CN113285174B - Sea-island polyphenylene sulfide composite battery diaphragm and preparation method thereof - Google Patents
Sea-island polyphenylene sulfide composite battery diaphragm and preparation method thereof Download PDFInfo
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 202
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 202
- 239000002131 composite material Substances 0.000 title claims abstract description 172
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000000835 fiber Substances 0.000 claims abstract description 88
- 239000002121 nanofiber Substances 0.000 claims abstract description 75
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 36
- 238000007731 hot pressing Methods 0.000 claims description 26
- 238000010009 beating Methods 0.000 claims description 14
- 229920000728 polyester Polymers 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000009960 carding Methods 0.000 claims description 9
- 239000002612 dispersion medium Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000004642 Polyimide Substances 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 238000002074 melt spinning Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000011978 dissolution method Methods 0.000 claims description 3
- 238000001523 electrospinning Methods 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- VGRSPALDTNRXMC-UHFFFAOYSA-N [B].[N].[Si] Chemical compound [B].[N].[Si] VGRSPALDTNRXMC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 1
- 238000005213 imbibition Methods 0.000 claims 1
- 238000004537 pulping Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 description 19
- 238000002485 combustion reaction Methods 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 10
- 238000010586 diagram Methods 0.000 description 10
- 239000003063 flame retardant Substances 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 238000009987 spinning Methods 0.000 description 9
- 229920001410 Microfiber Polymers 0.000 description 6
- 238000013507 mapping Methods 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 230000006837 decompression Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- ODPYDILFQYARBK-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2SC2=C1 ODPYDILFQYARBK-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical group C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
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- A62C3/00—Fire prevention, containment or extinguishing specially adapted for particular objects or places
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
本发明属于电池隔膜制造技术领域,公开了一种海岛型聚苯硫醚复合电池隔膜及其制备方法,该方法为将聚苯硫醚和碱溶性聚酯混合后经过熔融纺丝即得海岛型聚苯硫醚复合纤维,再将海岛型聚苯硫醚复合纤维经过热处理后切短,再与纳米纤维混合,经过分散打浆、疏解、抄纸、热压即得海岛型聚苯硫醚复合电池隔膜。本发明制备过程简单方便,无需使用有机溶剂,适合大规模生产,提高了电池隔膜的电解液吸液性,制得的海岛型聚苯硫醚复合电池隔膜,具有良好的热稳定性、化学稳定性、机械性能及阻燃性等。本发明的制备方法适用于制备海岛型聚苯硫醚复合电池隔膜,制得的海岛型聚苯硫醚复合电池隔膜适用于锂电池。The invention belongs to the technical field of battery diaphragm manufacturing, and discloses a sea-island type polyphenylene sulfide composite battery diaphragm and a preparation method thereof. Polyphenylene sulfide composite fibers, and then heat-treated sea-island-type polyphenylene sulfide composite fibers are cut short, and then mixed with nanofibers. diaphragm. The preparation process of the invention is simple and convenient, does not need to use an organic solvent, is suitable for large-scale production, improves the electrolyte absorption of the battery diaphragm, and the prepared sea-island type polyphenylene sulfide composite battery diaphragm has good thermal stability and chemical stability. properties, mechanical properties and flame retardancy. The preparation method of the invention is suitable for preparing the separator of the sea-island type polyphenylene sulfide composite battery, and the prepared sea-island type polyphenylene sulfide composite battery separator is suitable for the lithium battery.
Description
技术领域technical field
本发明属于电池隔膜制造技术领域,涉及聚苯硫醚复合纤维,具体地说是一种海岛型聚苯硫醚复合电池隔膜及其制备方法。The invention belongs to the technical field of battery diaphragm manufacturing, and relates to polyphenylene sulfide composite fibers, in particular to a sea-island type polyphenylene sulfide composite battery diaphragm and a preparation method thereof.
背景技术Background technique
锂离子电池因其具有能量密度高、自放电小、循环寿命长、无记忆效应以及对环境污染小等一系列优点而成为目前高性能电池的代表,在智能手机、笔记本电脑、数码相机、MP3等小型家电领域已得到广泛的应用。在锂离子电池的组成中,隔膜占据非常重要的地位,直接影响到锂离子电池的使用性能及其安全性。目前聚烯烃隔膜由于化学性质稳定,成本低,孔径分布均匀等优点在隔膜市场占据主导地位。然而,聚烯烃隔膜也存在着电解液润湿性很差、热稳定不佳等缺点。为了满足大功率锂离子电池对隔膜高温尺寸稳定性和电解液吸收性能的要求,开发出高性能的隔膜成为研究人员关注的焦点。Lithium-ion batteries have become the representative of high-performance batteries because of their advantages such as high energy density, small self-discharge, long cycle life, no memory effect, and low environmental pollution. They are used in smartphones, notebook computers, digital cameras, MP3 And other small household appliances have been widely used. In the composition of lithium-ion batteries, the diaphragm occupies a very important position, which directly affects the performance and safety of lithium-ion batteries. At present, polyolefin separators occupy a dominant position in the separator market due to their stable chemical properties, low cost, and uniform pore size distribution. However, polyolefin separators also have disadvantages such as poor electrolyte wettability and poor thermal stability. In order to meet the high-temperature dimensional stability and electrolyte absorption performance requirements of high-power lithium-ion batteries, the development of high-performance separators has become the focus of researchers.
聚苯硫醚(PPS)是分子中含有对亚苯基硫醚重复结构单元的聚合物,是一种新型功能性工程塑料,具有良好的耐热性、优异的耐化学腐蚀性和阻燃性,可作为锂离子电池隔膜的一种有前途的替代品。Polyphenylene sulfide (PPS) is a polymer containing repeating structural units of p-phenylene sulfide in the molecule. It is a new type of functional engineering plastic with good heat resistance, excellent chemical resistance and flame retardancy. , which can serve as a promising substitute for lithium-ion battery separators.
中国专利号CN104795525A的发明专利公开了“一种熔喷聚苯硫醚无纺布锂电池隔膜及其制备方法”,该专利中的制备方法为通过熔喷法制备聚苯硫醚超细纤维,再对超细纤维网进行热轧和热定型处理得到熔喷聚苯硫醚无纺布锂电池隔膜。熔喷法制备的PPS无纺布基材通过缠结在一起的纤维构成了三维的纤维网络结构,这种结构为锂离子电池隔膜提供高的孔隙率,但是熔喷法制备的纤维强度低、隔膜孔径较大且分布不均匀。中国专利号CN112054146A的发明专利公开了“一种PPS材料用于生产电池隔膜的方法及制成的薄膜”,该专利中的制备方法为将PPS材料按照占比1%-70%的重量比加入到PP和PE中,再按照PE成膜工艺通过挤出、拉伸、延展等步骤生产出填充了PPS材料的具有丰富纳米级微孔的薄膜,但是该方法过程复杂、技术难度大、不适合大规模生产。The invention patent of China Patent No. CN104795525A discloses "a melt-blown polyphenylene sulfide non-woven lithium battery separator and its preparation method". Then, the superfine fiber web is subjected to hot rolling and heat setting treatment to obtain a melt-blown polyphenylene sulfide non-woven lithium battery separator. The PPS non-woven fabric substrate prepared by the melt-blown method forms a three-dimensional fiber network structure through entangled fibers. This structure provides high porosity for the lithium-ion battery separator, but the fibers prepared by the melt-blown method have low strength, The diaphragm pore size is large and unevenly distributed. The invention patent of Chinese Patent No. CN112054146A discloses "a method for producing battery separators made of PPS materials and the film made thereof". The preparation method in this patent is to add PPS materials in a weight ratio of 1%-70% into PP and PE, and then produce a film filled with PPS material with rich nano-scale pores according to the PE film-forming process through steps such as extrusion, stretching, and extension. However, this method is complicated in process, technically difficult, and not suitable for Mass production.
发明内容Contents of the invention
本发明的目的,是要提供一种海岛型聚苯硫醚复合电池隔膜及其制备方法,以克服现有技术中的缺点。The purpose of the present invention is to provide a sea-island type polyphenylene sulfide composite battery separator and its preparation method, so as to overcome the shortcomings in the prior art.
本发明为实现上述目的,所采用的技术方法如下:The present invention is for realizing the above object, and the technical method adopted is as follows:
一种海岛型聚苯硫醚复合电池隔膜的制备方法,包括以下步骤:A method for preparing a sea-island type polyphenylene sulfide composite battery diaphragm, comprising the following steps:
S1、海岛型聚苯硫醚复合纤维的制备:将聚苯硫醚和碱溶性聚酯混合后经过熔融纺丝即得海岛型聚苯硫醚复合纤维;S1. Preparation of sea-island polyphenylene sulfide composite fibers: mixing polyphenylene sulfide and alkali-soluble polyester and then melt-spinning to obtain sea-island polyphenylene sulfide composite fibers;
S2、海岛型聚苯硫醚复合电池隔膜的制备:将海岛型聚苯硫醚复合纤维经过热处理后切短,再与纳米纤维混合,经过分散打浆、疏解、抄纸、热压即得海岛型聚苯硫醚复合电池隔膜。S2. Preparation of sea-island type polyphenylene sulfide composite battery separator: the sea-island type polyphenylene sulfide composite fiber is cut short after heat treatment, and then mixed with nanofibers, dispersed and beaten, thawed, paper-making, and hot-pressed to obtain the sea-island type Polyphenylene sulfide composite battery separator.
作为限定:步骤S1中聚苯硫醚的熔融指数为50-500g/10min,碱溶性聚酯的熔融指数为10-50g/10min,聚苯硫醚和碱溶性聚酯混合前先进行干燥,干燥温度为80-160℃,干燥时间为12-24h。As a limitation: the melt index of polyphenylene sulfide in step S1 is 50-500g/10min, the melt index of alkali-soluble polyester is 10-50g/10min, and the polyphenylene sulfide and alkali-soluble polyester are dried before mixing. The temperature is 80-160°C, and the drying time is 12-24h.
作为进一步限定:聚苯硫醚和碱溶性聚酯的质量比为3:7-7:3。As a further limitation: the mass ratio of polyphenylene sulfide to alkali-soluble polyester is 3:7-7:3.
作为更进一步限定:步骤S1中制得的海岛型聚苯硫醚复合纤维的纤度为0.9-5μm,其纤维为圆形;步骤S2中切短后的海岛型聚苯硫醚复合纤维中长度5-8mm的海岛型聚苯硫醚复合纤维的质量分数为0-25%,长度1-2mm的海岛型聚苯硫醚复合纤维的质量分数为0-25%,长度2-5mm的海岛型聚苯硫醚复合纤维的质量分数为50-100%。As a further limitation: the fineness of the sea-island type polyphenylene sulfide composite fiber prepared in step S1 is 0.9-5 μm, and its fiber is round; the length of the sea-island type polyphenylene sulfide composite fiber cut short in step S2 is 5 The mass fraction of sea-island polyphenylene sulfide composite fibers of -8mm is 0-25%, the mass fraction of sea-island polyphenylene sulfide composite fibers of 1-2mm length is 0-25%, and the sea-island polyphenylene sulfide composite fibers of 2-5mm The mass fraction of the phenylene sulfide composite fiber is 50-100%.
作为另一种限定:步骤S2中热处理的温度为80-150℃,热处理时间为10-60min。As another limitation: the heat treatment temperature in step S2 is 80-150° C., and the heat treatment time is 10-60 min.
作为限定:步骤S2中的纳米纤维采用芳香族纳米纤维,芳香族纳米纤维是通过静电纺丝和高速梳理机切断而成的,其纤维为圆形,直径为100-1000nm,纤维长度为1-3mm,芳香族纳米纤维与切短后的聚苯硫醚复合纤维的混合物中切短后的聚苯硫醚复合纤维的质量分数为80-95%,其余为芳香族纳米纤维,分散介质为水,打浆浓度为3-5%wt,疏解过程中搅拌叶轮转速为3000-3500rad/min,疏解时间为10-15min,抄纸过程中上网浓度为0.03-0.8%,热压过程中热压压力为10-20MPa,热压温度为150-230℃。As a limitation: the nanofibers in step S2 are aromatic nanofibers, which are cut by electrospinning and high-speed carding machine, and the fibers are round, with a diameter of 100-1000nm and a fiber length of 1- 3mm, the mass fraction of chopped polyphenylene sulfide composite fibers in the mixture of aromatic nanofibers and chopped polyphenylene sulfide composite fibers is 80-95%, the rest is aromatic nanofibers, and the dispersion medium is water , the beating concentration is 3-5%wt, the stirring impeller speed is 3000-3500rad/min during the flaking process, the flaking time is 10-15min, the online concentration is 0.03-0.8% in the papermaking process, and the hot pressing pressure in the hot pressing process is 10-20MPa, hot pressing temperature is 150-230℃.
作为另一种限定:步骤S2中的纳米纤维采用天然纳米纤维,天然纳米纤维是通过溶解法和高速梳理机切断而成的,其纤维为圆形,直径为100-1000nm,纤维长度为1-3mm,天然纳米纤维与切短后的聚苯硫醚复合纤维的混合物中切短后的聚苯硫醚复合纤维的质量分数为80-95%,其余为天然纳米纤维,分散介质为水,打浆浓度为3-5%wt,疏解过程中搅拌叶轮转速为3000-3500rad/min,疏解时间为10-15min,抄纸过程中上网浓度为0.03-0.8%,热压过程中热压压力为10-20MPa,热压温度为150-230℃。As another limitation: the nanofibers in step S2 are natural nanofibers, which are cut by a dissolution method and a high-speed carding machine, and the fibers are round, with a diameter of 100-1000nm and a fiber length of 1- 3mm, the mass fraction of chopped polyphenylene sulfide composite fibers in the mixture of natural nanofibers and chopped polyphenylene sulfide composite fibers is 80-95%, the rest is natural nanofibers, the dispersion medium is water, and beating The concentration is 3-5%wt, the rotation speed of the stirring impeller is 3000-3500rad/min during the decompression process, the decompression time is 10-15min, the online concentration is 0.03-0.8% during the papermaking process, and the hot pressing pressure during the hot pressing process is 10- 20MPa, hot pressing temperature is 150-230℃.
作为再一种限定:步骤S2中的纳米纤维采用无机纳米纤维,无机纳米纤维是通过火焰法和高速梳理机切断而成的,其纤维为圆形,直径为100-1000nm,纤维长度为1-3mm,无机纳米纤维与切短后的聚苯硫醚复合纤维的混合物中切短后的聚苯硫醚复合纤维的质量分数为80-95%,其余为无机纳米纤维,分散介质为水,打浆浓度为3-5%wt,疏解过程中搅拌叶轮转速为3000-3500rad/min,疏解时间为10-15min,抄纸过程中上网浓度为0.03-0.8%,热压过程中热压压力为10-20MPa,热压温度为150-230℃。As another limitation: the nanofibers in step S2 are inorganic nanofibers, which are cut by a flame method and a high-speed carding machine, and the fibers are round, with a diameter of 100-1000nm and a fiber length of 1- 3mm, the mass fraction of chopped polyphenylene sulfide composite fibers in the mixture of inorganic nanofibers and chopped polyphenylene sulfide composite fibers is 80-95%, the rest is inorganic nanofibers, the dispersion medium is water, and the beating The concentration is 3-5%wt, the rotation speed of the stirring impeller is 3000-3500rad/min during the decompression process, the decompression time is 10-15min, the online concentration is 0.03-0.8% during the papermaking process, and the hot pressing pressure during the hot pressing process is 10- 20MPa, hot pressing temperature is 150-230℃.
本发明还提供了上述的海岛型PPS复合电池隔膜的制备方法制得的海岛型聚苯硫醚复合电池隔膜,制得的海岛型聚苯硫醚复合电池隔膜孔隙率为40-70%,孔径为0.1-1μm,厚度为10-30μm,电解液吸液率250-350%,拉伸强度为15-50MPa,极限氧指数38-40。The present invention also provides the sea-island type polyphenylene sulfide composite battery diaphragm obtained by the above-mentioned preparation method of the sea-island type PPS composite battery diaphragm. The prepared sea-island type polyphenylene sulfide composite battery diaphragm has a porosity of 40-70%, and 0.1-1μm, thickness 10-30μm, electrolyte absorption rate 250-350%, tensile strength 15-50MPa, limiting oxygen index 38-40.
本发明由于采用了上述方案,与现有技术相比,所取得的有益效果是:The present invention has adopted above-mentioned scheme, compared with prior art, the beneficial effect that obtains is:
(1)本发明提供的海岛型聚苯硫醚复合电池隔膜的制备方法,聚苯硫醚(PPS)具有良好的耐热性、优异的耐化学腐蚀性和阻燃性,芳香族纳米纤维具有优良的热稳定性、机械性能、化学稳定性、耐腐蚀性等性能,天然纳米纤维它们具有优异的机械性能、良好的生物可降解性等性能,无机纳米纤维具有优异的热稳定性、阻燃性等性能,通过将海岛型聚苯硫醚复合纤维与纳米纤维混合、分散打浆、疏解、抄纸、热压,制得的海岛型聚苯硫醚复合电池隔膜具有优良的力学强度、均匀性、阻燃性、抗穿刺能力、热稳定性、化学稳定性等性能,而且制备过程简单方便,无需使用有机溶剂,适合大规模生产;(1) The preparation method of the sea-island type polyphenylene sulfide composite battery diaphragm provided by the present invention, polyphenylene sulfide (PPS) has good heat resistance, excellent chemical corrosion resistance and flame retardancy, and aromatic nanofibers have Excellent thermal stability, mechanical properties, chemical stability, corrosion resistance and other properties, natural nanofibers have excellent mechanical properties, good biodegradability and other properties, inorganic nanofibers have excellent thermal stability, flame retardant Sea-island type polyphenylene sulfide composite battery separator has excellent mechanical strength and uniformity by mixing sea-island polyphenylene sulfide composite fibers with nanofibers, dispersing and beating, dispersing, papermaking, and hot pressing. , flame retardancy, puncture resistance, thermal stability, chemical stability and other properties, and the preparation process is simple and convenient, without the use of organic solvents, suitable for large-scale production;
(2)本发明提供的海岛型聚苯硫醚复合电池隔膜及其制备方法,通过将不同长度、不同纤度的海岛型聚苯硫醚复合纤维初步调控电池隔膜的孔隙率、孔径及隔膜厚度,再混入少量纳米纤维,进一步实现电池隔膜孔径的均匀化、微细化,同时,提高了电池隔膜的电解液吸液性;(2) The island-in-the-sea type polyphenylene sulfide composite battery separator provided by the present invention and the preparation method thereof, by preliminarily regulating the porosity, pore diameter and thickness of the battery separator by using island-in-sea type polyphenylene sulfide composite fibers of different lengths and deniers, Then mix a small amount of nanofibers to further realize the homogenization and miniaturization of the pore size of the battery diaphragm, and at the same time, improve the electrolyte liquid absorption of the battery diaphragm;
(3)本发明提供的制备方法制备的海岛型聚苯硫醚复合电池隔膜,具有较高的电解液吸液性,且具有良好的热稳定性、化学稳定性、机械性能及阻燃性等,满足锂离子电池隔膜需求,提高了锂离子电池的安全性并延长了其使用寿命。(3) The sea-island type polyphenylene sulfide composite battery diaphragm prepared by the preparation method provided by the present invention has high electrolyte liquid absorption, and has good thermal stability, chemical stability, mechanical properties and flame retardancy, etc. , to meet the needs of lithium-ion battery separators, improve the safety of lithium-ion batteries and prolong their service life.
综上所述,本发明提供的海岛型聚苯硫醚复合电池隔膜的制备方法,制备过程简单方便,无需使用有机溶剂,适合大规模生产,对电池隔膜进行调控,提高了电池隔膜的电解液吸液性,制得的海岛型聚苯硫醚复合电池隔膜,具有良好的热稳定性、化学稳定性、机械性能及阻燃性等,提高了锂离子电池的安全性并延长了其使用寿命。In summary, the preparation method of the sea-island type polyphenylene sulfide composite battery diaphragm provided by the present invention is simple and convenient in the preparation process, does not need to use organic solvents, is suitable for large-scale production, regulates the battery diaphragm, and improves the electrolyte of the battery diaphragm. Liquid absorption, the prepared sea-island polyphenylene sulfide composite battery separator has good thermal stability, chemical stability, mechanical properties and flame retardancy, which improves the safety of lithium-ion batteries and prolongs their service life .
本发明的制备方法适用于制备海岛型聚苯硫醚复合电池隔膜,制得的海岛型聚苯硫醚复合电池隔膜适用于锂电池。The preparation method of the invention is suitable for preparing the sea-island type polyphenylene sulfide composite battery diaphragm, and the prepared sea-island type polyphenylene sulfide composite battery diaphragm is suitable for lithium batteries.
附图说明Description of drawings
下面结合附图及具体实施例对本发明作更进一步详细说明。The present invention will be described in further detail below in conjunction with the accompanying drawings and specific embodiments.
图1a和图1b为聚苯硫醚超细纤维的扫描电镜图,图1c和图1d为聚酰亚胺纳米纤维的扫描电镜图,图1e和图1f为本发明实施例1制得的海岛型聚苯硫醚复合电池隔膜的扫描电镜图;Figure 1a and Figure 1b are scanning electron micrographs of polyphenylene sulfide ultrafine fibers, Figure 1c and Figure 1d are scanning electron micrographs of polyimide nanofibers, and Figure 1e and Figure 1f are sea-islands prepared in Example 1 of the present invention The scanning electron microscope image of the type polyphenylene sulfide composite battery separator;
图2为本发明实施例1制备的海岛型聚苯硫醚复合电池隔膜的mapping图;Fig. 2 is the mapping diagram of the sea-island type polyphenylene sulfide composite battery separator prepared in Example 1 of the present invention;
图3a-e为本发明实施例1制备的海岛型聚苯硫醚复合电池隔膜与Celgard商业膜的热稳定性能比较图;Fig. 3a-e is the thermal stability performance comparison diagram of the island-in-the-sea polyphenylene sulfide composite battery diaphragm prepared in Example 1 of the present invention and Celgard commercial film;
图4a和图4b为Celgard商业膜的阻燃性能测试图;图4c和图4d为本发明实施例1制备的海岛型聚苯硫醚复合电池隔膜的阻燃性能测试图;Fig. 4a and Fig. 4b are the flame retardant performance test diagrams of Celgard commercial film; Fig. 4c and Fig. 4d are the flame retardant performance test diagrams of the island-in-the-sea polyphenylene sulfide composite battery diaphragm prepared in Example 1 of the present invention;
图5a和图5b为聚苯硫醚超细纤维的扫描电镜图,图5c和图5d为纤维素纳米纤维的扫描电镜图,图5e和图5f为本发明实施例7制得的海岛型聚苯硫醚复合电池隔膜的扫描电镜图;Figure 5a and Figure 5b are scanning electron micrographs of polyphenylene sulfide ultrafine fibers, Figure 5c and Figure 5d are scanning electron micrographs of cellulose nanofibers, Figure 5e and Figure 5f are island-in-the-sea polymers prepared in Example 7 of the present invention. Scanning electron microscope image of phenylene sulfide composite battery separator;
图6为本发明实施例7制备的海岛型聚苯硫醚复合电池隔膜的mapping图;Fig. 6 is a mapping diagram of the sea-island polyphenylene sulfide composite battery separator prepared in Example 7 of the present invention;
图7a-e为本发明实施例7制备的海岛型聚苯硫醚复合电池隔膜与Celgard商业膜的热稳定性能比较图;Figure 7a-e is a comparison chart of the thermal stability performance of the sea-island type polyphenylene sulfide composite battery separator prepared in Example 7 of the present invention and Celgard's commercial film;
图8a和图8b为Celgard商业膜的阻燃性能测试图;图8c和图8d为本发明实施例7制备的海岛型聚苯硫醚复合电池隔膜的阻燃性能测试图;Figure 8a and Figure 8b are the flame retardant performance test charts of Celgard commercial membranes; Figure 8c and Figure 8d are the flame retardant performance test charts of the sea-island polyphenylene sulfide composite battery separator prepared in Example 7 of the present invention;
图9a和图9b为聚苯硫醚超细纤维的扫描电镜图,图9c和图9d为玻璃纳米纤维的扫描电镜图,图9e和图9f为本发明实施例13制得的海岛型聚苯硫醚复合电池隔膜的扫描电镜图;Figure 9a and Figure 9b are scanning electron micrographs of polyphenylene sulfide ultrafine fibers, Figure 9c and Figure 9d are scanning electron micrographs of glass nanofibers, Figure 9e and Figure 9f are sea-island polyphenylene sulfide prepared in Example 13 of the present invention Scanning electron microscope image of thioether composite battery separator;
图10为本发明实施例13制备的海岛型聚苯硫醚复合电池隔膜的mapping图;Figure 10 is a mapping diagram of the sea-island type polyphenylene sulfide composite battery separator prepared in Example 13 of the present invention;
图11a-e为本发明实施例13制备的海岛型聚苯硫醚复合电池隔膜与Celgard商业膜的热稳定性能比较图;Figures 11a-e are comparison diagrams of the thermal stability of the sea-island type polyphenylene sulfide composite battery separator prepared in Example 13 of the present invention and Celgard's commercial film;
图12a和图12b为Celgard商业膜的阻燃性能测试图;图12c和图12d为本发明实施例13制备的海岛型聚苯硫醚复合电池隔膜的阻燃性能测试图。Figure 12a and Figure 12b are the flame retardant performance test charts of Celgard's commercial film; Figure 12c and Figure 12d are the flame retardant performance test charts of the sea-island type polyphenylene sulfide composite battery separator prepared in Example 13 of the present invention.
具体实施方式Detailed ways
下面结合实施例对本发明作进一步说明,但本领域的技术人员应当理解,本发明并不限于以下实施例,任何在本发明具体实施例基础上做出的改进和等效变化,都在本发明权利要求保护的范围之内。The present invention will be further described below in conjunction with the examples, but those skilled in the art should understand that the present invention is not limited to the following examples, and any improvements and equivalent changes made on the basis of the specific examples of the present invention are within the scope of the present invention within the scope of the claims.
实施例1-6海岛型聚苯硫醚复合电池隔膜的制备方法Example 1-6 Preparation method of sea-island polyphenylene sulfide composite battery diaphragm
实施例1-6分别为一种海岛型聚苯硫醚复合电池隔膜的制备方法,制备过程中的工艺参数如表1所示,具体制备过程包括以下步骤:Examples 1-6 are respectively a preparation method of a sea-island type polyphenylene sulfide composite battery diaphragm, and the process parameters in the preparation process are shown in Table 1. The specific preparation process includes the following steps:
S1、海岛型聚苯硫醚复合纤维的制备:将熔融指数为50-500g/10min的聚苯硫醚(PPS)和熔融指数为10-50g/10min的碱溶性聚酯(PET),进行干燥,干燥温度为80-160℃,干燥时间为12-24h,再以质量比为3:7-7:3的比例混合,经过熔融纺丝即得纤度为0.9-5μm,纤维为圆形的海岛型聚苯硫醚复合纤维;熔融纺丝过程中螺杆挤出温度为315-325℃,螺杆熔压为60-120bar,纺丝箱体温度为315-325℃,纺丝组件压力为小于60kgf/cm2,纺丝速度为600-1000m/min,牵伸倍数为3.6-4.3倍。S1. Preparation of sea-island polyphenylene sulfide composite fibers: dry polyphenylene sulfide (PPS) with a melt index of 50-500g/10min and alkali-soluble polyester (PET) with a melt index of 10-50g/10min , the drying temperature is 80-160°C, the drying time is 12-24h, and then mixed at a mass ratio of 3:7-7:3, and melt-spun to obtain islands with a fineness of 0.9-5μm and round fibers Type polyphenylene sulfide composite fiber; during the melt spinning process, the extrusion temperature of the screw is 315-325°C, the melting pressure of the screw is 60-120bar, the temperature of the spinning box is 315-325°C, and the pressure of the spinning assembly is less than 60kgf/ cm 2 , the spinning speed is 600-1000m/min, and the draft ratio is 3.6-4.3 times.
S2、海岛型聚苯硫醚复合电池隔膜的制备:将海岛型聚苯硫醚复合纤维经过热处理后切短,热处理的温度为80-150℃,热处理时间为10-60min,按表1中的相关数据称取切短后的海岛型聚苯硫醚复合纤维中长度5-8mm的海岛型聚苯硫醚复合纤维的质量分数为0-25%,长度1-2mm的海岛型聚苯硫醚复合纤维的质量分数为0-25%,长度2-5mm的海岛型聚苯硫醚复合纤维的质量分数为50-100%,切短后的海岛型聚苯硫醚复合纤维与通过静电纺丝和高速梳理机切断而成的,纤维为圆形,直径为100-1000nm,纤维长度为1-3mm的芳香族纳米纤维混合,其中,切短后的聚苯硫醚复合纤维的质量分数为80-95%,其余为芳香族纳米纤维,以水位分散介质进行分散打浆,打浆浓度为3-5%wt,再以搅拌叶轮3000-3500rad/min的转速进行疏解,疏解时间为10-15min,之后以0.03-0.8%的上网浓度进行抄纸,最后热压,热压压力为10-20MPa,热压温度为150-230℃,即得海岛型聚苯硫醚复合电池隔膜。S2. Preparation of sea-island polyphenylene sulfide composite battery diaphragm: heat-treat the sea-island polyphenylene sulfide composite fiber and cut it short. Relevant data Weigh the sea-island type polyphenylene sulfide composite fiber with a length of 5-8mm in the mass fraction of 0-25% in the shortened sea-island type polyphenylene sulfide composite fiber, and the sea-island type polyphenylene sulfide with a length of 1-2mm The mass fraction of composite fibers is 0-25%, the mass fraction of sea-island polyphenylene sulfide composite fibers with a length of 2-5mm is 50-100%, and the chopped sea-island polyphenylene sulfide composite fibers are combined with electrospinning It is mixed with aromatic nanofibers cut by a high-speed carding machine, the fibers are round, the diameter is 100-1000nm, and the fiber length is 1-3mm, and the mass fraction of the chopped polyphenylene sulfide composite fiber is 80 -95%, and the rest are aromatic nanofibers, which are dispersed and beaten with a water level dispersion medium. Papermaking is carried out with a concentration of 0.03-0.8%, and finally hot-pressed, with a hot-pressing pressure of 10-20MPa and a hot-pressing temperature of 150-230°C, to obtain a sea-island type polyphenylene sulfide composite battery separator.
实施例1-6中的芳香族纳米纤维为聚酰亚胺纳米纤维、芳砜纶纳米纤维、芳纶纳米纤维、聚醚醚酮纳米纤维中的一种。The aromatic nanofibers in Examples 1-6 are one of polyimide nanofibers, polysulfone nanofibers, aramid nanofibers, and polyether ether ketone nanofibers.
表1实施例1-6海岛型聚苯硫醚复合电池隔膜制备中的工艺参数Table 1 Process parameters in the preparation of sea-island polyphenylene sulfide composite battery separators in Examples 1-6
由上述制备方法制得的海岛型聚苯硫醚复合电池隔膜,具体性能指标参见表2。See Table 2 for specific performance indicators of the sea-island type polyphenylene sulfide composite battery separator prepared by the above preparation method.
表2实施例1-6制得的海岛型聚苯硫醚复合电池隔膜的性能指标Table 2 The performance index of the sea-island type polyphenylene sulfide composite battery separator prepared in Examples 1-6
由表2可知,实施例1-6制得的海岛型聚苯硫醚复合电池隔膜孔隙率为40-70%,孔径为0.1-1μm,厚度为10-30μm,电池隔膜孔径均匀、微细,电解液吸液率250-350%,电解液吸液性能较高,拉伸强度为15-50MPa,机械性能良好。此外,实施例1-6制得的海岛型聚苯硫醚复合电池隔膜极限氧指数38-40,现有的Celgard商业膜的极限氧指数为18,所以本发明实施例1-6制得的海岛型聚苯硫醚复合电池隔膜的阻燃性能良好。It can be seen from Table 2 that the island-in-the-sea type polyphenylene sulfide composite battery separator prepared in Examples 1-6 has a porosity of 40-70%, a pore diameter of 0.1-1 μm, and a thickness of 10-30 μm. The liquid absorption rate is 250-350%, the electrolyte liquid absorption performance is high, the tensile strength is 15-50MPa, and the mechanical properties are good. In addition, the limiting oxygen index of the sea-island type polyphenylene sulfide composite battery diaphragm obtained in Examples 1-6 is 38-40, and the limiting oxygen index of the existing Celgard commercial film is 18, so the obtained in Examples 1-6 of the present invention The sea-island polyphenylene sulfide composite battery separator has good flame retardancy.
图1a和图1b为聚苯硫醚超细纤维的扫描电镜图,图1c和图1d为聚酰亚胺纳米纤维的扫描电镜图,图1e和图1f为实施例1制得的海岛型聚苯硫醚复合电池隔膜的扫描电镜图,由图1可知,加入聚酰亚胺纳米纤维之后的海岛型聚苯硫醚复合电池隔膜的孔径降低。实施例1制得的海岛型聚苯硫醚复合电池隔膜的mapping图如图2所示,海岛型聚苯硫醚复合电池隔膜与Celgard商业膜的热稳定性能比较图如图3所示,图3中a-e依次为25℃、150℃、175℃、200℃、230℃的海岛型聚苯硫醚复合电池隔膜和Celgard商业膜的尺寸变化,Celgard表示Celgard商业膜,PSS/PI表示实施例1海岛型聚苯硫醚复合电池隔膜,其中PSS为聚苯硫醚,PI为聚酰亚胺,由图3可以看出,海岛型聚苯硫醚复合电池隔膜在25℃、150℃、175℃、200℃、230℃的尺寸几乎没有变化,而Celgard商业膜在5℃、150℃、175℃、200℃、230℃的尺寸变化明显,所以海岛型聚苯硫醚复合电池隔膜的热稳定性能优于Celgard商业膜;海岛型聚苯硫醚复合电池隔膜与Celgard商业膜的阻燃性能比较图如图4所示,图4a为燃烧前的Celgard商业膜,图4b为燃烧后的Celgard商业膜,图4c为燃烧前的海岛型聚苯硫醚复合电池隔膜,图4d为燃烧后的海岛型聚苯硫醚复合电池隔膜,由图4可知,海岛型聚苯硫醚复合电池隔膜的阻燃性能优于Celgard商业膜,实施例2-6制得的海岛型聚苯硫醚复合电池隔膜与实施例1制得的海岛型聚苯硫醚复合电池隔膜性能相似。Fig. 1a and Fig. 1b are the scanning electron micrographs of polyphenylene sulfide ultrafine fibers, Fig. 1c and Fig. 1d are the scanning electron micrographs of polyimide nanofibers, Fig. 1e and Fig. 1f are the island-in-the-sea polymers prepared in Example 1. The scanning electron microscope image of the phenylene sulfide composite battery separator, as can be seen from Figure 1, the pore size of the sea-island polyphenylene sulfide composite battery separator is reduced after adding polyimide nanofibers. The mapping diagram of the sea-island type polyphenylene sulfide composite battery diaphragm prepared in Example 1 is shown in Figure 2, and the thermal stability performance comparison between the sea-island type polyphenylene sulfide composite battery diaphragm and the Celgard commercial film is shown in Figure 3. In 3, a-e are the dimensional changes of sea-island polyphenylene sulfide composite battery separators and Celgard commercial membranes at 25°C, 150°C, 175°C, 200°C, and 230°C, Celgard means Celgard commercial membranes, and PSS/PI means Example 1 Island-in-the-sea polyphenylene sulfide composite battery separator, in which PSS is polyphenylene sulfide and PI is polyimide. It can be seen from Figure 3 that the island-in-sea polyphenylene sulfide composite battery separator is at 25°C, 150°C, and 175°C , 200°C, and 230°C have little change in size, while the size of Celgard commercial membranes changes significantly at 5°C, 150°C, 175°C, 200°C, and 230°C, so the thermal stability of sea-island polyphenylene sulfide composite battery separators Better than Celgard commercial membrane; the flame retardant performance comparison of sea-island polyphenylene sulfide composite battery separator and Celgard commercial membrane is shown in Figure 4, Figure 4a is the Celgard commercial membrane before combustion, and Figure 4b is the Celgard commercial membrane after combustion , Figure 4c is the island-in-sea polyphenylene sulfide composite battery separator before combustion, and Figure 4d is the island-in-sea polyphenylene sulfide composite battery separator after combustion. The performance is better than that of Celgard commercial film, and the performance of the sea-island type polyphenylene sulfide composite battery separator prepared in Examples 2-6 is similar to that of the sea-island type polyphenylene sulfide composite battery separator prepared in Example 1.
实施例7-12海岛型聚苯硫醚复合电池隔膜的制备方法Example 7-12 Preparation method of sea-island polyphenylene sulfide composite battery diaphragm
实施例7-12分别为一种海岛型聚苯硫醚复合电池隔膜的制备方法,制备过程中的工艺参数如表3所示,具体制备过程包括以下步骤:Examples 7-12 are respectively a preparation method of a sea-island type polyphenylene sulfide composite battery diaphragm, and the process parameters in the preparation process are shown in Table 3. The specific preparation process includes the following steps:
S1、海岛型聚苯硫醚复合纤维的制备:将熔融指数为50-500g/10min的聚苯硫醚(PPS)和熔融指数为10-50g/10min的碱溶性聚酯(PET),进行干燥,干燥温度为80-160℃,干燥时间为12-24h,再以质量比为3:7-7:3的比例混合,经过熔融纺丝即得纤度为0.9-5μm,纤维为圆形的海岛型聚苯硫醚复合纤维;熔融纺丝过程中螺杆挤出温度为315-325℃,螺杆熔压为60-120bar,纺丝箱体温度为315-325℃,纺丝组件压力为小于60kgf/cm2,纺丝速度为600-1000m/min,牵伸倍数为3.6-4.3倍。S1. Preparation of sea-island polyphenylene sulfide composite fibers: dry polyphenylene sulfide (PPS) with a melt index of 50-500g/10min and alkali-soluble polyester (PET) with a melt index of 10-50g/10min , the drying temperature is 80-160°C, the drying time is 12-24h, and then mixed at a mass ratio of 3:7-7:3, and melt-spun to obtain islands with a fineness of 0.9-5μm and round fibers Type polyphenylene sulfide composite fiber; during the melt spinning process, the extrusion temperature of the screw is 315-325°C, the melting pressure of the screw is 60-120bar, the temperature of the spinning box is 315-325°C, and the pressure of the spinning assembly is less than 60kgf/ cm 2 , the spinning speed is 600-1000m/min, and the draft ratio is 3.6-4.3 times.
S2、海岛型聚苯硫醚复合电池隔膜的制备:将海岛型聚苯硫醚复合纤维经过热处理后切短,热处理的温度为80-150℃,热处理时间为10-60min,按表3中的相关数据称取切短后的海岛型聚苯硫醚复合纤维中长度5-8mm的海岛型聚苯硫醚复合纤维的质量分数为0-25%,长度1-2mm的海岛型聚苯硫醚复合纤维的质量分数为0-25%,长度2-5mm的海岛型聚苯硫醚复合纤维的质量分数为50-100%,切短后的海岛型聚苯硫醚复合纤维与通过溶解法和高速梳理机切断而成的,纤维为圆形,直径为100-1000nm,纤维长度为1-3mm的天然纳米纤维混合,其中,切短后的聚苯硫醚复合纤维的质量分数为80-95%,其余为天然纳米纤维,以水位分散介质进行分散打浆,打浆浓度为3-5%wt,再以搅拌叶轮3000-3500rad/min的转速进行疏解,疏解时间为10-15min,之后以0.03-0.8%的上网浓度进行抄纸,最后热压,热压压力为10-20MPa,热压温度为150-230℃,即得海岛型聚苯硫醚复合电池隔膜。S2. Preparation of sea-island polyphenylene sulfide composite battery diaphragm: heat-treat the sea-island polyphenylene sulfide composite fiber and cut it short. Relevant data Weigh the sea-island type polyphenylene sulfide composite fiber with a length of 5-8mm in the mass fraction of 0-25% in the shortened sea-island type polyphenylene sulfide composite fiber, and the sea-island type polyphenylene sulfide with a length of 1-2mm The mass fraction of the composite fiber is 0-25%, the mass fraction of the sea-island type polyphenylene sulfide composite fiber with a length of 2-5mm is 50-100%, and the sea-island type polyphenylene sulfide composite fiber after being chopped is combined with the dissolution method and Cut by a high-speed carding machine, the fiber is round, the diameter is 100-1000nm, and the fiber length is 1-3mm mixed with natural nanofibers, wherein the mass fraction of the chopped polyphenylene sulfide composite fiber is 80-95 %, the rest are natural nanofibers, and the water level dispersion medium is used for dispersing and beating. Papermaking is carried out at a concentration of 0.8%, and finally hot-pressed with a hot-pressing pressure of 10-20MPa and a hot-pressing temperature of 150-230°C to obtain a sea-island type polyphenylene sulfide composite battery separator.
实施例7-12中的天然纳米纤维为纤维素纳米纤维、甲壳素纳米纤维、木质素纳米纤维中的一种。The natural nanofibers in Examples 7-12 are one of cellulose nanofibers, chitin nanofibers and lignin nanofibers.
表3实施例7-12海岛型聚苯硫醚复合电池隔膜制备中的工艺参数及性能指标Table 3 Process parameters and performance indicators in the preparation of sea-island polyphenylene sulfide composite battery separators in Examples 7-12
由上述制备方法制得的海岛型聚苯硫醚复合电池隔膜,具体性能指标参见表4。For the sea-island type polyphenylene sulfide composite battery separator prepared by the above preparation method, see Table 4 for specific performance indicators.
表4实施例7-12制得的海岛型聚苯硫醚复合电池隔膜的性能指标The performance index of the sea-island type polyphenylene sulfide composite battery diaphragm that table 4 embodiment 7-12 makes
由表4可知,实施例7-12制得的海岛型聚苯硫醚复合电池隔膜孔隙率为40-70%,孔径为0.1-1μm,厚度为10-30μm,电池隔膜孔径均匀、微细,电解液吸液率250-350%,电解液吸液性能较高,拉伸强度为15-50MPa,机械性能良好。此外,实施例7-12制得的海岛型聚苯硫醚复合电池隔膜极限氧指数38-40,现有的Celgard商业膜的极限氧指数为18,所以本发明实施例7-12制得的海岛型聚苯硫醚复合电池隔膜的阻燃性能良好。It can be seen from Table 4 that the island-in-the-sea type polyphenylene sulfide composite battery separator prepared in Examples 7-12 has a porosity of 40-70%, a pore diameter of 0.1-1 μm, and a thickness of 10-30 μm. The liquid absorption rate is 250-350%, the electrolyte liquid absorption performance is high, the tensile strength is 15-50MPa, and the mechanical properties are good. In addition, the limiting oxygen index of the sea-island type polyphenylene sulfide composite battery diaphragm obtained in Examples 7-12 is 38-40, and the limiting oxygen index of the existing Celgard commercial film is 18, so the obtained in Examples 7-12 of the present invention The sea-island polyphenylene sulfide composite battery separator has good flame retardancy.
图5a和图5b为聚苯硫醚超细纤维的扫描电镜图,图5c和图5d为纤维素纳米纤维的扫描电镜图,图5e和图5f为实施例7制得的海岛型聚苯硫醚复合电池隔膜的扫描电镜图,由图5可知,加入纤维素纳米纤维之后的海岛型聚苯硫醚复合电池隔膜的孔径降低。实施例7制得的海岛型聚苯硫醚复合电池隔膜的mapping图如图6所示,海岛型聚苯硫醚复合电池隔膜与Celgard商业膜的热稳定性能比较图如图7所示,图7中a-e依次为25℃、150℃、175℃、200℃、230℃的海岛型聚苯硫醚复合电池隔膜和Celgard商业膜的尺寸变化,Celgard表示Celgard商业膜,PSS/CNF表示实施例7的海岛型聚苯硫醚复合电池隔膜,其中PSS为聚苯硫醚,CNF为纤维素纳米纤维,由图7可以看出,海岛型聚苯硫醚复合电池隔膜在25℃、150℃、175℃、200℃、230℃的尺寸几乎没有变化,而Celgard商业膜在5℃、150℃、175℃、200℃、230℃的尺寸变化明显,所以海岛型聚苯硫醚复合电池隔膜的热稳定性能优于Celgard商业膜;海岛型聚苯硫醚复合电池隔膜与Celgard商业膜的阻燃性能比较图如图8所示,图8a为燃烧前的Celgard商业膜,图8b为燃烧后的Celgard商业膜,图8c为燃烧前的海岛型聚苯硫醚复合电池隔膜,图8d为燃烧后的海岛型聚苯硫醚复合电池隔膜,由图8可知,海岛型聚苯硫醚复合电池隔膜的阻燃性能优于Celgard商业膜,实施例8-12制得的海岛型聚苯硫醚复合电池隔膜与实施例7制得的海岛型聚苯硫醚复合电池隔膜性能相似。Figure 5a and Figure 5b are scanning electron micrographs of polyphenylene sulfide ultrafine fibers, Figure 5c and Figure 5d are scanning electron micrographs of cellulose nanofibers, and Figure 5e and Figure 5f are sea-island polyphenylene sulfide prepared in Example 7 The scanning electron microscope image of the ether composite battery separator. It can be seen from Figure 5 that the pore size of the sea-island polyphenylene sulfide composite battery separator is reduced after adding cellulose nanofibers. The mapping diagram of the sea-island type polyphenylene sulfide composite battery diaphragm prepared in Example 7 is shown in Figure 6, and the thermal stability performance comparison between the sea-island type polyphenylene sulfide composite battery diaphragm and the Celgard commercial film is shown in Figure 7. In 7, a-e are the dimensional changes of sea-island polyphenylene sulfide composite battery separators and Celgard commercial membranes at 25°C, 150°C, 175°C, 200°C, and 230°C, Celgard means Celgard commercial membranes, and PSS/CNF means Example 7 The island-in-the-sea polyphenylene sulfide composite battery separator, in which PSS is polyphenylene sulfide, and CNF is cellulose nanofiber. It can be seen from Figure 7 that the island-in-sea polyphenylene sulfide composite battery separator is °C, 200 °C, and 230 °C have almost no change in size, while the size of Celgard commercial membranes changes significantly at 5 °C, 150 °C, 175 °C, 200 °C, and 230 °C, so the thermal stability of the sea-island polyphenylene sulfide composite battery separator The performance is better than that of Celgard commercial film; the flame retardant performance comparison of sea-island polyphenylene sulfide composite battery separator and Celgard commercial film is shown in Figure 8, Figure 8a is the Celgard commercial film before combustion, and Figure 8b is the Celgard commercial film after combustion Figure 8c is the separator of the sea-island type polyphenylene sulfide composite battery before combustion, and Figure 8d is the diaphragm of the sea-island type polyphenylene sulfide composite battery after combustion. Combustibility is better than Celgard commercial film, and the performance of the sea-island polyphenylene sulfide composite battery separator prepared in Examples 8-12 is similar to that of the sea-island polyphenylene sulfide composite battery separator prepared in Example 7.
实施例13-18海岛型聚苯硫醚复合电池隔膜的制备方法Example 13-18 Preparation method of sea-island polyphenylene sulfide composite battery diaphragm
实施例13-18分别为一种海岛型聚苯硫醚复合电池隔膜的制备方法,制备过程中的工艺参数如表5所示,具体制备过程包括以下步骤:Examples 13-18 are respectively a preparation method of a sea-island type polyphenylene sulfide composite battery separator. The process parameters during the preparation process are shown in Table 5. The specific preparation process includes the following steps:
S1、海岛型聚苯硫醚复合纤维的制备:将熔融指数为50-500g/10min的聚苯硫醚(PPS)和熔融指数为10-50g/10min的碱溶性聚酯(PET),进行干燥,干燥温度为80-160℃,干燥时间为12-24h,再以质量比为3:7-7:3的比例混合,经过熔融纺丝即得纤度为0.9-5μm,纤维为圆形的海岛型聚苯硫醚复合纤维;熔融纺丝过程中螺杆挤出温度为315-325℃,螺杆熔压为60-120bar,纺丝箱体温度为315-325℃,纺丝组件压力为小于60kgf/cm2,纺丝速度为600-1000m/min,牵伸倍数为3.6-4.3倍。S1. Preparation of sea-island polyphenylene sulfide composite fibers: dry polyphenylene sulfide (PPS) with a melt index of 50-500g/10min and alkali-soluble polyester (PET) with a melt index of 10-50g/10min , the drying temperature is 80-160°C, the drying time is 12-24h, and then mixed at a mass ratio of 3:7-7:3, and melt-spun to obtain islands with a fineness of 0.9-5μm and round fibers Type polyphenylene sulfide composite fiber; during the melt spinning process, the extrusion temperature of the screw is 315-325°C, the melting pressure of the screw is 60-120bar, the temperature of the spinning box is 315-325°C, and the pressure of the spinning assembly is less than 60kgf/ cm 2 , the spinning speed is 600-1000m/min, and the draft ratio is 3.6-4.3 times.
S2、海岛型聚苯硫醚复合电池隔膜的制备:将海岛型聚苯硫醚复合纤维经过热处理后切短,热处理的温度为80-150℃,热处理时间为10-60min,按表5中的相关数据称取切短后的海岛型聚苯硫醚复合纤维中长度5-8mm的海岛型聚苯硫醚复合纤维的质量分数为0-25%,长度1-2mm的海岛型聚苯硫醚复合纤维的质量分数为0-25%,长度2-5mm的海岛型聚苯硫醚复合纤维的质量分数为50-100%,切短后的海岛型聚苯硫醚复合纤维与通过火焰法和高速梳理机切断而成的,纤维为圆形,直径为100-1000nm,纤维长度为1-3mm的无机纳米纤维混合,其中,切短后的聚苯硫醚复合纤维的质量分数为80-95%,其余为无机纳米纤维,以水位分散介质进行分散打浆,打浆浓度为3-5%wt,再以搅拌叶轮3000-3500rad/min的转速进行疏解,疏解时间为10-15min,之后以0.03-0.8%的上网浓度进行抄纸,最后热压,热压压力为10-20MPa,热压温度为150-230℃,即得海岛型聚苯硫醚复合电池隔膜。S2. Preparation of sea-island polyphenylene sulfide composite battery diaphragm: heat-treat the sea-island polyphenylene sulfide composite fiber and cut it short. Relevant data Weigh the sea-island type polyphenylene sulfide composite fiber with a length of 5-8mm in the mass fraction of 0-25% in the shortened sea-island type polyphenylene sulfide composite fiber, and the sea-island type polyphenylene sulfide with a length of 1-2mm The mass fraction of composite fibers is 0-25%, the mass fraction of sea-island polyphenylene sulfide composite fibers with a length of 2-5mm is 50-100%, and the chopped sea-island polyphenylene sulfide composite fibers are combined with flame method and Cut by a high-speed carding machine, the fiber is round, the diameter is 100-1000nm, and the fiber length is 1-3mm Inorganic nanofiber mix, wherein, the mass fraction of the polyphenylene sulfide composite fiber after cutting is 80-95 %, the rest are inorganic nanofibers, and the water level dispersion medium is used for dispersing and beating. Papermaking is carried out at a concentration of 0.8%, and finally hot-pressed with a hot-pressing pressure of 10-20MPa and a hot-pressing temperature of 150-230°C to obtain a sea-island type polyphenylene sulfide composite battery separator.
实施例7-12中的无机纳米纤维为玻璃纳米纤维、陶瓷纳米纤维、石英纳米纤维、硅硼氮纳米纤维中的一种。The inorganic nanofibers in Examples 7-12 are one of glass nanofibers, ceramic nanofibers, quartz nanofibers, and silicon boron nitrogen nanofibers.
表5实施例13-18海岛型聚苯硫醚复合电池隔膜制备中的工艺参数及性能指标Table 5 Process parameters and performance indicators in the preparation of sea-island polyphenylene sulfide composite battery separators in Examples 13-18
由上述制备方法制得的海岛型聚苯硫醚复合电池隔膜,具体性能指标参见表6。For the sea-island type polyphenylene sulfide composite battery separator prepared by the above preparation method, see Table 6 for specific performance indicators.
表6实施例13-18制得的海岛型聚苯硫醚复合电池隔膜的性能指标The performance index of the sea-island type polyphenylene sulfide composite battery diaphragm that table 6 embodiment 13-18 makes
由表6可知,实施例13-18制得的海岛型聚苯硫醚复合电池隔膜孔隙率为40-70%,孔径为0.1-1μm,厚度为10-30μm,电池隔膜孔径均匀、微细,电解液吸液率250-350%,电解液吸液性能较高,拉伸强度为15-50MPa,机械性能良好。此外,实施例13-18制得的海岛型聚苯硫醚复合电池隔膜极限氧指数38-40,现有的Celgard商业膜的极限氧指数为18,所以本发明实施例13-18制得的海岛型聚苯硫醚复合电池隔膜的阻燃性能良好。It can be seen from Table 6 that the island-in-the-sea type polyphenylene sulfide composite battery separator prepared in Examples 13-18 has a porosity of 40-70%, a pore diameter of 0.1-1 μm, and a thickness of 10-30 μm. The liquid absorption rate is 250-350%, the electrolyte liquid absorption performance is high, the tensile strength is 15-50MPa, and the mechanical properties are good. In addition, the limiting oxygen index of the sea-island type polyphenylene sulfide composite battery diaphragm obtained in Examples 13-18 is 38-40, and the limiting oxygen index of the existing Celgard commercial film is 18, so the obtained in Examples 13-18 of the present invention The sea-island polyphenylene sulfide composite battery separator has good flame retardancy.
图9a和图9b为聚苯硫醚超细纤维的扫描电镜图,图9c和图9d为玻璃纳米纤维的扫描电镜图,图9e和图9f为实施例13制得的海岛型聚苯硫醚复合电池隔膜的扫描电镜图,由图9可知,加入聚酰亚胺纳米纤维之后的海岛型聚苯硫醚复合电池隔膜的孔径降低。实施例13制得的海岛型聚苯硫醚复合电池隔膜的mapping图如图10所示,海岛型聚苯硫醚复合电池隔膜与Celgard商业膜的热稳定性能比较图如图11所示,图11中a-e依次为25℃、150℃、175℃、200℃、230℃的海岛型聚苯硫醚复合电池隔膜和Celgard商业膜的尺寸变化,Celgard表示Celgard商业膜,PSS/GNF表示实施例13的海岛型聚苯硫醚复合电池隔膜,其中PSS为聚苯硫醚,GNF为玻璃纳米纤维,由图11可以看出,海岛型聚苯硫醚复合电池隔膜在25℃、150℃、175℃、200℃、230℃的尺寸几乎没有变化,而Celgard商业膜在5℃、150℃、175℃、200℃、230℃的尺寸变化明显,所以海岛型聚苯硫醚复合电池隔膜的热稳定性能优于Celgard商业膜;海岛型聚苯硫醚复合电池隔膜与Celgard商业膜的阻燃性能比较图如图12所示,图12a为燃烧前的Celgard商业膜,图12b为燃烧后的Celgard商业膜,图12c为燃烧前的海岛型聚苯硫醚复合电池隔膜,图12d为燃烧后的海岛型聚苯硫醚复合电池隔膜,由图12可知,海岛型聚苯硫醚复合电池隔膜的阻燃性能优于Celgard商业膜,实施例14-18制得的海岛型聚苯硫醚复合电池隔膜与实施例13制得的海岛型聚苯硫醚复合电池隔膜性能相似。Figure 9a and Figure 9b are scanning electron micrographs of polyphenylene sulfide ultrafine fibers, Figure 9c and Figure 9d are scanning electron micrographs of glass nanofibers, and Figure 9e and Figure 9f are sea-island polyphenylene sulfide prepared in Example 13 The scanning electron microscope image of the composite battery separator, as can be seen from Figure 9, the pore size of the sea-island type polyphenylene sulfide composite battery separator is reduced after adding polyimide nanofibers. The mapping diagram of the sea-island type polyphenylene sulfide composite battery diaphragm prepared in Example 13 is shown in Figure 10, and the thermal stability performance comparison between the sea-island type polyphenylene sulfide composite battery diaphragm and Celgard commercial membrane is shown in Figure 11, Fig. In 11, a-e are the dimensional changes of sea-island polyphenylene sulfide composite battery separators and Celgard commercial membranes at 25°C, 150°C, 175°C, 200°C, and 230°C, Celgard means Celgard commercial membranes, and PSS/GNF means Example 13 The sea-island type polyphenylene sulfide composite battery separator, in which PSS is polyphenylene sulfide, and GNF is glass nanofiber. It can be seen from Figure 11 that the sea-island type polyphenylene sulfide composite battery separator is at , 200°C, and 230°C have little change in size, while the size of Celgard commercial membranes changes significantly at 5°C, 150°C, 175°C, 200°C, and 230°C, so the thermal stability of sea-island polyphenylene sulfide composite battery separators Better than Celgard commercial membrane; the flame retardant performance comparison of island-type polyphenylene sulfide composite battery separator and Celgard commercial membrane is shown in Figure 12, Figure 12a is the Celgard commercial membrane before combustion, and Figure 12b is the Celgard commercial membrane after combustion , Figure 12c is the island-in-sea polyphenylene sulfide composite battery separator before combustion, and Figure 12d is the island-in-sea polyphenylene sulfide composite battery separator after combustion. The performance is better than that of Celgard commercial film, and the performance of the sea-island type polyphenylene sulfide composite battery separator prepared in Examples 14-18 is similar to that of the sea-island type polyphenylene sulfide composite battery separator prepared in Example 13.
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