 20 ⁇ 5°C
  • the ambient humidity is less than 30%
  • the spinning voltage is 20kv
  • the spinning solution propulsion flow rate is 0.25mL/h.
  • the acid leaching and drying process after electrospinning is the same as that in Example 1.
  • Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the manganese ion sieve of the core layer fiber is replaced by a titanium ion sieve, and the titanium ion sieve of the cladding layer fiber is replaced by a manganese ion sieve.
  • Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that the core layer spinning solution of Example 1 is used as the coating layer spinning solution, and the coating layer spinning solution is used as the core layer spinning solution, but the ion sieve of the core layer spinning solution is still a manganese ion sieve, and the ion sieve of the coating layer spinning solution is still a titanium ion sieve.
  • the details are as follows:
  • a double-layer lithium ion sieve fiber material comprises a core layer and a coating layer, wherein the core layer comprises the following components in parts by weight: 25 parts of manganese ion sieve, 45 parts of poly(p-phenylene terephthalamide), 25 parts of poly(hexamethylene adipamide), 90 parts of methanesulfonic acid, 50 parts of meta-cresol, and 15 parts of sodium carbonate; and the coating layer comprises the following components in parts by weight: 25 parts of titanium ion sieve, 70 parts of soft polyvinyl chloride, 25 parts of hydrophilic polyether sulfone, 75 parts of dimethylformamide, 60 parts of N-methylpyrrolidone, and 15 parts of sodium bicarbonate.
  • the fiber material obtained in Comparative Example 3 is soft on the outside and hard on the inside, and the coating layer has a stronger hydrophilicity.
  • Comparative Example 4 The difference between Comparative Example 4 and Example 1 is that in the core layer material, the amount of soft polyvinyl chloride is adjusted to 95 parts, and the hydrophilic polyethersulfone is omitted. In the coating layer material, the amount of poly(p-phenylene terephthalamide) is adjusted to 70 parts, and poly(hexamethylene adipamide) is omitted, the amount of methanesulfonic acid is adjusted to 140 parts, and m-cresol is omitted.
  • Comparative Example 5 The difference between Comparative Example 5 and Example 1 is that: in the core layer material, the amount of hydrophilic polyethersulfone is adjusted to 95 parts, and the soft polyvinyl chloride is omitted. In the coating layer material, the amount of polyhexamethylene adipamide is adjusted to 70 parts, polyparaphenylene terephthalamide is omitted, the amount of meta-cresol is adjusted to 140 parts, and methanesulfonic acid is omitted.
  • Comparative Example 6 The difference between Comparative Example 6 and Example 1 is that in the core layer material, the pore-forming agent is adjusted to sodium carbonate, which is the same as the pore-forming agent of the coating layer material.
  • the fiber material obtained in Comparative Example 1 is not a double-layer material, the manganese ion sieve is not protected by the coating layer fiber, and the hydrophilic fiber material is not placed in the core layer, which will lead to a large dissolution loss of the manganese ion sieve, thereby causing a decrease in adsorption cycle performance.
  • the high molecular polymer used in the formula is blended with the two ion sieves, which may also affect the uniform distribution of the ion sieve, or block the adsorption sites of the ion sieve, resulting in a decrease in adsorption energy.
  • the manganese ion sieve is placed in the fiber material coating layer, and the titanium ion sieve is placed in the fiber material core layer.
  • the manganese ion sieve in the coating layer has a large dissolution loss, resulting in poor adsorption cycle performance.
  • Comparative Example 3 The core layer spinning solution of Example 1 is used as the coating layer spinning solution, and the coating layer spinning solution is used as the core layer spinning solution.
  • the fiber material coating layer obtained in Comparative Example 3 has a stronger hydrophilicity, which will increase the dissolution loss of the ion sieve and lead to a decrease in the adsorption cycle performance.
  • the pore-forming agent of the fiber materials of the core layer and the coating layer is sodium carbonate.
  • the speed and ability of the core layer fiber to generate bubbles during pore formation are weaker than those in Example 1, which will affect the pore formation of the fiber material, resulting in a decrease in the adsorption amount and adsorption cycle performance.
  • the double-layer lithium ion sieve fiber materials obtained in Examples 1-6 have relatively large elongations at break, which indicates that the fiber materials are relatively strong and not prone to breakage, and are suitable for long-term use in brine.
  • the fiber material of Comparative Example 1 is not a double-layer material, but a single-layer fiber formed by blending all materials. Its elongation at break is lower than that of the embodiment, and it is more prone to breakage.
  • the core layer spinning solution of Example 1 is used as the coating layer spinning solution, and the coating layer spinning solution is used as the core layer spinning solution.
  • the fiber obtained is soft on the outside and hard on the inside, and its mechanical properties are weaker than those of Example 1, and it is easier to break.
  • the double-layer lithium ion sieve fiber material provided by the present invention optimizes the formula of the core layer material and the coating layer material, and obtains a fiber material that is rigid on the outside and soft on the inside.
  • the coating layer fiber has good rigidity, high strength, and is not easy to break, and plays a good supporting role. It can resist water pressure well and better maintain the structural integrity of the fiber material; the core layer fiber has good flexibility, which can further reduce the probability of material breakage during use.
  • the core layer material does not directly contact brine during use, and the present invention modifies the core layer material by using hydrophilic polyethersulfone, which improves the inward penetration and infiltration of brine, thereby improving the adsorption performance of lithium ions.
  • the double-layer lithium ion sieve fiber material provided by the present invention places the manganese ion sieve, which is more easily dissolved, in the core layer of the fiber material, and the coating layer fiber material forms a protective layer for the manganese ion sieve, thereby reducing the direct contact between the acid and the manganese ion sieve, inhibiting the corrosion of the acid to the manganese ion sieve, thereby reducing the dissolution of the manganese ion sieve and ensuring the circulation performance of the fiber material.
  • the double-layer lithium ion sieve fiber material provided by the present invention adopts sodium carbonate as the pore-forming agent for the coating layer fibers and sodium bicarbonate as the pore-forming agent for the core layer fibers, so that the fibers can form more pores.
  • the bubbles generated when the core layer fibers are pore-formed are discharged from the inside to the outside, further promoting the formation of pores.
  • the preparation method of the double-layer lithium ion sieve fiber material provided in the present invention adopts the spinning process technology.
  • the fiber material obtained by spinning has high porosity and large specific surface area.
  • pores are formed by an acid leaching pore-forming process.
  • the precipitation of carbon dioxide further increases the porosity of the fiber material, so that the lithium ion sieve exposes more adsorption sites, thereby increasing the adsorption amount of lithium ions.
  • the preparation method of the double-layer lithium ion sieve fiber material provided by the present disclosure can obtain a fiber material that can be a fiber membrane or a fiber line.
  • the specific form can be set according to actual needs.
  • the membrane fiber can be directly used for lithium extraction; the linear fiber can be first filled into a column and then used for lithium extraction.
  • the linear fiber can be spun to form a fiber yarn with a larger diameter, and the fiber yarn is integrated into a fiber bundle, and lithium is directly extracted in brine through the fiber bundle.
  • the double-layer lithium ion sieve fiber material optimizes the formula of the core layer material and the coating layer material, and obtains a fiber material that is rigid on the outside and soft on the inside.
  • the coating layer fiber has good rigidity, high strength, and is not easy to break, which plays a good supporting role, can well resist water pressure, and better maintain the structural integrity of the fiber material; the core layer fiber has good flexibility, which can further reduce the probability of material breakage during use.
  • the core layer material does not directly contact the brine during use, and the present disclosure improves the inward penetration and infiltration of brine by using hydrophilic polyethersulfone to modify the core layer material, thereby improving the adsorption performance of lithium ions.
  • the double-layer lithium ion sieve fiber material provided by the present disclosure places the manganese ion sieve that is more easily dissolved in the core layer of the fiber material, and the coating layer fiber material forms a protective layer for the manganese ion sieve, reducing the direct contact between the acid and the manganese ion sieve, inhibiting the corrosion of the acid to the manganese ion sieve, thereby reducing the dissolution of the manganese ion sieve and ensuring the circulation performance of the fiber material.
  • the preparation method of the double-layer lithium ion sieve fiber material provided in the present invention is prepared by a spinning process technology.
  • the fiber material obtained by spinning has a high porosity and a large specific surface area.
  • pores are formed by an acid leaching pore-forming process. Since the present invention adopts sodium carbonate as a coating layer fiber pore-forming agent and sodium bicarbonate as a core layer fiber pore-forming agent, the fiber can form more pores. At the same time, the bubbles generated when the core layer fiber is pore-formed are discharged from the inside to the outside, further promoting the formation of pores. During the acid leaching process, the precipitation of carbon dioxide further increases the porosity of the fiber material, so that the lithium ion sieve exposes more adsorption sites and increases the adsorption amount of lithium ions.
  • the prepared double-layer lithium ion sieve fiber material can be widely used in brine for lithium extraction.

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Abstract

本公开公开了一种双层锂离子筛纤维材料及其制备方法和应用，涉及锂资源技术领域。该双层锂离子筛纤维材料包括芯层和包覆层，芯层包括柔性载体和分散于柔性载体内的锰离子筛，柔性载体的成分包括软质聚氯乙烯和亲水性聚醚砜，柔性载体上构建有多个第一孔洞；包覆层包括刚性载体和分散于刚性载体内的钛离子筛，刚性载体的成分包括聚对苯二甲酰对苯二胺和聚己二酰己二胺，柔性载体上构建有多个第二孔洞。本公开提供的双层锂离子筛纤维材料为外刚内柔，具有良好的抗水压和断裂性能，同时锰离子筛的溶损少，具有优异的循环性能和锂离子吸附性能，可以广泛应用于卤水提锂。

Description

一种双层锂离子筛纤维材料及其制备方法和应用 技术领域
本公开涉及锂资源技术领域，具体而言，涉及一种双层锂离子筛纤维材料及其制备方法和应用。
背景技术
在盐湖提锂技术领域，吸附法选择性好，对于镁锂比高的卤水也可通过吸附法实现锂离子吸附。离子筛是盐湖提锂常用的一种重要的吸附剂，但是离子筛一般为粉体原料，存在流动性差、难回收的问题。对此，一般通过造粒或铸膜来解决，造粒后的离子筛填充柱体使用，回收较容易，但是造粒后和铸膜后的离子筛其吸附性能一般会比粉体离子筛下降。
目前，利用吸附法进行盐湖提锂的创新研究层出不穷，开发一种吸附能力强，同时离子筛溶损小，循环性能好的吸附材料具有重要的意义。
鉴于此，特提出本公开。
发明内容
本公开的目的在于提供一种双层锂离子筛纤维材料及其制备方法和应用。
本公开是这样实现的：
第一方面，本公开提供一种双层锂离子筛纤维材料，其由内至外依次包括芯层和包覆层；
所述芯层包括柔性载体和分散于所述柔性载体内的锰离子筛，所述柔性载体由软质聚氯乙烯和亲水性聚醚砜构成，所述柔性载体上构建有多个第一孔洞；
所述包覆层包括刚性载体和分散于所述刚性载体内的钛离子筛，所述刚性载体是由聚对苯二甲酰对苯二胺和聚己二酰己二胺构成，所述柔性载体上构建有多个第二孔洞。
在可选的实施方式中，所述芯层和所述包覆层的厚度比为1：(1-3)。
在可选的实施方式中，所述芯层的比表面积为5m2/g-12m2/g。
在可选的实施方式中，所述包覆层的比表面积为5m2/g-12m2/g。
在可选的实施方式中，所述锰离子筛、所述软质聚氯乙烯和所述亲水性聚醚砜的质量比为(25-40)：(70-100)：(25-50)。
在可选的实施方式中，所述钛离子筛、所述聚对苯二甲酰对苯二胺和所述聚己二酰己 二胺的质量比为(25-40)：(45-80)：(25-50)。
在可选的实施方式中，所述软质聚氯乙烯的密度为1.2g/cm3-1.3g/cm3，屈服强度为15MPa～25MPa。
在可选的实施方式中，所述双层锂离子筛纤维材料为纤维膜或纤维线。
在可选的实施方式中，所述纤维线的直径为0.5μm-100μm。
第二方面，本公开提供一种双层锂离子筛纤维材料的制备方法，其包括：
将锰离子筛、软质聚氯乙烯、亲水性聚醚砜、芯层溶剂和碳酸氢钠混合形成芯层纺丝液；
将钛离子筛、聚对苯二甲酰对苯二胺、聚己二酰己二胺、包覆层溶剂和碳酸钠混合形成包覆层纺丝液；
将所述芯层纺丝液和所述包覆层纺丝液经纺丝形成包覆层包覆芯层的双层纤维中间品；
将所述双层纤维中间品经酸浸造孔，随后干燥即得所述双层锂离子筛纤维材料。
在可选的实施方式中，所述锰离子筛、所述软质聚氯乙烯、所述亲水性聚醚砜、所述芯层溶剂和所述碳酸氢钠的质量比为(25-40)：(70-100)：(25-50)：(135-235)：(15-30)。
在可选的实施方式中，所述芯层溶剂包括二甲基甲酰胺和N-甲基吡咯烷酮中的至少一种。
在可选的实施方式中，所述芯层溶剂包括质量比为(75-135)：(60-100)的二甲基甲酰胺和N-甲基吡咯烷酮。
在可选的实施方式中，所述钛离子筛、所述聚对苯二甲酰对苯二胺、所述聚己二酰己二胺、所述包覆层溶剂和所述碳酸钠的质量比为(25-40)：(45-80)：(25-50)：(140-250)：(15-30)。
在可选的实施方式中，所述包覆层溶剂包括甲磺酸和间苯甲酚中的至少一种。
在可选的实施方式中，所述包覆层溶剂包括质量比为(90-150)：(50-100)的甲磺酸和间苯甲酚。
在可选的实施方式中，所述纺丝包括干法纺丝、湿法纺丝或静电纺丝。
在可选的实施方式中，所述纺丝为同轴静电纺丝。
在可选的实施方式中，所述同轴静电纺丝的纺丝环境温度为15℃-25℃，环境湿度小于30％，纺丝电压为15kv-25kv。
在可选的实施方式中，所述同轴静电纺丝时，所述芯层纺丝液的推进流速为0.18 mL/h-0.25mL/h，所述包覆层纺丝液的推进流速为0.10mL/h-0.15mL/h。
在可选的实施方式中，所述酸浸用酸为盐酸。
在可选的实施方式中，所述酸浸的时间为0.5h-1.5h。
在可选的实施方式中，所述芯层纺丝液的制备方法包括：将所述芯层溶剂与所述软质聚氯乙烯和亲水性聚醚砜混合，升温至70℃-85℃，搅拌5h-7h，降至室温，然后加入所述碳酸氢钠，搅拌均匀后，再加入所述锰离子筛，搅拌均匀，得到所述芯层纺丝液。
在可选的实施方式中，所述包覆层溶剂包括甲磺酸和间苯甲酚，所述包覆层纺丝液的制备方法包括：先将所述甲磺酸和所述聚对苯二甲酰对苯二胺混合，加热至70℃-85℃，搅拌5h-6h，得到聚对苯二甲酰对苯二胺溶液；然后将所述间苯甲酚与所述聚己二酰己二胺混合，加热至70℃-85℃，搅拌5h-6h，得到聚己二酰己二胺溶液；将所述聚对苯二甲酰对苯二胺溶液和所述聚己二酰己二胺溶液混合，搅拌均匀，降至室温，然后加入所述碳酸钠，搅拌均匀后，再加入所述钛离子筛，搅拌均匀，得到所述包覆层纺丝液。
第三方面，本公开提供如前述实施方式任一项所述的双层锂离子筛纤维材料或如前述实施方式任一项所述的双层锂离子筛纤维材料的制备方法制备获得的双层锂离子筛纤维材料在盐湖卤水提锂中作为吸附剂的应用。
在可选的实施方式中，所述盐湖卤水包括原卤和老卤中的至少一种。
本公开具有以下有益效果：
本公开提供的双层锂离子筛纤维材料优化了芯层材料和包覆层材料的配方，获得了外刚内柔的纤维材料，包覆层纤维刚性较好，强度较大，不易断裂，起到很好的支撑作用，能够很好地抗水压，更好地维护纤维材料的结构完整性；芯层纤维柔韧性较好，能够进一步减少材料在使用过程中的断裂机率，芯层材料在使用过程中并没有直接与卤水接触，而本公开通过采用亲水性聚醚砜对芯层材料进行改性，提高了卤水向内的渗透与浸润，从而提高了锂离子的吸附性能。本公开提供的双层锂离子筛纤维材料，将较易溶损的锰离子筛置于纤维材料的芯层，包覆层纤维材料对锰离子筛形成保护层，减少了酸液与锰离子筛的直接接触，抑制了酸液对锰离子筛的腐蚀，从而减少了锰离子筛的溶损，保证纤维材料的循环性能。
本公开提供的双层锂离子筛纤维材料的制备方法，采用纺丝工艺技术制备，纺丝获得的纤维材料孔隙率高，比表面积大，再通过酸浸造孔工艺造孔，由于本公开采用碳酸钠为包覆层纤维造孔剂，碳酸氢钠为芯层纤维造孔剂，使得纤维能够形成更多的孔隙，同时芯层纤维造孔时产生的气泡由内向外排出，进一步促进了孔隙的形成。酸浸过程中，二氧化碳的析出进一步使得纤维材料的孔隙率提高，使得锂离子筛暴露更多的吸附位点，提高锂 离子的吸附量。制备获得的双层锂离子筛纤维材料可以广泛应用于卤水中进行提锂。
具体实施方式
为使本公开实施例的目的、技术方案和优点更加清楚，下面将对本公开实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
本公开提供一种双层锂离子筛纤维材料，其包括芯层和包覆层，芯层和包覆层的厚度比为1：(1-3)。
其中，芯层包括柔性载体和分散于柔性载体内的锰离子筛，柔性载体由软质聚氯乙烯和亲水性聚醚砜构成，柔性载体上构建有多个第一孔洞，芯层的比表面积为5m2/g-12m2/g包覆层包括刚性载体和分散于刚性载体内的钛离子筛，刚性载体是由聚对苯二甲酰对苯二胺和聚己二酰己二胺构成，柔性载体上构建有多个第二孔洞，包覆层的比表面积为5m2/g-12m2/g。
具体来说，芯层的原料按照重量份计包括以下组分：锰离子筛25份-40份、软质聚氯乙烯70份-100份、亲水性聚醚砜25份-50份、芯层溶剂135份-235份和碳酸氢钠15份-30份；包覆层的原料按照重量份计包括以下组分：钛离子筛25份-40份、聚对苯二甲酰对苯二胺45份-80份、聚己二酰己二胺25份-50份、包覆层溶剂140份-250份和碳酸钠15份-30份。
锰系离子筛对锂离子具有较高的亲和力，对锂离子的吸附性能较好。但是，锰系离子筛在锂离子的吸附和解吸过程中，尤其是在解吸阶段，锰溶损现象比较严重，实际应用过程中会造成一定的水体污染。而钛系离子筛的溶损较小，钛系离子筛基本是对水体污染最小的一种离子筛。
本公开中，通过将锰离子筛设置在芯层，钛离子筛设置在包覆层，由于钛离子筛的溶损率较小，其能够充分与卤水接触进行锂离子吸附，且包覆层纤维强度较大，不易断裂，能够很好地抗水压，更好地维护纤维材料的结构完整性；锰离子筛置于芯层，包覆层纤维材料能够对芯层的锰离子筛形成保护，减少了锰离子筛解吸时与酸液的直接接触，抑制酸液对锰离子筛的腐蚀作用，能够减少锰离子筛的溶损，同时芯层材料的亲水性较大，能够提高卤水向内的渗透性，提高芯层材料的润湿性，提高锂离子的吸附量。
其中，包覆层纤维材料中，聚对苯二甲酰对苯二胺的分子链呈现刚性，强度好，具有 高的抗拉强度又兼具韧性；聚己二酰己二胺机械强度高，刚性大，抗拉强度高。本公开以聚对苯二甲酰对苯二胺和聚己二酰己二胺为包覆层纤维的骨架材料，获得的包覆层材料机械强度较大，对材料起到支撑作用，同时能够使材料兼顾合适的柔韧性，材料不易断裂，能够很好地抗水压，更好地维护纤维材料的结构完整性，提高纤维材料的使用寿命。
芯层纤维材料中，软质聚氯乙烯的密度为1.2g/cm3-1.3g/cm3，屈服强度为15MPa-25MPa，其具有很好的柔软性，具有较高的断裂伸长率，使得材料形成外刚内柔的特性，不易断裂又具有较好的强度。同时，芯层材料加入亲水性聚醚砜进行改性，能够提高芯层纤维材料的亲水性，提高芯层纤维材料的渗透性和润湿性，确保芯层材料的锂离子吸附效果。
碳酸钠是包覆层纤维材料的造孔剂，碳酸氢钠是芯层纤维材料的造孔剂，纤维材料纺丝完成后，将纤维材料置于酸液中进行浸泡，碳酸钠和碳酸氢钠会与酸液发生化学反应产生二氧化碳，二氧化碳的析出会使得材料形成很多孔隙，提高纤维材料的孔隙率。芯层纤维材料被包覆层纤维材料包覆，酸浸时，酸首先与包覆层纤维材料接触并与其上的碳酸钠发生反应产生二氧化碳，酸经过包覆层纤维材料后再进入芯层纤维材料并与芯层纤维上的碳酸氢钠发生反应产生二氧化碳，而碳酸氢钠与酸的反应会比碳酸钠与酸的反应更加剧烈，芯层纤维通过更加剧烈的反应来确保芯层纤维材料产生更多的气泡，芯层产生的气泡由内往外析出，又进一步促进包覆层材料产生更多的孔隙。本公开中，利用碳酸钠和碳酸氢钠与酸反应进行造孔，可以显著增大芯层和包覆层的比表面积，从而具有更优异的吸附效果。
进一步地，芯层按照重量份计包括以下组分：锰离子筛28份-38份、软质聚氯乙烯80份-90份、亲水性聚醚砜30份-45份、芯层溶剂155份-210份和碳酸氢钠20份-28份；包覆层按照重量份计包括以下组分：钛离子筛28份-38份、聚对苯二甲酰对苯二胺50份-75份、聚己二酰己二胺30份-45份、包覆层溶剂160份-220份和碳酸钠18份-28份。
在某些实施方式中，锰离子筛的重量份例如可以为28份、30份、32份、35份、36份或38份中的任一者或者任意两者之间的范围值；软质聚氯乙烯的重量份例如可以为80份、82份、85份、87份、88份、90份中的任一者或者任意两者之间的范围值；亲水性聚醚砜的重量份例如可以为30份、32份、35份、38份、40份或45份中的任一者或者任意两者之间的范围值；芯层溶剂的重量份例如可以为155份、165份、175份、185份、195份、200份、205份或210份中的任一者或者任意两者之间的范围值；碳酸氢钠的重量份例如可以为20份、22份、25份、26份、27份或28份中的任一者或者任意两者之间的范围值；钛离子筛的重量份例如可以为28份、30份、32份、35份、36份或38份中的任一 者或者任意两者之间的范围值；聚对苯二甲酰对苯二胺的重量份例如可以为50份、55份、60份、65份、70份、75份中的任一者或者任意两者之间的范围值；聚己二酰己二胺的重量份例如可以为30份、34份、38份、42份或45份中的任一者或者任意两者之间的范围值；包覆层溶剂的重量份例如可以为160份-220份中的任一者或者任意两者之间的范围值；碳酸钠的重量份例如可以为18份-28份中的任一者或者任意两者之间的范围值。
本公开中，芯层溶剂只要能够实现对芯层的组分进行溶解即可，同样的，包覆层溶剂也只要能够实现对包覆层的组分进行溶解即可，其选择不做具体的限制。在本公开的某些典型但非限制性的实施方式中，芯层溶剂包括二甲基甲酰胺和N-甲基吡咯烷酮中的至少一种。芯层溶剂包括质量比为(75-135)：(60-100)的二甲基甲酰胺和N-甲基吡咯烷酮。芯层溶剂包括质量比为(85-120)：(70-90)的二甲基甲酰胺和N-甲基吡咯烷酮。包覆层溶剂包括甲磺酸和间苯甲酚中的至少一种。包覆层溶剂包括质量比为(90-150)：(50-100)的甲磺酸和间苯甲酚。包覆层溶剂包括质量比为(100-130)：(60-90)的甲磺酸和间苯甲酚。
双层锂离子筛纤维材料为纤维膜或纤维线。当双层锂离子筛纤维材料为纤维线时其直径为0.5μm～100μm，例如为纳米级(500～1000nm)或微米级(1～100μm)。
本公开提供一种双层锂离子筛纤维材料的制备方法，其包括：将双层锂离子筛纤维材料的芯层和包覆层的组分配制成芯层纺丝液和包覆层纺丝液，将芯层纺丝液置于芯层储罐和包覆层纺丝液分别经纺丝形成双层纤维中间品；将双层纤维中间品经酸浸造孔，随后干燥即得双层锂离子筛纤维材料。
具体来说，包括如下步骤：
S1、配制芯层纺丝液。
将芯层溶剂与软质聚氯乙烯和亲水性聚醚砜混合，升温至70℃-85℃，搅拌5h-7h，降至室温，然后加入碳酸氢钠，搅拌均匀后，再加入锰离子筛，搅拌均匀，得到芯层纺丝液。
本公开中，通过先将软质聚氯乙烯和亲水性聚醚砜采用芯层溶剂进行混合，使其充分混合均匀后再加入碳酸氢钠和锰离子筛，可以实现其均匀分散在溶液中，各个组分之间的混合效果更均匀。
S2、配制包覆层纺丝液。
包覆层溶剂包括甲磺酸和间苯甲酚，包覆层纺丝液的制备方法包括：先将甲磺酸和聚对苯二甲酰对苯二胺混合，加热至70℃-85℃，搅拌5h-6h，得到聚对苯二甲酰对苯二胺溶液。然后将间苯甲酚与聚己二酰己二胺混合，加热至70℃-85℃，搅拌5h-6h，得到聚 己二酰己二胺溶液。将聚对苯二甲酰对苯二胺溶液和聚己二酰己二胺溶液混合，搅拌均匀，降至室温，然后加入碳酸钠，搅拌均匀后，再加入钛离子筛，搅拌均匀，得到包覆层纺丝液。
本公开中，通过分别用溶剂将聚对苯二甲酰对苯二胺和聚己二酰己二胺配制成溶液，更便于这两者的混合，随后加入碳酸钠和钛离子筛，可以实现其均匀分散在溶液中，各个组分之间的混合效果更均匀。
S3、纺丝。
本公开中利用纺丝技术来实现制备双层材料，纺丝的方式包括但不限于干法纺丝、湿法纺丝或静电纺丝。
本公开提供了一个典型但非限制性的示例，纺丝选用同轴静电纺丝。具体地，同轴静电纺丝的纺丝环境温度为15℃-25℃，环境湿度小于30％，纺丝电压为15kv-25kv。同轴静电纺丝时，芯层纺丝液的推进流速为0.18mL/h-0.25mL/h，包覆层纺丝液的推进流速为0.28mL/h-0.3mL/h。
其中，纺丝环境温度例如可以为15℃、18℃、20℃、22℃或25℃中的任一者或者任意两者之间的范围值。纺丝电压例如可以为15kv、18kv、20kv、22kv或25kv中的任一者或者任意两者之间的范围值。同轴静电纺丝时，芯层纺丝液的推进流速例如可以为0.18mL/h、0.20mL/h、0.22mL/h、0.24mL/h或0.25mL/h中的任一者或者任意两者之间的范围值。包覆层纺丝液的推进流速为0.28mL/h、0.29mL/h或0.3mL/h中的任一者或者任意两者之间的范围值。
应理解的是，在选用其他纺丝方式时，具体的工艺参数可以根据实际情况进行调整。
S4、酸浸。
将双层纤维中间品浸泡于酸液中，酸浸用酸为盐酸，酸浸的时间为0.5h-1.5h。
本公开中，利用酸液与包覆层的致孔剂(碳酸钠)和芯层的致孔剂(碳酸氢钠)进行反应，产生二氧化碳，二氧化碳的析出会使得材料形成很多孔隙，提高纤维材料的孔隙率。
S5、干燥。
将酸浸完成后的双层纤维材料进行干燥，即得。本公开中的干燥方式有多种，例如通风干燥、烘箱干燥等等，只要能够实现对双层纤维材料进行干燥即可。
本公开通过上述方法制备获得的双层锂离子筛纤维材料可以广泛应用于盐湖卤水提锂中作为吸附剂。盐湖卤水包括原卤和老卤中的至少一种。
以下结合实施例对本公开的特征和性能作进一步的详细描述。
实施例1
本实施例提供了一种双层锂离子筛纤维材料，包括芯层和包覆层，芯层包括按照重量份计的以下组分：锰离子筛25份，软质聚氯乙烯70份，亲水性聚醚砜25份，二甲基甲酰胺75份，N-甲基吡咯烷酮60份，碳酸氢钠15份；包覆层包括按照重量份计的以下组分：钛离子筛25份，聚对苯二甲酰对苯二胺45份，聚己二酰己二胺25份，甲磺酸90份，间苯甲酚50份，碳酸钠15份。
其制备方法包括如下步骤：
(1)芯层纺丝液制备：将配方量的二甲基甲酰胺和N-甲基吡咯烷酮混合，然后加入配方量的软质聚氯乙烯和亲水性聚醚砜，升温至80℃，搅拌6小时，降至室温，然后加入配方量的碳酸氢钠，搅拌均匀后，再加入配方量的锰离子筛，搅拌均匀，得到芯层纺丝液。
(2)包覆层纺丝液制备：取配方量的甲磺酸，加入配方量的聚对苯二甲酰对苯二胺，加热至80℃，搅拌5.5小时，得到聚对苯二甲酰对苯二胺溶液；然后取配方量的间苯甲酚，加入配方量的聚己二酰己二胺，加热至80℃，搅拌5.5小时，得到聚己二酰己二胺溶液；将聚对苯二甲酰对苯二胺溶液和聚己二酰己二胺溶液混合，搅拌均匀，降至室温，然后加入配方量的碳酸钠，搅拌均匀后，再加入配方量的钛离子筛，搅拌均匀，得到包覆层纺丝液。
(3)同轴静电纺丝：将芯层纺丝液置于芯层纺丝液存储罐中，包覆层纺丝液置于包覆层纺丝液存储罐中，芯层纺丝液存储罐与喷头内管连接，包覆层纺丝液存储罐与喷头外管连接，启动设备同轴静电纺丝设备，芯层纺丝液和包覆层纺丝液同时从喷液口喷出，在接收设备上形成双层纤维材料，材料为膜状；同轴静电纺丝过程中，设置环境温度为20±5℃，环境湿度小于30％，纺丝电压为20kv，包覆层溶体纺丝液推进流速为0.29mL/h，芯层纺丝液推进流速为0.12mL/h。
(4)酸浸：将获得双层纤维材料置于盐酸溶液中浸泡1h。
(5)干燥：将酸浸完成后的双层纤维材料进行干燥，即得。
实施例2
本实施例与实施例1基本相同，区别仅在于双层锂离子筛纤维材料的配方不同，具体如下：
一种双层锂离子筛纤维材料，包括芯层和包覆层，芯层包括按照重量份计的以下组分：锰离子筛40份，软质聚氯乙烯100份，亲水性聚醚砜50份，二甲基甲酰胺135份， N-甲基吡咯烷酮100份，碳酸氢钠30份；包覆层包括按照重量份计的以下组分：钛离子筛40份，聚对苯二甲酰对苯二胺80份，聚己二酰己二胺50份，甲磺酸150份，间苯甲酚100份，碳酸钠30份。
实施例3
本实施例与实施例1基本相同，区别仅在于双层锂离子筛纤维材料的配方不同，具体如下：
一种双层锂离子筛纤维材料，包括芯层和包覆层，芯层包括按照重量份计的以下组分：锰离子筛28份，软质聚氯乙烯80份，亲水性聚醚砜30份，二甲基甲酰胺85份，N-甲基吡咯烷酮70份，碳酸氢钠20份；包覆层包括按照重量份计的以下组分：钛离子筛28份，聚对苯二甲酰对苯二胺50份，聚己二酰己二胺30份，甲磺酸100份，间苯甲酚60份，碳酸钠18份。
实施例4
本实施例与实施例1基本相同，区别仅在于双层锂离子筛纤维材料的配方不同，具体如下：
一种双层锂离子筛纤维材料，包括芯层和包覆层，芯层包括按照重量份计的以下组分：锰离子筛38份，软质聚氯乙烯90份，亲水性聚醚砜45份，二甲基甲酰胺120份，N-甲基吡咯烷酮90份，碳酸氢钠28份；包覆层包括按照重量份计的以下组分：钛离子筛38份，聚对苯二甲酰对苯二胺75份，聚己二酰己二胺45份，甲磺酸130份，间苯甲酚90份，碳酸钠28份。
实施例5
本实施例与实施例1基本相同，区别仅在于双层锂离子筛纤维材料的配方不同，具体如下：
一种双层锂离子筛纤维材料，包括芯层和包覆层，芯层包括按照重量份计的以下组分：锰离子筛30份，软质聚氯乙烯85份，亲水性聚醚砜35份，二甲基甲酰胺110份，N-甲基吡咯烷酮80份，碳酸氢钠27份；包覆层包括按照重量份计的以下组分：钛离子筛30份，聚对苯二甲酰对苯二胺65份，聚己二酰己二胺35份，甲磺酸120份，间苯甲酚80份，碳酸钠25份。
实施例6
本实施例与实施例1基本相同，区别仅在于，制备方法不同，具体如下：
(1)芯层纺丝液制备：将配方量的二甲基甲酰胺和N-甲基吡咯烷酮混合，然后加入配方量的软质聚氯乙烯和亲水性聚醚砜，升温至70℃，搅拌7小时，降至室温，然后加入配方量的碳酸氢钠，搅拌均匀后，再加入配方量的锰离子筛，搅拌均匀，得到芯层纺丝液。
(2)包覆层纺丝液制备：取配方量的甲磺酸，加入配方量的聚对苯二甲酰对苯二胺，加热至70℃，搅拌6小时，得到聚对苯二甲酰对苯二胺溶液；然后取配方量的间苯甲酚，加入配方量的聚己二酰己二胺，加热至70℃，搅拌6小时，得到聚己二酰己二胺溶液；将聚对苯二甲酰对苯二胺溶液和聚己二酰己二胺溶液混合，搅拌均匀，降至室温，然后加入配方量的碳酸钠，搅拌均匀后，再加入配方量的钛离子筛，搅拌均匀，得到包覆层纺丝液。
(3)同轴静电纺丝：将芯层纺丝液置于芯层纺丝液存储罐中，包覆层纺丝液置于包覆层纺丝液存储罐中，芯层纺丝液存储罐与喷头内管连接，包覆层纺丝液存储罐与喷头外管连接，启动设备同轴静电纺丝设备，芯层纺丝液和包覆层纺丝液同时从喷液口喷出，在接收设备上形成双层纤维材料，材料为膜状；同轴静电纺丝过程中，设置环境温度为20±5℃，环境湿度小于30％，纺丝电压为15kv，包覆层溶体纺丝液推进流速为0.28mL/h，芯层纺丝液推进流速为0.18mL/h。
(4)酸浸：将获得双层纤维材料置于盐酸溶液中浸泡1h。
(5)干燥：将酸浸完成后的双层纤维材料进行干燥，即得。
对比例1
对比例1与实施例1的不同之处在于：将实施例1的芯层纺丝液和包覆层纺丝液共混形成共混液，共混合液采用静电纺丝工艺制作而成，但静电纺丝工艺并不是同轴静电纺丝，而是常规的静电纺丝。静电纺丝过程中，设置环境温度为20±5℃，环境湿度小于30％，纺丝电压为20kv，纺丝液推进流速为0.25mL/h。
静电纺丝后的酸浸、干燥工艺与实施例1相同。
对比例2
对比例2与实施例1的不同之处在于：将芯层纤维的锰离子筛替换为钛离子筛，包覆层纤维的钛离子筛替换为锰离子筛。
对比例3
对比例3与实施例1的不同之处在于：将实施例1的芯层纺丝液作为包覆层纺丝液，包覆层纺丝液作为芯层纺丝液，但芯层纺丝液的离子筛依然为锰离子筛，包覆层纺丝液的离子筛依然为钛离子筛。具体如下：
一种双层锂离子筛纤维材料，包括芯层和包覆层，芯层包括按照重量份计的以下组分：锰离子筛25份，聚对苯二甲酰对苯二胺45份，聚己二酰己二胺25份，甲磺酸90份，间苯甲酚50份，碳酸钠15份；包覆层包括按照重量份计的以下组分：钛离子筛25份，软质聚氯乙烯70份，亲水性聚醚砜25份，二甲基甲酰胺75份，N-甲基吡咯烷酮60份，碳酸氢钠15份。
对比例3获得的纤维材料是外柔内刚，且包覆层的亲水性更强。
对比例4
对比例4与实施例1的不同之处在于：芯层材料中，将软质聚氯乙烯的用量调整为95份，省略亲水性聚醚砜。包覆层材料中，将聚对苯二甲酰对苯二胺的用量调整为70份，省略聚己二酰己二胺，将甲磺酸的用量调整为140份，省略间苯甲酚。
对比例5
对比例5与实施例1的不同之处在于：芯层材料中，将亲水性聚醚砜的用量调整为95份，省略软质聚氯乙烯。包覆层材料中，将聚己二酰己二胺的用量调整为70份，省略聚对苯二甲酰对苯二胺，将间苯甲酚的用量调整为140份，省略甲磺酸。
对比例6
对比例6与实施例1的不同之处在于，芯层材料中，将造孔剂调整为碳酸钠，与包覆层材料的造孔剂相同。
实验例一：吸附容量检测
分别取100g实施例1-6和对比例1-6获得的纤维材料进行锂离子吸附实验，分别将100g纤维材料置于实验用卤水中进行卤水提锂，浸泡5h后，用0.4mol/L的盐酸溶液浸泡吸附锂离子后的纤维材料，进行解吸，解吸完成后。纤维材料进行下一轮的吸附实验，每组材料重复3轮吸附实验。采用电感耦合等离子体原子发射光谱法(ICP-OES)测定水 中的锂含量。实验用卤水的组成如下表1所示。计算离子筛纤维材料对锂离子的吸附容量，结果如下表2所示。
表1.实验用卤水的组成
表2.吸附容量结果记录表
从表2中的记录可得，实施例1-6的双层锂离子筛纤维材料的对锂离子的吸附容量较大，且循环性能较好，说明了在吸附和解吸过程中，离子筛在材料中的溶损是较小的。
而对比例1获得纤维材料并非双层材料，锰离子筛并没有得到包覆层纤维的保护，且亲水纤维材料也没置于芯层，这会导致锰离子筛的溶损较大，从而导致吸附循环性能下降。并且，配方中所用的高分子聚合物与两种离子筛共混，可能也影响了离子筛的均匀分布，或者堵塞了离子筛的吸附位点，导致吸附性能量下降。
对比例2将锰离子筛置于纤维材料包覆层，钛离子筛置于纤维材料芯层，包覆层的锰离子筛溶损较大，导致了吸附循环性能变差。
对比例3将实施例1的芯层纺丝液作为包覆层纺丝液，包覆层纺丝液作为芯层纺丝 液，对比例3获得的纤维材料包覆层的亲水性更强，会加大离子筛的溶损，导致吸附循环性能下降。
对比例4的芯层材料中省略了亲水性聚醚砜，包覆层材料中省略了聚己二酰己二胺和间苯甲酚，此时，缺少了亲水性聚醚砜对芯层的改性，会显著降低纤维材料的亲水性、渗透性和润湿性，同时，由于聚己二酰己二胺和聚对苯二甲酰对苯二胺均可以为骨架材料提供强度，这两者配合使用效果更佳，而省略其中的聚己二酰己二胺后会导致骨架材料的强度降低，在亲水性和强度受到影响的情况下，同时也会影响锂离子在材料中的分布，导致吸附量下降，循环性能下降。
对比例5的亲水性更强，有利于纤维膜在水中的润湿，从而提高吸附性，但由于水溶性加大，使得吸附循环稳定性较差。
对比例6的纤维材料，芯层和包覆层的纤维材料的造孔剂均为碳酸钠，芯层纤维在造孔时产生气泡的速度和能力弱于实施例1，会影响纤维材料的孔隙形成，导致吸附量和吸附循环性能下降。
实验例二：断裂拉伸率测试
在室温条件下，采用伸长率试验机FL-8610A分别对实施例1-6和对比例1-6获得纤维材料进行断裂拉伸率测试。断裂拉伸率测试方法依据仪器的使用说明书进行。结果如下表3所示。
表3.断裂伸长率测试结果记录表

从表3中可得，实施例1-6获得的双层锂离子筛纤维材料，其断裂伸长率均较大，说明了纤维材料强度较大，不易发生断裂现象，适用于在卤水中长期使用。而对比例1的纤维材料并非双层材料，而是将所有材料共混形成的单层纤维，其断裂伸长率相比实施例有所下降，较易发生断裂现象。对比例3将实施例1的芯层纺丝液作为包覆层纺丝液，包覆层纺丝液作为芯层纺丝液，获得的是外柔内刚的纤维，其机械性能弱于实施例1，较易断裂。对比例4和对比例5的纤维材料其芯层和包覆层的组成均进行了调整，导致了断裂伸长率下降。对比例6中孔隙的形成欠佳，导致其断裂伸长率也略低于实施例1。
综上所述，本公开提供的双层锂离子筛纤维材料优化了芯层材料和包覆层材料的配方，获得了外刚内柔的纤维材料，包覆层纤维刚性较好，强度较大，不易断裂，起到很好的支撑作用，能够很好地抗水压，更好地维护纤维材料的结构完整性；芯层纤维柔韧性较好，能够进一步减少材料在使用过程中的断裂机率，芯层材料在使用过程中并没有直接与卤水接触，而本公开通过采用亲水性聚醚砜对芯层材料进行改性，提高了卤水向内的渗透与浸润，从而提高了锂离子的吸附性能。
本公开提供的双层锂离子筛纤维材料，将较易溶损的锰离子筛置于纤维材料的芯层，包覆层纤维材料对锰离子筛形成保护层，减少了酸液与锰离子筛的直接接触，抑制了酸液对锰离子筛的腐蚀，从而减少了锰离子筛的溶损，保证纤维材料的循环性能。
本公开提供的双层锂离子筛纤维材料，采用碳酸钠为包覆层纤维造孔剂，碳酸氢钠为芯层纤维造孔剂，使得纤维能够形成更多的孔隙，同时芯层纤维造孔时产生的气泡由内向外排出，进一步促进了孔隙的形成。
本公开提供的双层锂离子筛纤维材料的制备方法，采用纺丝工艺技术制备，纺丝获得的纤维材料孔隙率高，比表面积大，再通过酸浸造孔工艺造孔，酸浸过程中，二氧化碳的析出进一步使得纤维材料的孔隙率提高，使得锂离子筛暴露更多的吸附位点，提高锂离子的吸附量。
本公开提供的双层锂离子筛纤维材料的制备方法，获得的纤维材料可以为纤维膜或纤维线，具体的形式可以根据实际需要设定，膜状纤维可以直接用于提锂；线状纤维可以先进行柱体填充，再进行提锂。或者，线状纤维可以经过纺纱形成直径更大的纤维纱线，纤维纱线集成纤维束，直接通过纤维束在卤水中进行提锂。
以上详细描述了本公开的可选实施方式，但是，本公开并不限于此。在本公开的技术构思范围内，可以对本公开的技术方案进行多种简单变型，包括各个技术特征以任何 其它的合适方式进行组合，这些简单变型和组合同样应当视为本公开所公开的内容，均属于本公开的保护范围。
工业实用性
本公开提供的双层锂离子筛纤维材料优化了芯层材料和包覆层材料的配方，获得了外刚内柔的纤维材料，包覆层纤维刚性较好，强度较大，不易断裂，起到很好的支撑作用，能够很好地抗水压，更好地维护纤维材料的结构完整性；芯层纤维柔韧性较好，能够进一步减少材料在使用过程中的断裂机率，芯层材料在使用过程中并没有直接与卤水接触，而本公开通过采用亲水性聚醚砜对芯层材料进行改性，提高了卤水向内的渗透与浸润，从而提高了锂离子的吸附性能。本公开提供的双层锂离子筛纤维材料，将较易溶损的锰离子筛置于纤维材料的芯层，包覆层纤维材料对锰离子筛形成保护层，减少了酸液与锰离子筛的直接接触，抑制了酸液对锰离子筛的腐蚀，从而减少了锰离子筛的溶损，保证纤维材料的循环性能。本公开提供的双层锂离子筛纤维材料的制备方法，采用纺丝工艺技术制备，纺丝获得的纤维材料孔隙率高，比表面积大，再通过酸浸造孔工艺造孔，由于本公开采用碳酸钠为包覆层纤维造孔剂，碳酸氢钠为芯层纤维造孔剂，使得纤维能够形成更多的孔隙，同时芯层纤维造孔时产生的气泡由内向外排出，进一步促进了孔隙的形成。酸浸过程中，二氧化碳的析出进一步使得纤维材料的孔隙率提高，使得锂离子筛暴露更多的吸附位点，提高锂离子的吸附量。制备获得的双层锂离子筛纤维材料可以广泛应用于卤水中进行提锂。

Claims (26)

  1. 一种双层锂离子筛纤维材料，其特征在于，其由内至外依次包括芯层和包覆层；
    所述芯层包括柔性载体和分散于所述柔性载体内的锰离子筛，所述柔性载体由软质聚氯乙烯和亲水性聚醚砜构成，所述柔性载体上构建有多个第一孔洞；
    所述包覆层包括刚性载体和分散于所述刚性载体内的钛离子筛，所述刚性载体是由聚对苯二甲酰对苯二胺和聚己二酰己二胺构成，所述柔性载体上构建有多个第二孔洞。
  2. 根据权利要求1所述的双层锂离子筛纤维材料，其特征在于，所述芯层和所述包覆层的厚度比为1：(1-3)。
  3. 根据权利要求1-2任一项所述的双层锂离子筛纤维材料，其特征在于，所述芯层的比表面积为5m2/g-12m2/g。
  4. 根据权利要求1-3任一项所述的双层锂离子筛纤维材料，其特征在于，所述包覆层的比表面积为5m2/g-12m2/g。
  5. 根据权利要求1-4任一项所述的双层锂离子筛纤维材料，其特征在于，所述锰离子筛、所述软质聚氯乙烯和所述亲水性聚醚砜的质量比为(25-40)：(70-100)：(25-50)。
  6. 根据权利要求1-5任一项所述的双层锂离子筛纤维材料，其特征在于，所述钛离子筛、所述聚对苯二甲酰对苯二胺和所述聚己二酰己二胺的质量比为(25-40)：(45-80)：(25-50)。
  7. 根据权利要求1-6任一项所述的双层锂离子筛纤维材料，其特征在于，所述软质聚氯乙烯的密度为1.2g/cm3-1.3g/cm3，屈服强度为15MPa-25MPa。
  8. 根据权利要求1-7任一项所述的双层锂离子筛纤维材料，其特征在于，所述双层锂离子筛纤维材料为纤维膜或纤维线。
  9. 根据权利要求8所述的双层锂离子筛纤维材料，其特征在于，所述纤维线的直径为0.5μm-100μm。
  10. 一种双层锂离子筛纤维材料的制备方法，其特征在于，其包括：
    将锰离子筛、软质聚氯乙烯、亲水性聚醚砜、芯层溶剂和碳酸氢钠混合形成芯层纺丝液；
    将钛离子筛、聚对苯二甲酰对苯二胺、聚己二酰己二胺、包覆层溶剂和碳酸钠混合形成包覆层纺丝液；
    将所述芯层纺丝液和所述包覆层纺丝液经纺丝形成包覆层包覆芯层的双层纤维中间品；
    将所述双层纤维中间品经酸浸造孔，随后干燥即得所述双层锂离子筛纤维材料。
  11. 根据权利要求10所述的双层锂离子筛纤维材料的制备方法，其特征在于，所述锰离子筛、所述软质聚氯乙烯、所述亲水性聚醚砜、所述芯层溶剂和所述碳酸氢钠的质量比为(25-40)：(70-100)：(25-50)：(135-235)：(15-30)。
  12. 根据权利要求10-11任一项所述的双层锂离子筛纤维材料的制备方法，其特征在于，所述芯层溶剂包括二甲基甲酰胺和N-甲基吡咯烷酮中的至少一种。
  13. 根据权利要求12所述的双层锂离子筛纤维材料的制备方法，其特征在于，所述芯层溶剂包括质量比为(75-135)：(60-100)的二甲基甲酰胺和N-甲基吡咯烷酮。
  14. 根据权利要求10-12任一项所述的双层锂离子筛纤维材料的制备方法，其特征在于，所述钛离子筛、所述聚对苯二甲酰对苯二胺、所述聚己二酰己二胺、所述包覆层溶剂和所述碳酸钠的质量比为(25-40)：(45-80)：(25-50)：(140-250)：(15-30)。
  15. 根据权利要求10-13任一项所述的双层锂离子筛纤维材料的制备方法，其特征在于，所述包覆层溶剂包括甲磺酸和间苯甲酚中的至少一种。
  16. 根据权利要求15所述的双层锂离子筛纤维材料的制备方法，其特征在于，所述包覆层溶剂包括质量比为(90-150)：(50-100)的甲磺酸和间苯甲酚。
  17. 根据权利要求10-15任一项所述的双层锂离子筛纤维材料的制备方法，其特征在于，所述纺丝包括干法纺丝、湿法纺丝或静电纺丝。
  18. 根据权利要求10-16任一项所述的双层锂离子筛纤维材料的制备方法，其特征在于，所述纺丝为同轴静电纺丝。
  19. 根据权利要求18所述的双层锂离子筛纤维材料的制备方法，其特征在于，所述同轴静电纺丝的纺丝环境温度为15℃-25℃，环境湿度小于30％，纺丝电压为15kv-25kv。
  20. 根据权利要求18-19任一项所述的双层锂离子筛纤维材料的制备方法，其特征在于，所述同轴静电纺丝时，所述芯层纺丝液的推进流速为0.18-0.25mL/h，所述包覆层纺丝液的推进流速为0.10mL/h-0.15mL/h。
  21. 根据权利要求10-20任一项所述的双层锂离子筛纤维材料的制备方法，其特征在于，所述酸浸用酸为盐酸。
  22. 根据权利要求10-21任一项所述的双层锂离子筛纤维材料的制备方法，其特征在于，所述酸浸的时间为0.5h-1.5h。
  23. 根据权利要求10-22任一项所述的双层锂离子筛纤维材料的制备方法，其特征在于，所述芯层纺丝液的制备方法包括：将所述芯层溶剂与所述软质聚氯乙烯和亲水性聚醚砜混合，升温至70℃-85℃，搅拌5h-7h，降至室温，然后加入所述碳酸氢钠，搅拌均匀 后，再加入所述锰离子筛，搅拌均匀，得到所述芯层纺丝液。
  24. 根据权利要求10-23任一项所述的双层锂离子筛纤维材料的制备方法，其特征在于，所述包覆层溶剂包括甲磺酸和间苯甲酚，所述包覆层纺丝液的制备方法包括：先将所述甲磺酸和所述聚对苯二甲酰对苯二胺混合，加热至70℃-85℃，搅拌5h-6h，得到聚对苯二甲酰对苯二胺溶液；然后将所述间苯甲酚与所述聚己二酰己二胺混合，加热至70℃-85℃，搅拌5h-6h，得到聚己二酰己二胺溶液；将所述聚对苯二甲酰对苯二胺溶液和所述聚己二酰己二胺溶液混合，搅拌均匀，降至室温，然后加入所述碳酸钠，搅拌均匀后，再加入所述钛离子筛，搅拌均匀，得到所述包覆层纺丝液。
  25. 如权利要求1-9任一项所述的双层锂离子筛纤维材料或如权利要求10-24任一项所述的双层锂离子筛纤维材料的制备方法制备获得的双层锂离子筛纤维材料在盐湖卤水提锂中作为吸附剂的应用。
  26. 根据权利要求25所述的应用，其特征在于，所述盐湖卤水包括原卤和老卤中的至少一种。
PCT/CN2023/140705 2023-12-21 2023-12-21 一种双层锂离子筛纤维材料及其制备方法和应用 Pending WO2025129574A1 (zh)

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