WO2016095771A1 - Composite nanofiber separator with thermal shutdown function, preparation method therefor and energy storage components - Google Patents

Composite nanofiber separator with thermal shutdown function, preparation method therefor and energy storage components Download PDF

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WO2016095771A1
WO2016095771A1 PCT/CN2015/097248 CN2015097248W WO2016095771A1 WO 2016095771 A1 WO2016095771 A1 WO 2016095771A1 CN 2015097248 W CN2015097248 W CN 2015097248W WO 2016095771 A1 WO2016095771 A1 WO 2016095771A1
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composite nanofiber
separator
nanofiber membrane
closed cell
cell function
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PCT/CN2015/097248
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French (fr)
Chinese (zh)
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宣萱
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宁波艾特米克锂电科技有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—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
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention belongs to the technical field of batteries, and the battery comprises a lithium ion battery, a lithium sulfur battery, a super capacitor, a lead acid battery, an alkaline battery, a zinc air battery and a sodium ion battery.
  • the invention relates to a composite nanofiber membrane with closed pore function and a preparation method thereof.
  • the invention also relates to the production of such membranes and the use of such membranes as battery separators.
  • the composite nanofiber membrane can be used as a separator for batteries such as lithium ion batteries, lithium sulfur batteries, super capacitors, lead acid batteries, zinc air batteries, and sodium ion batteries.
  • batteries such as lithium ion batteries, lithium sulfur batteries, super capacitors, lead acid batteries, zinc air batteries, and sodium ion batteries.
  • lithium-ion batteries have been widely used in portable electronic products such as mobile phones, notebook computers, and cameras because of their high energy density, long cycle life, fast charge and discharge, no pollution, and no memory effect.
  • the required rechargeable batteries are also gradually expanding into electric vehicles, aerospace, energy storage and other fields.
  • Battery separator is a key component related to battery safety performance. Its main function is to isolate the positive and negative electrodes and prevent electrons from passing freely. At the same time, the ions can pass freely. The performance determines the interface structure and internal resistance of the battery. The overall performance of the lithium battery.
  • Lithium battery safety is a very urgent problem, especially power lithium-ion batteries, which have entered many fields such as automobiles, robots, power tools, aerospace, etc. Power lithium batteries are more likely to be exposed to high temperatures due to large current consumption. High, its security has received much attention. So the diaphragm The full performance should mention a higher level (when the battery temperature is too high, the diaphragm can block the conduction of current through the closed hole, prevent explosion, and the diaphragm size is stable after the closed hole does not shrink).
  • the mainstream products of lithium ion battery separators are polypropylene and polyethylene porous membranes and composite membranes thereof with porous ceramic coatings.
  • the outstanding problems are poor wettability, weak liquid absorption ability, difficulty in achieving high rate charge and discharge, easy formation of dendrites under high temperature cycling conditions, and large deformation due to heat, and there are serious safety hazards.
  • the researchers mainly adopt the following methods: First, the heat resistance of the nanofiber membrane is improved by in situ formation or addition of nanoparticles by sol-gel or coating of a solution containing nanoparticles.
  • these methods are complicated in preparation process, generally require coating process, hot pressing treatment or extraction process, and the membrane shrinks with closed volume, the membrane area shrinks, and the diaphragm loses positive and negative electrodes.
  • the patent of CN103688387A of Dreamweave Company of the United States discloses a microporous polymer battery separator, which combines polymer nanometers into a matrix of polymer microfibers by high shear treatment to form a nanofiber web with good pore size effect, in heat resistance, Dimensional stability and good liquid absorption, wettability, etc.
  • CN103270639 A, CN103943806 A, etc. can not meet the excellent thermal dimensional stability and good self-closing performance of the diaphragm material, which may cause potential damage to the battery such as burning and explosion.
  • the technical problem to be solved by the present invention is to provide a manufacturing process that is simple, A composite nanofiber separator with low cost and excellent performance and a preparation method thereof.
  • the present invention firstly provides a nanofiber separator having a heat sealing function, the raw material of which comprises fibrillated cellulose nanofibers and low melting point polymer nanofibers, between the fibrillated cellulose nanofibers
  • the fibrillated cellulose nanofibers and the low melting point polymer nanofibers are combined by long-chain molecular cross-linking mainly by hydrogen bonding and intermolecular force;
  • the composite nanofiber membrane has The pores allow electrolyte ions to pass through and prevent electrons from passing through; in a temperature environment of 130 to 170 ° C, the composite nanofiber membrane pores are closed to prevent excessive and undesired ions from passing through the battery after damage.
  • the composite nanofiber membrane When the composite nanofiber membrane has a closed pore state, the composite nanofiber membrane has a stable size, and is heated within a temperature of 200 ° C for 30 minutes, and the heat shrinkage rate is less than 2%.
  • the composite nanofiber membrane having a closed cell function has a thickness of 10 to 80 ⁇ m.
  • the invention discloses a method for preparing a composite nanofiber membrane having a closed cell function, which is prepared by using a fibrillated cellulose nanofiber and a low melting point polymer nanofiber with a mass ratio of 1:9 to 9:1 as a raw material.
  • the preparation method of the composite nanofiber membrane having the closed cell function comprises the following specific steps:
  • the fibrillated cellulose nanofibers and the at least one low-melting polymer nanofibers are respectively dispersed in a solvent at a mass ratio of 1:9 to 9:1, and rapidly stirred to form a slurry;
  • Adding a binder to the slurry of step I; adding a binder can increase the mechanical strength thereof, and the binder can be selected in a wide range, such as polyethylene glycol, polyvinyl alcohol, butadiene and styrene. Polymer, acrylonitrile polymer, polyvinylidene fluoride and epoxy resin.
  • the slurry after step II is diluted to a concentration of 0.01% to 0.05%;
  • the diluted slurry is subjected to dehydration molding, pressing, drying and hot rolling forming on the Internet to obtain the composite nanofiber separator having a closed cell function.
  • the fibrillated cellulose nanofibers have a diameter of 10 to 1000 nm and a length of 10 to 3000 ⁇ m.
  • the fibrillated cellulose nanofibers include cellulose nanofibers separated from nanosized wood materials, seaweed cellulose nanofibers, and bacterial cellulose nanofibers obtained by culturing strains.
  • the low melting point polymer nanofibers have a diameter of 10 to 1000 nm.
  • the low melting point polymer nanofibers are polymethyl methacrylate, vinylidene fluoride polymer, polyurethane, polyvinyl chloride, polyolefin, polyethylene-vinyl acetate copolymer, polybutylene succinate One or more combinations of esters.
  • the solvent is a low molecular weight alcohol, deionized water, or a mixture of a low molecular weight alcohol and deionized water.
  • Another aspect of the present invention is to provide an energy storage device prepared by using the composite nanofiber membrane having the closed cell function, including a lithium ion battery, a lithium sulfur battery, an alkaline battery, a super capacitor, a lead acid battery, and zinc air. Battery, sodium ion battery.
  • the preparation method of the invention has low cost, simple production process, convenient transfer and is suitable for large-scale production.
  • the closed-cell functional composite nanofiber membrane prepared by the invention exhibits excellent physical properties including: closed cell, heat resistance, dimensional stability, gas permeability, good wettability with respect to electrolyte and high liquid absorption Rate and other characteristics.
  • the closed cell temperature is 130-170 ° C. After the closed cell, the fiber membrane does not shrink, and the heat shrinkage rate is less than 2% when heated at 200 ° C for 30 min.
  • Figure 1 is a SEM photograph of a polyolefin-based separator of a comparative example
  • Example 3 is a SEM photograph of the closed-cell functional composite nanofiber membrane of Example 5 after heat treatment at 200 ° C for 2 hours;
  • Example 4 is a photograph of the heat shrinkability of the comparative example and the closed-cell functional composite nanofiber membrane of Example 3 at 150 ° C and 200 ° C;
  • the separator is prepared using a fibrillated fibrillated cellulose nanofiber and a low melting polymer nanofiber slurry.
  • the fibrillated cellulose nanofibers may have a diameter of 10 to 1000 nm.
  • the separator When the diameter of the fibrillated cellulose nanofibers is less than 10 nm, it is very difficult to form fibrillated cellulose nanofibers, but when the diameter of the fibrillated cellulose nanofibers exceeds 1000 nm, the separator has a rough surface, which makes the electrodes Not in good contact with the diaphragm.
  • the value diameter of the fibrillated cellulose nanofibers is more preferably between 10 and 200 nm.
  • the separator is prepared using a fibrillated fibrillated cellulose nanofiber and a low melting polymer nanofiber slurry.
  • the low melting point polymer nanofibers may have a diameter of 10 to 1000 nm.
  • the fibrillated cellulose nanofibers may be selected from the group consisting of fibrillated cellulose nanofibers separated from nanosized wood materials, algae fibrillated cellulose nanofibers, and bacterial fibrillated cellulose nanometers obtained by culturing strains. At least one of the fibers.
  • the type of the low-melting polymer nanofiber can be used all without limitation, as long as it is a nanofiber having a low melting point, and includes a slurry in which the low-melting polymer nanofiber in the slurry can be uniformly mixed with the fibril The cellulose nanofibers are mixed and are not soluble during the preparation of the slurry.
  • the low melting point polymer nanofiber is selected from the group consisting of: low melting point polymer nanofibers, polymethyl methacrylate, vinylidene fluoride polymer, polyurethane, polyvinyl chloride, polyolefin, polyethylene-vinyl acetate copolymer One or more combinations of polyethylene succinate.
  • a solvent in which fibrillated cellulose nanofibers and low melting point polymer nanofibers are stably dispersed can be used as a solvent.
  • a solvent for example, deionized water, a low molecular weight alcohol, and a mixture of a low molecular weight alcohol and deionized water can be selected as the solvent.
  • the separator Compared with the fibrillated cellulose nanofibers in the preparation method, when the mixing ratio of the fibrillated cellulose nanofibers and the low melting point polymer nanofibers is less than 1:9, the separator does not reach the closed pores due to heat. On the other hand, when the mixing ratio of the fibrillated cellulose nanofibers to the low melting point polymer nanofibers exceeds 9:1, the heat resistance and dimensional stability of the separator are seriously affected and it is difficult to transfer.
  • a solution containing fibrillated cellulose nanofibers and low-melting polymer nanofibers was prepared by high-speed stirring, and the slurry was subjected to a papermaking method to prepare a separator of the present invention.
  • a method of preparing a separator for example, a conventional method of preparing paper, is used to prepare a fibrillated cellulose nanofiber into a nonwoven fabric.
  • all methods of preparing the separator can be used to prepare a separator for a lithium ion battery.
  • the thickness of the separator can be in the range of approximately 10-80 ⁇ m. When the thickness of the separator exceeds 80 ⁇ m, the charge and discharge efficiency of the battery will be seriously affected. When the thickness of the separator is less than 10 ⁇ m, the self-discharge and short-circuit rate of the battery are greatly improved.
  • fibrillated cellulose nanofibers when a binder is used in the preparation of the separator, the -OH group present in the functional group is reduced, which is due to an increase in hydrogen bonding, when fibrillated cellulose nanofibers When used for a lithium secondary battery separator, the reaction between Li ions and -OH groups in the fibrillated cellulose nanofibers does not occur anymore, which leads to an increase in stability.
  • the binder can be uniformly mixed with the fibrillated cellulose nanofibers.
  • the energy storage device prepared by using the above composite nanofiber membrane with closed cell function includes lithium ion battery, lithium sulfur battery, alkaline battery, super capacitor, lead acid battery, zinc air battery, sodium ion.
  • the battery must effectively improve the safety and reliability of the energy storage device.
  • the glycol ester is dispersed in a solvent, and then the slurry is uniformly homogenized by high-speed mechanical stirring to prepare a slurry.
  • the solvent is diluted to 0.01% by adding a solvent, and the diluted slurry is dehydrated by the net; pressed and dried; hot-rolled at a molding temperature of 100 ° C and a line pressure of 100 kg/cm, and then rolled, Rewinding, slitting and packaging to produce a battery separator.
  • the above closed-cell composite separator exhibits excellent characteristics, for example, a porosity of 56% and 55% before and after heat treatment at 200 ° C for 2 hours, a heat shrinkage rate of almost 0 at 30 ° C for 30 minutes, and an absorbance of 31% at 200 ° C;
  • the Gutley value (s/100 cc) before and after the 2 h heat treatment was 23 and 23.
  • low melting point polymer nanofibers 7:3 algae cellulose nanofibers and low melting polymer nanofibers (vinylidene fluoride polymer) in a solvent, and then passing high speed machinery
  • the slurry was prepared by stirring to bring the solution to an overall uniformity.
  • the solvent is diluted to 0.01% by adding a solvent, and the diluted slurry is dehydrated by the net; pressed and dried; hot-rolled at a molding temperature of 100 ° C and a line pressure of 100 kg/cm, and then rolled, Rewinding, slitting and packaging to produce a battery separator.
  • the above closed-cell composite separator exhibits excellent characteristics, for example, a porosity of 56% and 30% before and after heat treatment at 200 ° C for 2 hours, and a heat shrinkage rate of almost 1% at 200 ° C for 30 minutes;
  • the Gutley value (s/100 cc) before and after heat treatment at 200 ° C for 2 h was 23 and 800.
  • the solvent is diluted to 0.01% by adding a solvent, and the diluted slurry is dehydrated by the net; pressed and dried; hot-rolled at a molding temperature of 100 ° C and a line pressure of 100 kg/cm, and then rolled, Rewinding, slitting and packaging to produce a battery separator.
  • the above closed-cell composite membrane exhibits excellent characteristics, for example, a porosity of 54% and 18% before and after heat treatment at 200 ° C for 2 hours, a heat shrinkage of 1.4% at 200 ° C, 30 minutes, and a percentage of absorbance of 285%;
  • Gurley value (s/100 cc) before and after the heat treatment at °C for 2 h was 23 and 2020.
  • low melting point polymer nanofibers 3:7 algae cellulose nanofibers and low melting polymer nanofibers (polyethylene-vinyl acetate copolymer) in a solvent, and then passing The slurry is prepared by high-speed mechanical agitation to achieve uniformity of the solution.
  • the solvent is diluted to 0.01% by adding a solvent, and the diluted slurry is dehydrated by the net; pressed and dried; hot-rolled at a molding temperature of 100 ° C and a line pressure of 100 kg/cm, and then rolled, Rewinding, slitting and packaging to produce a battery separator.
  • the above closed-cell composite membrane exhibits excellent closed cell characteristics, for example, 200 ° C, and a porosity of 58% and 5% before and after heat treatment for 2 hours, and a heat shrinkage rate of 5% at 200 ° C, 30 minutes;
  • Gurley value (s/100 cc) before and after heat treatment at 200 ° C for 2 h was 25 and 3867.
  • Cellulose nanofibers and low melting point polymer nanofibers (polyurethane) separated from nanosized wood materials of fibrillated cellulose nanofibers: low melting point polymer nanofibers 1:9 are dispersed in a solvent, and then passed through a high speed
  • the slurry is prepared by mechanical agitation to achieve uniformity of the solution.
  • the solvent is diluted to 0.01% by adding a solvent, and the diluted slurry is dehydrated by the net; pressed and dried; hot-rolled at a molding temperature of 100 ° C and a line pressure of 100 kg/cm, and then rolled, Rewinding, slitting and packaging to produce a battery separator.
  • the above closed-cell composite membrane exhibits excellent characteristics, for example, 200 ° C, 2 h heat treatment before and after the hole
  • the gap ratios were 57% and 1%, respectively; at 20 °C, 18% heat shrinkage at 30 min; 235% absorbance percentage; 200 °C, Gurley value (s/100 cc) before and after 2 h heat treatment was 23 and substantially no aeration.
  • the method of preparing a composite nanofiber membrane having a closed cell function has an advantage in that it is suitable for mass production due to its competitive price due to its simple preparation process and preparation cost.
  • a separator having excellent physical characteristics such as closed cell properties, gas permeability, thermal stability, dimensional stability, thickness adjustable, and impregnation properties can be prepared.
  • the mechanical properties of the closed-cell nanofiber composite separator prepared in the examples were tested below.
  • the test method is as follows:
  • Comparative Example 1 and Comparative Example 1 were examined by scanning electron microscopy at 200 ° C for 2 h.
  • the SEM images are shown in Figures 1, 2 and 3.
  • the pore volume of the membrane can be obtained by dividing the mass of n-butanol (Wb) by the density of n-butanol ( ⁇ b), the ratio of this volume to the volume of the dry membrane (Vp) and the porosity of the membrane. The calculation formula is:
  • Wd is the mass of the membrane
  • Ww is the mass of the membrane after soaking
  • Wb is the absorption of the membrane
  • Vp is the volume of the dry membrane
  • ⁇ b is the density of n-butanol
  • the Gurley densitometer measures the time (sec) required for 100 mL of air through a sample with an effective test area of 1.0 Sqinch (0.01, 0.25 Sqinch optional) as the gas permeability value of the film (at least 5 parallels) test).
  • the closed-cell composite separator obtained in the examples was heat-treated at 200 ° C for 0.5 h, and the dimensional change of the statistical separator was observed (at least 5 parallel tests).
  • Comparative Example 1 the separator of Example 5 was compared at 200 ° C for 2 h before and after the SEM photograph of the surface
  • Figure 1 is a SEM photograph of the PE separator of the comparative example, the pore structure of which is a uniformly distributed pore formed by stretching.
  • Figure 2 is a SEM photograph of the closed-cell composite membrane before it is heated. It can be seen that the cross-linking between the nanofibers exhibits a three-dimensional pore structure.
  • Fig. 3 is a SEM photograph of the closed-cell membrane after heating at 200 ° C for 2 h, substantially no visible pore structure exists, and the pores formed by cross-linking between the fibers are closed.
  • Example 4 is a photograph of a comparative example olefin-based separator and the porous separator of Example 3 taken before the separator was exposed to high temperature, and after exposure to 150 ° C and 30 ° C at 30 ° C.
  • the olefin-based separator of the comparative example had a lower melting point, when the olefin-based separator was exposed to a temperature of 200 ° C, the frame of the olefin-based separator was completely lost. Therefore, when the olefin-based separator of Comparative Example 1 was used as a separator of a lithium ion battery, its safety was not secured.
  • the closed-cell nanocomposite separator is suitable as a separator for a lithium secondary battery in terms of dimensional stability and heat shrinkage.
  • the comparative example and the separator of Example 3 were prepared, and the electrolyte was dropped into the comparative example and the separator of Example 3 with a micro-adjusting syringe, and the results were obtained after 2 s and 15 minutes. As shown in Figure 5.
  • Example 3 It is assumed that the cell infiltration property of the closed cell function composite nanofiber separator of the lithium secondary battery has a large influence on the cell yield and efficiency, and the closed cell nanocomposite in Example 3 can be seen to be suitable for the separator of a lithium secondary battery.

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Abstract

The present invention provides a composite nanofiber separator with a thermal shutdown function, a preparation method therefor and energy storage components, and relates to lithium-ion batteries, lithium-sulphur batteries, supercapacitors, lead-acid batteries, alkaline batteries, zinc-air batteries, sodium-ion batteries and fiber separators thereof. The composite nanofiber separator with a thermal shutdown function is of a non-woven fabric structure and is formed by cross-linking a fibrillated cellulose nanofiber and at least one low-melting-point polymer nanofiber, the low-melting-point polymer nanofiber being a polyolefin- and polyester-containing nanofiber. The thickness of the composite nanofiber separator with a thermal shutdown function may range from 10 μm to 80 μm, and the shutdown temperature ranges from 130°C to 170°C. The nanofiber separator does not shrink after shutdown, and the heat shrinkage rate is less than 2％ after heating at 200°C for 30 min. The composite nanofiber separator can achieve a thermal shutdown function, thereby preventing the direct contact between the positive and negative electrodes of a battery due to thermal inertia and significantly improving the safety of the aforementioned energy storage components.

Description

具有热闭孔功能复合纳米纤维隔膜、制备方法和储能器件Composite nanofiber membrane with heat closed pore function, preparation method and energy storage device 技术领域Technical field
本发明属于电池技术领域，所述电池包括锂离子电池，锂硫电池，超级电容器，铅酸电池，碱性电池，锌空气电池，钠离子电池。涉及一种具有闭孔功能的复合纳米纤维隔膜及其制备方法。本发明还涉及这种膜的生产以及该膜作为电池隔膜的应用。The invention belongs to the technical field of batteries, and the battery comprises a lithium ion battery, a lithium sulfur battery, a super capacitor, a lead acid battery, an alkaline battery, a zinc air battery and a sodium ion battery. The invention relates to a composite nanofiber membrane with closed pore function and a preparation method thereof. The invention also relates to the production of such membranes and the use of such membranes as battery separators.
背景技术Background technique
复合纳米纤维隔膜可作为隔膜应用于电池如锂离子电池，锂硫电池，超级电容器，铅酸电池，锌空气电池，钠离子电池。目前，锂离子电池因其具有较高的能量密度、较长的循环寿命、可快速充放电、无污染和无记忆效应等优点，已被广泛应用于便携式电子产品如：手机、笔记本电脑、摄像机等所需的充电电池，也逐渐扩展到电动汽车、航天航空、储能以及其他领域。The composite nanofiber membrane can be used as a separator for batteries such as lithium ion batteries, lithium sulfur batteries, super capacitors, lead acid batteries, zinc air batteries, and sodium ion batteries. At present, lithium-ion batteries have been widely used in portable electronic products such as mobile phones, notebook computers, and cameras because of their high energy density, long cycle life, fast charge and discharge, no pollution, and no memory effect. The required rechargeable batteries are also gradually expanding into electric vehicles, aerospace, energy storage and other fields.
电池隔膜作为关乎电池安全性能的关键部件，其主要作用是隔离正负极并使电子不能自由穿过，同时能让离子自由通过，其性能决定了电池的界面结构、内阻等，直接关系到锂电池的整体性能。在锂电池隔离正负极的情况下，发生电池过度充电或短路，或者错误连接，产生不正常电流，以及在动力大、容量高时使用，均会造成电池内温度急剧升高，电池隔膜应有足够的耐温功能；因电池温度升高，造成隔膜孔径缩小，锂离子不能正常通过，导致电池温度升高，达到锂的熔点或电解质的引燃点，将引起电池的燃烧和爆炸事故的发生。Battery separator is a key component related to battery safety performance. Its main function is to isolate the positive and negative electrodes and prevent electrons from passing freely. At the same time, the ions can pass freely. The performance determines the interface structure and internal resistance of the battery. The overall performance of the lithium battery. In the case where the lithium battery is isolated from the positive and negative poles, battery overcharging or short circuit occurs, or incorrect connection occurs, abnormal current is generated, and when the power is large and the capacity is high, the temperature inside the battery is sharply increased, and the battery separator should be There is sufficient temperature resistance; due to the increase of battery temperature, the diaphragm aperture is reduced, lithium ions can not pass normally, resulting in the battery temperature rising, reaching the melting point of lithium or the ignition point of the electrolyte, which will cause the burning and explosion of the battery. occur.
锂电池安全问题是十分迫切的问题，特别是动力锂离子电池，目前已经进入汽车、机器人、电动工具、航空航天等诸多领域，动力锂电池由于电流量较大，暴露于高温下的可能性比较高，其安全性备受关注。所以隔膜的安 全性能应提到更高的层次(电池温度过高时，隔膜可通过闭孔来阻隔电流的传导，防止爆炸，且闭孔后隔膜尺寸稳定不发生收缩)。Lithium battery safety is a very urgent problem, especially power lithium-ion batteries, which have entered many fields such as automobiles, robots, power tools, aerospace, etc. Power lithium batteries are more likely to be exposed to high temperatures due to large current consumption. High, its security has received much attention. So the diaphragm The full performance should mention a higher level (when the battery temperature is too high, the diaphragm can block the conduction of current through the closed hole, prevent explosion, and the diaphragm size is stable after the closed hole does not shrink).
目前锂离子电池隔膜的主流产品为聚丙烯和聚乙烯多孔膜及其与多孔陶瓷涂层的复合膜。其突出的问题是润湿性差、吸液能力弱，难以实现高倍率充放电，在高温循环条件下容易形成枝晶及受热形变大，存在严重的安全隐患。At present, the mainstream products of lithium ion battery separators are polypropylene and polyethylene porous membranes and composite membranes thereof with porous ceramic coatings. The outstanding problems are poor wettability, weak liquid absorption ability, difficulty in achieving high rate charge and discharge, easy formation of dendrites under high temperature cycling conditions, and large deformation due to heat, and there are serious safety hazards.
为了提高隔膜的耐热性，科研人员主要采取以下几种方法：一是通过溶胶-凝胶原位生成或者添加纳米颗粒或者涂覆含纳米颗粒的溶液的方式提高纳米纤维隔膜的耐热性，如CN200810244343.7、CN201110434221.6，这些方法制备工艺复杂，一般需要涂覆工艺、热压处理或者萃取等工序，同时隔膜闭孔时伴随着体积收缩，膜面积缩小，使隔膜失去正负极之间的隔断作用，造成不安全隐患；二是使用高耐热性的聚合物溶液进行静电纺丝，如CN201210486465.3、CN201210425855.X、CN201010166400.1和CN201210169182.6，该方法制备的纤维膜功能单一，且制备过程繁琐，成本高。三是纳米纤维材料的无纺布隔膜在锂离子电池隔膜领域的使用，是目前开发高端锂离子电池隔膜的重要课题之一。纳米基电池隔膜可明显改善隔膜材料的可润湿性，有效提高隔膜的耐热性和离子传导性能。美国Dreamweave公司的专利CN103688387A公布了多微孔聚合物电池隔膜，通过高剪切处理将聚合物纳米组合到聚合物微纤维矩阵内，制成孔隙尺寸效应好的纳米纤维网，在耐热性，尺寸稳定性以及良好的吸液能力，可润湿性等。同样，还有专利CN103270639 A，CN103943806 A等，但还是不能同时满足隔膜材料所应具有的优异的热尺寸稳定性和良好的自关闭性能，会使电池发生燃烧、爆炸等潜在危害。In order to improve the heat resistance of the separator, the researchers mainly adopt the following methods: First, the heat resistance of the nanofiber membrane is improved by in situ formation or addition of nanoparticles by sol-gel or coating of a solution containing nanoparticles. Such as CN200810244343.7, CN201110434221.6, these methods are complicated in preparation process, generally require coating process, hot pressing treatment or extraction process, and the membrane shrinks with closed volume, the membrane area shrinks, and the diaphragm loses positive and negative electrodes. Inter-segmentation, causing unsafe hidden dangers; second, electrospinning using a highly heat-resistant polymer solution, such as CN201210486465.3, CN201210425855.X, CN201010166400.1, and CN201210169182.6, the fiber membrane function prepared by the method It is single and the preparation process is cumbersome and costly. Third, the use of non-woven membranes of nanofiber materials in the field of lithium ion battery separators is one of the important topics in the development of high-end lithium-ion battery separators. The nano-based battery separator can significantly improve the wettability of the separator material and effectively improve the heat resistance and ion conductivity of the separator. The patent of CN103688387A of Dreamweave Company of the United States discloses a microporous polymer battery separator, which combines polymer nanometers into a matrix of polymer microfibers by high shear treatment to form a nanofiber web with good pore size effect, in heat resistance, Dimensional stability and good liquid absorption, wettability, etc. Similarly, there are patents CN103270639 A, CN103943806 A, etc., but still can not meet the excellent thermal dimensional stability and good self-closing performance of the diaphragm material, which may cause potential damage to the battery such as burning and explosion.
发明内容Summary of the invention
本发明所要解决的技术问题是针对以上缺陷，提供一种制造工艺简单、 低成本且性能优异的复合纳米纤维隔膜及其制备方法。The technical problem to be solved by the present invention is to provide a manufacturing process that is simple, A composite nanofiber separator with low cost and excellent performance and a preparation method thereof.
为解决上述技术问题，本发明首先提供一种具有热闭合功能的纳米纤维隔膜，其原料包括原纤化纤维素纳米纤维和低熔点聚合物纳米纤维，所述原纤化纤维素纳米纤维之间主要通过氢键、分子间作用力结合，所述原纤化纤维素纳米纤维与所述低熔点聚合物纳米纤维之间通过长径分子间的交联作用结合；所述复合纳米纤维隔膜上具有孔隙以便电解液离子穿过、且阻止电子穿过；在130～170℃温度环境下，所述复合纳米纤维隔膜孔隙闭合，以防止电池受损后的过量和不期望的离子通过。In order to solve the above technical problems, the present invention firstly provides a nanofiber separator having a heat sealing function, the raw material of which comprises fibrillated cellulose nanofibers and low melting point polymer nanofibers, between the fibrillated cellulose nanofibers The fibrillated cellulose nanofibers and the low melting point polymer nanofibers are combined by long-chain molecular cross-linking mainly by hydrogen bonding and intermolecular force; the composite nanofiber membrane has The pores allow electrolyte ions to pass through and prevent electrons from passing through; in a temperature environment of 130 to 170 ° C, the composite nanofiber membrane pores are closed to prevent excessive and undesired ions from passing through the battery after damage.
所述复合纳米纤维隔膜孔隙闭合状态下，所述复合纳米纤维隔膜的尺寸稳定，在200℃高温下加热30min以内，热收缩率小于2％。When the composite nanofiber membrane has a closed pore state, the composite nanofiber membrane has a stable size, and is heated within a temperature of 200 ° C for 30 minutes, and the heat shrinkage rate is less than 2%.
所述具有闭孔功能的复合纳米纤维隔膜的厚度为10～80μm，The composite nanofiber membrane having a closed cell function has a thickness of 10 to 80 μm.
一种上述的具有闭孔功能的复合纳米纤维隔膜制备方法，用质量比为1∶9～9∶1原纤化纤维素纳米纤维与低熔点聚合物纳米纤维为原料，以造纸工艺制备。The invention discloses a method for preparing a composite nanofiber membrane having a closed cell function, which is prepared by using a fibrillated cellulose nanofiber and a low melting point polymer nanofiber with a mass ratio of 1:9 to 9:1 as a raw material.
所述的具有闭孔功能的复合纳米纤维隔膜的制备方法，包括以下具体步骤：The preparation method of the composite nanofiber membrane having the closed cell function comprises the following specific steps:
I、将质量比为1∶9～9∶1称取原纤化纤维素纳米纤维和至少一种低熔点聚合物纳米纤维分别分散在溶剂中，快速搅拌形成浆料；I. The fibrillated cellulose nanofibers and the at least one low-melting polymer nanofibers are respectively dispersed in a solvent at a mass ratio of 1:9 to 9:1, and rapidly stirred to form a slurry;
II、向步骤I的浆料中加入粘结剂；添加粘结剂可以增加其力学强度，粘结剂的可选择范围比较宽泛，如聚乙二醇、聚乙烯醇、丁二烯与苯乙烯的聚合物、丙烯晴的聚合物、聚偏氟乙烯及环氧树脂等。II. Adding a binder to the slurry of step I; adding a binder can increase the mechanical strength thereof, and the binder can be selected in a wide range, such as polyethylene glycol, polyvinyl alcohol, butadiene and styrene. Polymer, acrylonitrile polymer, polyvinylidene fluoride and epoxy resin.
III、将步骤II后的浆料稀释至浓度为0.01％～0.05％；III, the slurry after step II is diluted to a concentration of 0.01% to 0.05%;
IV、稀释后的浆料经上网脱水成型、压榨、干燥、热轧成型，即得到所述具有闭孔功能的复合纳米纤维隔膜。IV. The diluted slurry is subjected to dehydration molding, pressing, drying and hot rolling forming on the Internet to obtain the composite nanofiber separator having a closed cell function.
优选的，所述的原纤化纤维素纳米纤维的直径为10-1000nm，长度为10-3000μm。 Preferably, the fibrillated cellulose nanofibers have a diameter of 10 to 1000 nm and a length of 10 to 3000 μm.
所述的原纤化纤维素纳米纤维包括从纳米尺寸木质材料分离的纤维素纳米纤维，海藻纤维素纳米纤维，以及通过培养菌株获得的细菌纤维素纳米纤维。The fibrillated cellulose nanofibers include cellulose nanofibers separated from nanosized wood materials, seaweed cellulose nanofibers, and bacterial cellulose nanofibers obtained by culturing strains.
优选的，所述低熔点聚合物纳米纤维的直径为10-1000nm。Preferably, the low melting point polymer nanofibers have a diameter of 10 to 1000 nm.
所述的低熔点聚合物纳米纤维的为聚甲基丙烯酸甲酯，偏氟乙烯基聚合物，聚氨酯，聚氯乙烯，聚烯烃，聚乙烯-醋酸乙烯酯共聚物、聚丁二酸乙二醇酯的一种或者多种组合。The low melting point polymer nanofibers are polymethyl methacrylate, vinylidene fluoride polymer, polyurethane, polyvinyl chloride, polyolefin, polyethylene-vinyl acetate copolymer, polybutylene succinate One or more combinations of esters.
所述的溶剂为低分子量的醇类，去离子水，或低分子量的醇与去离子水的混合液。The solvent is a low molecular weight alcohol, deionized water, or a mixture of a low molecular weight alcohol and deionized water.
本发明的另一方面在于提供一种应用所述具有闭孔功能的复合纳米纤维隔膜制备的储能器件，包括锂离子电池，锂硫电池，碱性电池，超级电容器，铅酸电池，锌空气电池，钠离子电池。Another aspect of the present invention is to provide an energy storage device prepared by using the composite nanofiber membrane having the closed cell function, including a lithium ion battery, a lithium sulfur battery, an alkaline battery, a super capacitor, a lead acid battery, and zinc air. Battery, sodium ion battery.
本发明的制备方法成本低、生产工序简单、方便转移并且适宜大规模生产。The preparation method of the invention has low cost, simple production process, convenient transfer and is suitable for large-scale production.
本发明制备的闭孔功能复合纳米纤维隔膜展示出优良的物理性质，包括：闭孔性，耐热性，尺寸稳定性，透气性，以及相对于电解液的良好的浸润性和高的吸液率等特点。闭孔温度为130～170℃，闭孔后纤维膜不收缩，在200℃高温下加热30min热收缩率小于2％。The closed-cell functional composite nanofiber membrane prepared by the invention exhibits excellent physical properties including: closed cell, heat resistance, dimensional stability, gas permeability, good wettability with respect to electrolyte and high liquid absorption Rate and other characteristics. The closed cell temperature is 130-170 ° C. After the closed cell, the fiber membrane does not shrink, and the heat shrinkage rate is less than 2% when heated at 200 ° C for 30 min.
附图说明DRAWINGS
图1为对比例的聚烯烃基隔膜的SEM照片；Figure 1 is a SEM photograph of a polyolefin-based separator of a comparative example;
图2为实施例5的闭孔功能复合纳米纤维隔膜的SEM照片；2 is a SEM photograph of the closed-cell functional composite nanofiber membrane of Example 5;
图3为实施例5的闭孔功能复合纳米纤维隔膜在200℃，2h热处理后的SEM照片；3 is a SEM photograph of the closed-cell functional composite nanofiber membrane of Example 5 after heat treatment at 200 ° C for 2 hours;
图4为对比例和实施例3的闭孔功能复合纳米纤维隔膜在150℃及200℃下的热收缩性照片；4 is a photograph of the heat shrinkability of the comparative example and the closed-cell functional composite nanofiber membrane of Example 3 at 150 ° C and 200 ° C;
图5为对比例和实施例3的闭孔功能复合纳米纤维隔膜电解质浸润性照 片。5 is a comparative example and the closed-cell functional composite nanofiber membrane electrolyte infiltration of the comparative example 3 sheet.
具体实施方式detailed description
在此，根据说明书附图，结合实施例对本发明作进一步详细描述，但本发明并非受限于以下讨论的实施例，可以不同的形式来实施。以下的实施例用于本领域的技术人员来体现并实施本发明。The present invention is further described in detail with reference to the accompanying drawings, but the invention is not limited to the embodiments discussed below, and may be implemented in various forms. The following examples are intended to illustrate and practice the invention by those skilled in the art.
根据本发明实施例的使用原纤化纤维素纳米纤维和低熔点聚合物纳米纤维的闭孔功能复合纳米纤维隔膜的制备。Preparation of a closed cell functional composite nanofiber membrane using fibrillated cellulose nanofibers and low melting polymer nanofibers in accordance with an embodiment of the present invention.
使用包括原纤维化原纤化纤维素纳米纤维和低熔点聚合物纳米纤维浆液来制备隔膜。在此，原纤化纤维素纳米纤维可具有10-1000nm的直径。The separator is prepared using a fibrillated fibrillated cellulose nanofiber and a low melting polymer nanofiber slurry. Here, the fibrillated cellulose nanofibers may have a diameter of 10 to 1000 nm.
当原纤化纤维素纳米纤维的直径小于10nm时，非常困难形成原纤化纤维素纳米纤维，但是，当原纤化纤维素纳米纤维的直径超过1000nm时，隔膜具有粗糙的表面，这使得电极和隔膜没有良好接触。When the diameter of the fibrillated cellulose nanofibers is less than 10 nm, it is very difficult to form fibrillated cellulose nanofibers, but when the diameter of the fibrillated cellulose nanofibers exceeds 1000 nm, the separator has a rough surface, which makes the electrodes Not in good contact with the diaphragm.
同样，当原纤化纤维素纳米纤维的直径超过200nm时，不会均匀地形成孔。因此，原纤化纤维素纳米纤维的值直径更优选地为10-200nm之间。Also, when the diameter of the fibrillated cellulose nanofibers exceeds 200 nm, pores are not uniformly formed. Therefore, the value diameter of the fibrillated cellulose nanofibers is more preferably between 10 and 200 nm.
使用包括原纤维化原纤化纤维素纳米纤维和低熔点聚合物纳米纤维浆液来制备隔膜。在此，低熔点聚合物纳米纤维可具有10-1000nm的直径。The separator is prepared using a fibrillated fibrillated cellulose nanofiber and a low melting polymer nanofiber slurry. Here, the low melting point polymer nanofibers may have a diameter of 10 to 1000 nm.
该原纤化纤维素纳米纤维可选自包括：从纳米尺寸木质材料分离的原纤化纤维素纳米纤维，海藻原纤化纤维素纳米纤维，以及通过培养菌株获得的细菌原纤化纤维素纳米纤维中的至少其中一种。The fibrillated cellulose nanofibers may be selected from the group consisting of fibrillated cellulose nanofibers separated from nanosized wood materials, algae fibrillated cellulose nanofibers, and bacterial fibrillated cellulose nanometers obtained by culturing strains. At least one of the fibers.
该低熔点聚合物纳米纤维的种类可不受限制地全部使用，只要是熔点低的纳米纤维，并包括这样一种浆料，在该浆料中的低熔点聚合物纳米纤维可均匀地与原纤化纤维素纳米纤维混合，并在浆液制备过程中不可以溶解。The type of the low-melting polymer nanofiber can be used all without limitation, as long as it is a nanofiber having a low melting point, and includes a slurry in which the low-melting polymer nanofiber in the slurry can be uniformly mixed with the fibril The cellulose nanofibers are mixed and are not soluble during the preparation of the slurry.
该低熔点聚合物纳米纤维选自包括：低熔点聚合物纳米纤维的为聚甲基丙烯酸甲酯，偏氟乙烯基聚合物，聚氨酯，聚氯乙烯，聚烯烃，聚乙烯-醋酸乙烯酯共聚物、聚丁二酸乙二醇酯的一种或者多种组合。 The low melting point polymer nanofiber is selected from the group consisting of: low melting point polymer nanofibers, polymethyl methacrylate, vinylidene fluoride polymer, polyurethane, polyvinyl chloride, polyolefin, polyethylene-vinyl acetate copolymer One or more combinations of polyethylene succinate.
可使用其中原纤化纤维素纳米纤维和低熔点聚合物纳米纤维稳定分散的溶剂作为溶剂。例如，可选择去离子水、低分子量的醇以及低分子量的醇与去离子水混合液作为溶剂。A solvent in which fibrillated cellulose nanofibers and low melting point polymer nanofibers are stably dispersed can be used as a solvent. For example, deionized water, a low molecular weight alcohol, and a mixture of a low molecular weight alcohol and deionized water can be selected as the solvent.
相对于制备方法当中原纤化纤维素纳米纤维，当原纤化纤维素纳米纤维与低熔点聚合物纳米纤维的混合比例小于1∶9时，隔膜受热达不到闭孔的作用。另一方面，当原纤化纤维素纳米纤维与低熔点聚合物纳米纤维的混合比例超过9∶1时，隔膜的耐热性和尺寸稳定性受到严重影响，且较难转移。Compared with the fibrillated cellulose nanofibers in the preparation method, when the mixing ratio of the fibrillated cellulose nanofibers and the low melting point polymer nanofibers is less than 1:9, the separator does not reach the closed pores due to heat. On the other hand, when the mixing ratio of the fibrillated cellulose nanofibers to the low melting point polymer nanofibers exceeds 9:1, the heat resistance and dimensional stability of the separator are seriously affected and it is difficult to transfer.
其中含有原纤化纤维素纳米纤维和低熔点聚合物纳米纤维的溶液通过高速搅拌来制备浆料，该浆料经过造纸法来制成本发明的隔膜。A solution containing fibrillated cellulose nanofibers and low-melting polymer nanofibers was prepared by high-speed stirring, and the slurry was subjected to a papermaking method to prepare a separator of the present invention.
在这种情况下，根据本发明的一个实施例，使用一种制备隔膜的方法，例如：制备纸张的传统方法来将原纤化纤维素纳米纤维制备成无纺布织物。然而，所有制备隔膜的方法可用于制备锂离子电池的隔膜。In this case, according to an embodiment of the present invention, a method of preparing a separator, for example, a conventional method of preparing paper, is used to prepare a fibrillated cellulose nanofiber into a nonwoven fabric. However, all methods of preparing the separator can be used to prepare a separator for a lithium ion battery.
隔膜的厚度可在接近10-80μm的范围内。当隔膜的厚度超过80μm时，电池的充放电效率将受到严重的影响。当隔膜的厚度低于10μm时，电池的自放电和短路率会大大提高。The thickness of the separator can be in the range of approximately 10-80 μm. When the thickness of the separator exceeds 80 μm, the charge and discharge efficiency of the battery will be seriously affected. When the thickness of the separator is less than 10 μm, the self-discharge and short-circuit rate of the battery are greatly improved.
原纤化纤维素纳米纤维的优点是，当隔膜的制备过程中使用粘结剂时，会减少官能团中出现的-OH基，这是由于氢键增加的原因，当原纤化纤维素纳米纤维用于锂二次电池隔膜时，在原纤化纤维素纳米纤维中Li离子和-OH基之间的反应因此不再发生，这导致稳定性的增加。The advantage of fibrillated cellulose nanofibers is that when a binder is used in the preparation of the separator, the -OH group present in the functional group is reduced, which is due to an increase in hydrogen bonding, when fibrillated cellulose nanofibers When used for a lithium secondary battery separator, the reaction between Li ions and -OH groups in the fibrillated cellulose nanofibers does not occur anymore, which leads to an increase in stability.
因为粘结剂末端具有-OH基。因此，粘结剂可均匀地与原纤化纤维素纳米纤维混合。Because the end of the binder has an -OH group. Therefore, the binder can be uniformly mixed with the fibrillated cellulose nanofibers.
本领域技术人员可以理解，应用上述具有闭孔功能的复合纳米纤维隔膜制备的储能器件，包括锂离子电池，锂硫电池，碱性电池，超级电容器，铅酸电池，锌空气电池，钠离子电池，必定有效提高储能器件的安全性和可靠性。 Those skilled in the art can understand that the energy storage device prepared by using the above composite nanofiber membrane with closed cell function includes lithium ion battery, lithium sulfur battery, alkaline battery, super capacitor, lead acid battery, zinc air battery, sodium ion. The battery must effectively improve the safety and reliability of the energy storage device.
实施例1Example 1
将原纤化纤维素纳米纤维∶低熔点聚合物纳米纤维＝9∶1的从纳米尺寸木质材料分离的纤维素纳米纤维和低熔点聚合物纳米纤维(聚甲基丙烯酸甲酯与聚丁二酸乙二醇酯)分散在溶剂中，并随后通过高速机械搅拌使溶液达到整体的均匀来制备浆料。加入溶剂将浆料稀释至0.01％，将稀释好的浆料经上网脱水成型；压榨、干燥；在成型温度为100℃，线压力为100kg/cm条件下进行热轧成型，再经卷纸、复卷、分切和包装，制得电池隔膜。Cellulose nanofibers and low melting point polymer nanofibers (polymethyl methacrylate and polysuccinic acid) separated from nanosized wood materials by fibrillated cellulose nanofibers: low melting polymer nanofibers = 9:1 The glycol ester) is dispersed in a solvent, and then the slurry is uniformly homogenized by high-speed mechanical stirring to prepare a slurry. The solvent is diluted to 0.01% by adding a solvent, and the diluted slurry is dehydrated by the net; pressed and dried; hot-rolled at a molding temperature of 100 ° C and a line pressure of 100 kg/cm, and then rolled, Rewinding, slitting and packaging to produce a battery separator.
上述闭孔复合隔膜展示出优良的特性，例如，200℃，2h热处理前后孔隙率分别为56％和55％；在200℃，30min几乎为0的热收缩率；313％的吸收率；200℃，2h热处理前后的Gutley值(s/100cc)为23和23。The above closed-cell composite separator exhibits excellent characteristics, for example, a porosity of 56% and 55% before and after heat treatment at 200 ° C for 2 hours, a heat shrinkage rate of almost 0 at 30 ° C for 30 minutes, and an absorbance of 31% at 200 ° C; The Gutley value (s/100 cc) before and after the 2 h heat treatment was 23 and 23.
实施例2Example 2
将原纤化纤维素纳米纤维∶低熔点聚合物纳米纤维＝7∶3的海藻纤维素纳米纤维和低熔点聚合物纳米纤维(偏氟乙烯基聚合物)分散在溶剂中，并随后通过高速机械搅拌使溶液达到整体的均匀来制备浆料。加入溶剂将浆料稀释至0.01％，将稀释好的浆料经上网脱水成型；压榨、干燥；在成型温度为100℃，线压力为100kg/cm条件下进行热轧成型，再经卷纸、复卷、分切和包装，制得电池隔膜。Dispersing fibrillated cellulose nanofibers: low melting point polymer nanofibers = 7:3 algae cellulose nanofibers and low melting polymer nanofibers (vinylidene fluoride polymer) in a solvent, and then passing high speed machinery The slurry was prepared by stirring to bring the solution to an overall uniformity. The solvent is diluted to 0.01% by adding a solvent, and the diluted slurry is dehydrated by the net; pressed and dried; hot-rolled at a molding temperature of 100 ° C and a line pressure of 100 kg/cm, and then rolled, Rewinding, slitting and packaging to produce a battery separator.
上述闭孔复合隔膜展示出优良的特性，例如，200℃，2h热处理前后孔隙率分别为56％和30％；在200℃，30min时几乎为1％的热收缩率；300％的吸液百分比；200℃，2h热处理前后的Gutley值(s/100cc)为23和800。The above closed-cell composite separator exhibits excellent characteristics, for example, a porosity of 56% and 30% before and after heat treatment at 200 ° C for 2 hours, and a heat shrinkage rate of almost 1% at 200 ° C for 30 minutes; The Gutley value (s/100 cc) before and after heat treatment at 200 ° C for 2 h was 23 and 800.
实施例3Example 3
将原纤化纤维素纳米纤维∶低熔点聚合物纳米纤维＝5∶5的通过培养菌株获得的细菌纤维素纳米纤维和低熔点聚合物纳米纤维(聚氨酯，聚氯乙烯和聚烯烃)分散在溶剂中，并随后通过高速机械搅拌使溶液达到整体的均匀来 制备浆料。加入溶剂将浆料稀释至0.01％，将稀释好的浆料经上网脱水成型；压榨、干燥；在成型温度为100℃，线压力为100kg/cm条件下进行热轧成型，再经卷纸、复卷、分切和包装，制得电池隔膜。Dispersing bacterial cellulose nanofibers and low melting polymer nanofibers (polyurethane, polyvinyl chloride and polyolefin) obtained by culturing strains of fibrillated cellulose nanofibers: low melting polymer nanofibers = 5:5 in a solvent Medium and then through a high-speed mechanical agitation to achieve a uniform solution A slurry was prepared. The solvent is diluted to 0.01% by adding a solvent, and the diluted slurry is dehydrated by the net; pressed and dried; hot-rolled at a molding temperature of 100 ° C and a line pressure of 100 kg/cm, and then rolled, Rewinding, slitting and packaging to produce a battery separator.
上述闭孔复合隔膜展示出优良的特性，例如，200℃，2h热处理前后孔隙率分别为54％和18％；在200℃，30min时1.4％的热收缩率；285％的吸液百分比；200℃，2h热处理前后Gurley值(s/100cc)为23和2020。The above closed-cell composite membrane exhibits excellent characteristics, for example, a porosity of 54% and 18% before and after heat treatment at 200 ° C for 2 hours, a heat shrinkage of 1.4% at 200 ° C, 30 minutes, and a percentage of absorbance of 285%; The Gurley value (s/100 cc) before and after the heat treatment at °C for 2 h was 23 and 2020.
实施例4Example 4
将原纤化纤维素纳米纤维∶低熔点聚合物纳米纤维＝3∶7的海藻纤维素纳米纤维和低熔点聚合物纳米纤维(聚乙烯-醋酸乙烯酯共聚物)分散在溶剂中，并随后通过高速机械搅拌使溶液达到整体的均匀来制备浆液。加入溶剂将浆料稀释至0.01％，将稀释好的浆料经上网脱水成型；压榨、干燥；在成型温度为100℃，线压力为100kg/cm条件下进行热轧成型，再经卷纸、复卷、分切和包装，制得电池隔膜。Dispersing fibrillated cellulose nanofibers: low melting point polymer nanofibers = 3:7 algae cellulose nanofibers and low melting polymer nanofibers (polyethylene-vinyl acetate copolymer) in a solvent, and then passing The slurry is prepared by high-speed mechanical agitation to achieve uniformity of the solution. The solvent is diluted to 0.01% by adding a solvent, and the diluted slurry is dehydrated by the net; pressed and dried; hot-rolled at a molding temperature of 100 ° C and a line pressure of 100 kg/cm, and then rolled, Rewinding, slitting and packaging to produce a battery separator.
上述闭孔复合隔膜展示出优良的闭孔特性，例如，200℃，2h热处理前后孔隙率分别为58％和5％；在200℃，30min时5％的热收缩率；260％的吸液百分比；200℃，2h热处理前后Gurley值(s/100cc)为25和3867。The above closed-cell composite membrane exhibits excellent closed cell characteristics, for example, 200 ° C, and a porosity of 58% and 5% before and after heat treatment for 2 hours, and a heat shrinkage rate of 5% at 200 ° C, 30 minutes; The Gurley value (s/100 cc) before and after heat treatment at 200 ° C for 2 h was 25 and 3867.
实施例5Example 5
将原纤化纤维素纳米纤维∶低熔点聚合物纳米纤维＝1∶9的从纳米尺寸木质材料分离的纤维素纳米纤维和低熔点聚合物纳米纤维(聚氨酯)分散在溶剂中，并随后通过高速机械搅拌使溶液达到整体的均匀来制备浆液。加入溶剂将浆料稀释至0.01％，将稀释好的浆料经上网脱水成型；压榨、干燥；在成型温度为100℃，线压力为100kg/cm条件下进行热轧成型，再经卷纸、复卷、分切和包装，制得电池隔膜。Cellulose nanofibers and low melting point polymer nanofibers (polyurethane) separated from nanosized wood materials of fibrillated cellulose nanofibers: low melting point polymer nanofibers 1:9 are dispersed in a solvent, and then passed through a high speed The slurry is prepared by mechanical agitation to achieve uniformity of the solution. The solvent is diluted to 0.01% by adding a solvent, and the diluted slurry is dehydrated by the net; pressed and dried; hot-rolled at a molding temperature of 100 ° C and a line pressure of 100 kg/cm, and then rolled, Rewinding, slitting and packaging to produce a battery separator.
上述闭孔复合隔膜展示出优良的特性，例如，200℃，2h热处理前后孔 隙率分别为57％和1％；在200℃，30min时18％的热收缩率；235％的吸液百分比；200℃，2h热处理前后Gurley值(s/100cc)为23和基本不通气。The above closed-cell composite membrane exhibits excellent characteristics, for example, 200 ° C, 2 h heat treatment before and after the hole The gap ratios were 57% and 1%, respectively; at 20 °C, 18% heat shrinkage at 30 min; 235% absorbance percentage; 200 °C, Gurley value (s/100 cc) before and after 2 h heat treatment was 23 and substantially no aeration.
根据本发明，制备具有闭孔功能的复合纳米纤维隔膜的方法具有的优点是由于其简单的制备过程和制备成本所带来的有竞争性的价格，适合于大批量的生产。According to the present invention, the method of preparing a composite nanofiber membrane having a closed cell function has an advantage in that it is suitable for mass production due to its competitive price due to its simple preparation process and preparation cost.
同样，可制备具有优良物理特点，例如，闭孔性，透气性，热稳定性，尺寸稳定性，厚度可调和浸渍特性的隔膜。Also, a separator having excellent physical characteristics such as closed cell properties, gas permeability, thermal stability, dimensional stability, thickness adjustable, and impregnation properties can be prepared.
当通过特定的实施例来说明并展示本发明时，对于本领域的技术人员应该明白，在不偏离权利要求所限定的本发明的领域的情况下，可进行不同的形式的改变。While the invention has been illustrated and described with respect to the specific embodiments the embodiments of the invention
对比例：Comparative example:
商业化PE隔膜，未经任何处理，直接测试。Commercial PE diaphragms are tested directly without any treatment.
对比例隔膜的参数如表1所示。The parameters of the comparative membrane are shown in Table 1.
以下对实施例制备得到的闭孔纳米纤维复合隔膜机构性性能测试。测试方法如下：The mechanical properties of the closed-cell nanofiber composite separator prepared in the examples were tested below. The test method is as follows:
1.结构表征Structural characterization
采用扫描电子显微镜对对比例1，实施例4的隔膜在200℃，2h前后表面进行结构表征，SEM图片如图1、2、3所示。The surface of Comparative Example 1 and Comparative Example 1 were examined by scanning electron microscopy at 200 ° C for 2 h. The SEM images are shown in Figures 1, 2 and 3.
2.孔隙率测试2. Porosity test
将已称重的隔膜(Wd)在正丁醇中浸泡2h后取出，用滤纸将其表面的液体轻轻吸干，在进行称重(Ww)，即可得到隔膜所吸收正丁醇的质量Wb＝Ww-Wd。隔膜的孔体积可有正丁醇的质量(Wb)与正丁醇的密度(ρb)相除得到，此体积与干隔膜体积(Vp)之比及隔膜的孔隙率。计算公式为：The weighed separator (Wd) was immersed in n-butanol for 2 hours, and then the liquid on the surface was gently blotted with a filter paper. After weighing (Ww), the mass of n-butanol absorbed by the separator was obtained. Wb=Ww-Wd. The pore volume of the membrane can be obtained by dividing the mass of n-butanol (Wb) by the density of n-butanol (ρb), the ratio of this volume to the volume of the dry membrane (Vp) and the porosity of the membrane. The calculation formula is:
Figure PCTCN2015097248-appb-000001
Figure PCTCN2015097248-appb-000001
式中Wd为隔膜的质量，Ww为浸泡后的隔膜质量，Wb为隔膜吸收的正丁 醇质量，Vp是干隔膜的体积，ρb为正丁醇的密度。Where Wd is the mass of the membrane, Ww is the mass of the membrane after soaking, and Wb is the absorption of the membrane The mass of the alcohol, Vp is the volume of the dry membrane, and ρb is the density of n-butanol.
3.透气率(用Gurley值表述)3. Air permeability (expressed by Gurley value)
在室温，1.22KPa的静压下，Gurley密度计测量100mL空气通过有效测试面积为1.0Sqinch(0.01，0.25Sqinch自选)的样品所需要的时间(sec)作为膜的透气性值(至少5个平行试验)。At room temperature, under a static pressure of 1.22 KPa, the Gurley densitometer measures the time (sec) required for 100 mL of air through a sample with an effective test area of 1.0 Sqinch (0.01, 0.25 Sqinch optional) as the gas permeability value of the film (at least 5 parallels) test).
4.热收缩性4. Heat shrinkage
将实施例中获得的闭孔复合隔膜在200℃热处理0.5h，观察统计隔膜的尺寸变化(至少5个平行试验)。The closed-cell composite separator obtained in the examples was heat-treated at 200 ° C for 0.5 h, and the dimensional change of the statistical separator was observed (at least 5 parallel tests).
5.隔膜的亲液性测试5. Diaphragm lyophilic testing
将实施例中获得复合隔膜置于电解质溶液(乙烯基碳酸酯(EC)和二甲基碳酸酯(DMC)(v/v＝1∶1)的1.0M LiPF6电解质)中1h，取出后，迅速用滤纸洗出多余的电解质溶液，测试复合隔膜吸附前后的质量变化，计算吸液百分比，其计算公式如下：The composite separator obtained in the examples was placed in an electrolyte solution (1.0 M LiPF6 electrolyte of vinyl carbonate (EC) and dimethyl carbonate (DMC) (v/v = 1:1)) for 1 h, and quickly taken out. Excess electrolyte solution was washed out with filter paper, the mass change before and after adsorption of the composite membrane was tested, and the percentage of liquid absorption was calculated. The calculation formula is as follows:
Figure PCTCN2015097248-appb-000002
Figure PCTCN2015097248-appb-000002
结构分析：Structural analysis:
对比例1，实施例5的隔膜在200℃，2h前后表面的SEM照片图进行比对，图1为对比例的PE隔膜的SEM照片，其孔结构是由拉伸而形成的分布均匀的孔。图2是闭孔复合隔膜在在未加热前的SEM照片，可以看出，纳米纤维之间交联呈现三维孔结构。图3是闭孔隔膜在200℃加热2h之后的SEM照片，基本看不见孔结构存在，纤维之间相互交联形成的孔出现闭合。Comparative Example 1, the separator of Example 5 was compared at 200 ° C for 2 h before and after the SEM photograph of the surface, and Figure 1 is a SEM photograph of the PE separator of the comparative example, the pore structure of which is a uniformly distributed pore formed by stretching. . Figure 2 is a SEM photograph of the closed-cell composite membrane before it is heated. It can be seen that the cross-linking between the nanofibers exhibits a three-dimensional pore structure. Fig. 3 is a SEM photograph of the closed-cell membrane after heating at 200 ° C for 2 h, substantially no visible pore structure exists, and the pores formed by cross-linking between the fibers are closed.
表1实施例中所制备的闭孔纳米纤维复合隔膜和对比例的性能The properties of the closed cell nanofiber composite separator prepared in the examples of Table 1 and the comparative examples
Figure PCTCN2015097248-appb-000003
Figure PCTCN2015097248-appb-000003
图4为对比例的烯烃基隔膜以及实施例3的多孔隔膜的照片，该照片是在隔膜暴露在高温之前，以及暴露在150℃，及200℃下30min之后所拍摄的。4 is a photograph of a comparative example olefin-based separator and the porous separator of Example 3 taken before the separator was exposed to high temperature, and after exposure to 150 ° C and 30 ° C at 30 ° C.
由于对比例的烯烃基隔膜具有较低的熔点，当该烯烃基隔膜暴露在200℃的温度下时，该烯烃基隔膜的框架完全丧失。因此，当对比例1的烯烃基隔膜用作锂离子电池的隔膜时，其安全性得不到保证。Since the olefin-based separator of the comparative example had a lower melting point, when the olefin-based separator was exposed to a temperature of 200 ° C, the frame of the olefin-based separator was completely lost. Therefore, when the olefin-based separator of Comparative Example 1 was used as a separator of a lithium ion battery, its safety was not secured.
同时，由于实施例3的多孔隔膜的热稳定性持续到250℃，可见，该闭孔纳米复合隔膜在尺寸稳定性和热收缩方面适合用作锂二次电池的隔膜。Meanwhile, since the thermal stability of the porous separator of Example 3 was continued to 250 ° C, it was found that the closed-cell nanocomposite separator is suitable as a separator for a lithium secondary battery in terms of dimensional stability and heat shrinkage.
本发明的多孔隔膜的亲液性的测量。Measurement of lyophilicity of the porous membrane of the present invention.
为了确定根据本发明的多孔隔膜的电解液的浸润特点，制备对比例和实施例3的隔膜，用微量调节注射器将电解质滴入对比例和实施例3的隔膜中，结果在2s和15min之后获得，如图5所示。In order to determine the wetting characteristics of the electrolyte of the porous separator according to the present invention, the comparative example and the separator of Example 3 were prepared, and the electrolyte was dropped into the comparative example and the separator of Example 3 with a micro-adjusting syringe, and the results were obtained after 2 s and 15 minutes. As shown in Figure 5.
碳酸丙烯酯一点也没有浸渍到对比例中的隔膜上。然而，该电解质的滴入隔膜之后立即浸渍到实施例3的隔膜上。Propylene carbonate was not impregnated at all to the separator in the comparative example. However, the electrolyte was impregnated onto the separator of Example 3 immediately after it was dropped into the separator.
假设锂二次电池的闭孔功能复合纳米纤维隔膜的电池浸润性质对电池产率和效率具有很多影响，可见实施例3中的闭孔纳米复合适合用于锂二次电池的隔膜。It is assumed that the cell infiltration property of the closed cell function composite nanofiber separator of the lithium secondary battery has a large influence on the cell yield and efficiency, and the closed cell nanocomposite in Example 3 can be seen to be suitable for the separator of a lithium secondary battery.
以上所述的实施例仅仅用于说明本发明，并非对本发明的范围进行限定，在不脱离本发明设计精神的前提下，本领域普通技术人员对本发明的技术方案作出的各种配比和参数的改变，修饰、替代、组合、简化，等效的置换均应落入本发明权利要求书确定的保护范围内。 The above-mentioned embodiments are merely illustrative of the present invention, and are not intended to limit the scope of the present invention, and various ratios and parameters made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention. Changes, modifications, substitutions, combinations, simplifications, and equivalent substitutions are intended to fall within the scope of the invention as defined by the appended claims.

Claims (10)

  1. 一种具有闭孔功能的复合纳米纤维隔膜，其特征在于，其原料包括原纤化纤维素纳米纤维和低熔点聚合物纳米纤维，所述原纤化纤维素纳米纤维之间主要通过氢键、分子间作用力结合，所述原纤化纤维素纳米纤维与所述低熔点聚合物纳米纤维之间通过长径分子间的交联作用结合；所述复合纳米纤维隔膜上具有孔隙以便电解液离子穿过、且阻止电子穿过；在130～170℃温度环境下，所述复合纳米纤维隔膜孔隙闭合，以防止电池受损后的过量和不期望的离子通过。A composite nanofiber membrane having a closed cell function, characterized in that the raw material comprises fibrillated cellulose nanofibers and low melting point polymer nanofibers, and the fibrillated cellulose nanofibers mainly pass hydrogen bonding, Intermolecular force bonding, the fibrillated cellulose nanofibers and the low melting point polymer nanofibers are combined by long-term molecular cross-linking; the composite nanofiber membrane has pores for electrolyte ions Passing through and preventing electrons from passing through; the composite nanofiber membrane pores are closed at a temperature of 130 to 170 ° C to prevent excessive and undesired ions from passing through the battery after damage.
  2. 根据权利要求1所述的具有闭孔功能的复合纳米纤维隔膜，其特征在于，所述复合纳米纤维隔膜孔隙闭合状态下，所述复合纳米纤维隔膜的尺寸稳定，在200℃高温下加热30min以内，热收缩率小于2％。The composite nanofiber membrane having a closed cell function according to claim 1, wherein the composite nanofiber membrane has a pore size closed state, and the composite nanofiber membrane has a stable size and is heated within a temperature of 200 ° C for 30 minutes. The heat shrinkage rate is less than 2%.
  3. 根据权利要求1所述的具有闭孔功能的复合纳米纤维隔膜，其特征在于，所述具有闭孔功能的复合纳米纤维隔膜的厚度为10～80μm。The composite nanofiber membrane having a closed cell function according to claim 1, wherein the composite nanofiber membrane having a closed cell function has a thickness of 10 to 80 μm.
  4. 一种根据权利要求1所述的具有闭孔功能的复合纳米纤维隔膜制备方法，其特征在于，用质量比为1∶9～9∶1原纤化纤维素纳米纤维与低熔点聚合物纳米纤维为原料，以造纸工艺制备。A method for preparing a composite nanofiber membrane having a closed cell function according to claim 1, wherein the fibrillated cellulose nanofiber and the low melting polymer nanofiber are used in a mass ratio of 1:9 to 9:1. As a raw material, it is prepared by a papermaking process.
  5. 根据权利要求4所述的具有闭孔功能的复合纳米纤维隔膜的制备方法，其特征在于，包括以下具体步骤：The method for preparing a composite nanofiber membrane having a closed cell function according to claim 4, comprising the following specific steps:
    I、将质量比为1∶9～9∶1称取原纤化纤维素纳米纤维和至少一种低熔点聚合物纳米纤维分别分散在溶剂中，快速搅拌形成浆料；I. The fibrillated cellulose nanofibers and the at least one low-melting polymer nanofibers are respectively dispersed in a solvent at a mass ratio of 1:9 to 9:1, and rapidly stirred to form a slurry;
    II、向步骤I的浆料中加入粘结剂；II. adding a binder to the slurry of step I;
    III、将步骤II后的浆料稀释至浓度为0.01％～0.05％；III, the slurry after step II is diluted to a concentration of 0.01% to 0.05%;
    IV、稀释后的浆料经上网脱水成型、压榨、干燥、热轧成型，即得到所述具有闭孔功能的复合纳米纤维隔膜。IV. The diluted slurry is subjected to dehydration molding, pressing, drying and hot rolling forming on the Internet to obtain the composite nanofiber separator having a closed cell function.
  6. 根据权利要求4所述具有闭孔功能的复合纳米纤维隔膜的制备方法，其特征在于，所述的原纤化纤维素纳米纤维的直径为10-1000nm，长度为 10-3000μm。The method for preparing a composite nanofiber membrane having a closed cell function according to claim 4, wherein the fibrillated cellulose nanofiber has a diameter of 10 to 1000 nm and a length of 10-3000 μm.
  7. 根据权利要求4、5或6所述具有闭孔功能的复合纳米纤维隔膜的制备方法，其特征在于，所述的原纤化纤维素纳米纤维包括从纳米尺寸木质材料分离的纤维素纳米纤维，海藻纤维素纳米纤维，以及通过培养菌株获得的细菌纤维素纳米纤维。The method for preparing a composite nanofiber membrane having a closed cell function according to claim 4, 5 or 6, wherein the fibrillated cellulose nanofiber comprises cellulose nanofibers separated from a nanometer size wood material, Algae cellulose nanofibers, and bacterial cellulose nanofibers obtained by culturing strains.
  8. 根据权利要求4所述具有闭孔功能的复合纳米纤维隔膜的制备方法，其特征在于，所述低熔点聚合物纳米纤维的直径为10-1000nm。The method for preparing a composite nanofiber membrane having a closed cell function according to claim 4, wherein the low melting point polymer nanofiber has a diameter of 10 to 1000 nm.
  9. 根据权利要求4、5或8所述具有闭孔功能的复合纳米纤维隔膜的制备方法，其特征在于，所述的低熔点聚合物纳米纤维的为聚甲基丙烯酸甲酯，偏氟乙烯基聚合物，聚氨酯，聚氯乙烯，聚烯烃，聚乙烯-醋酸乙烯酯共聚物、聚丁二酸乙二醇酯的一种或者多种组合。The method for preparing a composite nanofiber membrane having a closed cell function according to claim 4, 5 or 8, wherein the low melting point polymer nanofiber is polymethyl methacrylate and a vinylidene fluoride polymerization. One or more combinations of polyurethane, polyvinyl chloride, polyolefin, polyethylene-vinyl acetate copolymer, polyethylene succinate.
  10. 一种应用权利要求1至3之一所述具有闭孔功能的复合纳米纤维隔膜制备的储能器件，包括锂离子电池，锂硫电池，碱性电池，超级电容器，铅酸电池，锌空气电池，钠离子电池。 An energy storage device prepared by using the composite nanofiber membrane with closed cell function according to one of claims 1 to 3, including a lithium ion battery, a lithium sulfur battery, an alkaline battery, a super capacitor, a lead acid battery, and a zinc air battery. , sodium ion battery.
PCT/CN2015/097248 2014-12-19 2015-12-14 Composite nanofiber separator with thermal shutdown function, preparation method therefor and energy storage components WO2016095771A1 (en)

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