技术领域Technical Field
本发明属于电池材料技术领域，具体涉及一种改性集流体基膜及其制备方法和应用。The invention belongs to the technical field of battery materials, and in particular relates to a modified current collector base film and a preparation method and application thereof.
背景技术Background Art
目前，基于高分子聚合物膜的复合集流体得到新能源行业的广泛关注和应用。该复合集流体的制备通常采用在物理气相沉积(PVD)的方法在高分子薄膜(如聚酯类、聚烯烃类等)上沉积一层金属，从而制备出导电良好的复合集流体。相比传统的集流体，基于高分子聚合物膜的复合集流体具备成本低、质量轻、内部绝缘性好等特点。这些特点使得复合集流体在电池中应用时能够降低电池的成本、并提升电池的能量密度及安全性。At present, composite current collectors based on polymer films have received widespread attention and application in the new energy industry. The preparation of the composite current collector usually uses a physical vapor deposition (PVD) method to deposit a layer of metal on a polymer film (such as polyesters, polyolefins, etc.) to prepare a composite current collector with good conductivity. Compared with traditional current collectors, composite current collectors based on polymer films have the characteristics of low cost, light weight, and good internal insulation. These characteristics enable the composite current collector to reduce the cost of the battery and improve the energy density and safety of the battery when used in the battery.
然而，高分子聚合物膜在集流体的制备过程中会遭受一定的损伤，尤其是在高温下，高分子层由于不稳定性，在遭受应力或化学试剂等伤害时，更易出现低性能或是缺陷，从而对复合集流体物化性能造成影响。However, the polymer film will suffer certain damage during the preparation of the current collector, especially at high temperatures. Due to its instability, the polymer layer is more likely to have low performance or defects when subjected to stress or chemical reagents, thereby affecting the physical and chemical properties of the composite current collector.
因此，有必要开发出一种具有优异力学性能的高分子聚合物膜，从而进一步提升基于此制备的复合集流体的性能，增强电池的物化性能和安全性能。Therefore, it is necessary to develop a high molecular polymer membrane with excellent mechanical properties, so as to further improve the performance of the composite current collector prepared based on it and enhance the physical and chemical properties and safety performance of the battery.
发明内容Summary of the invention
针对现有技术的不足，本发明的目的在于提供一种改性集流体基膜及其制备方法和应用。本发明采用改性聚脲涂层对聚合物膜进行改性，可以改善聚合物膜的极性，使其与导电层的接触更加紧密，增加粘结力，并且改性聚脲涂层具有高应变速率敏感性和优异的力学性能；其次，由于改性聚脲涂层具有良好的防腐性能、阻隔性能、高热分解温度和优异的热稳定性，因此有助于聚合物膜抵御电解液的侵蚀和高温环境。综上，本发明提供的改性集流体基膜具有优异的力学性能、热稳定性和粘结力，在后续复合集流体的制备过程中不易产生损伤，可促进复合集流体的推广和应用，基于此制备的电池具有优异的物化性能及安全性能。In view of the deficiencies of the prior art, the object of the present invention is to provide a modified current collector base film and a preparation method and application thereof. The present invention uses a modified polyurea coating to modify the polymer film, which can improve the polarity of the polymer film, make its contact with the conductive layer closer, increase the adhesion, and the modified polyurea coating has high strain rate sensitivity and excellent mechanical properties; secondly, because the modified polyurea coating has good corrosion resistance, barrier properties, high thermal decomposition temperature and excellent thermal stability, it helps the polymer film to resist the erosion of the electrolyte and high temperature environment. In summary, the modified current collector base film provided by the present invention has excellent mechanical properties, thermal stability and adhesion, is not easy to be damaged in the subsequent preparation process of the composite current collector, can promote the promotion and application of the composite current collector, and the battery prepared based on this has excellent physical and chemical properties and safety performance.
为达此目的，本发明采用以下技术方案：To achieve this object, the present invention adopts the following technical solutions:
第一方面，本发明提供一种改性集流体基膜，所述改性集流体基膜包括聚合物膜，以及设置在所述聚合物膜至少一侧表面上的改性聚脲涂层。In a first aspect, the present invention provides a modified current collector base film, comprising a polymer film and a modified polyurea coating disposed on at least one surface of the polymer film.
聚脲由于软硬段间的热力学不相容性及硬段间的氢键作用，使得聚脲结构内部呈现微相分离的独特形态，其在宏观层面上表现出卓越的综合力学性能：在静态和准静态加载下，聚脲表现出超弹性材料特性，具有优异的力学性能；在动态加载下，聚脲的力学行为变得复杂，表现出高应变率敏感性和非线性应力应变关系，随着应变率的不断增加，聚脲由柔软橡胶态转变为硬质塑料态，在此过程中会通过变形吸收耗散能量。Due to the thermodynamic incompatibility between the soft and hard segments and the hydrogen bonding between the hard segments, polyurea has a unique morphology of microphase separation inside its structure, and exhibits excellent comprehensive mechanical properties at the macro level: under static and quasi-static loading, polyurea exhibits superelastic material properties and has excellent mechanical properties; under dynamic loading, the mechanical behavior of polyurea becomes complex, showing high strain rate sensitivity and nonlinear stress-strain relationship. As the strain rate continues to increase, polyurea changes from a soft rubber state to a hard plastic state, and in this process it absorbs and dissipates energy through deformation.
因此，本发明采用改性聚脲涂层用于聚合物膜，可以改善聚合物膜的极性，使其与导电层的接触更加紧密，增加粘结力，并且改性聚脲涂层具有高应变速率敏感性和优异的力学性能，尤其是延伸率得到显著提升；其次，由于改性聚脲涂层具有良好的防腐性能、阻隔性能、高热分解温度和优异的热稳定性，其在遭受局部热量以及突然的机械冲击时，聚脲会转变成玻璃态并吸收部分能量，因此有助于聚合物膜抵御电解液的侵蚀和高温环境。综上，本发明提供的改性集流体基膜具有优异的力学性能、热稳定性和粘结力，在后续复合集流体的制备过程中不易产生损伤，可促进复合集流体的推广和应用，基于此制备的电池具有优异的物化性能及安全性能。Therefore, the present invention adopts a modified polyurea coating for the polymer film, which can improve the polarity of the polymer film, make it more closely contacted with the conductive layer, increase the bonding force, and the modified polyurea coating has high strain rate sensitivity and excellent mechanical properties, especially the elongation is significantly improved; secondly, because the modified polyurea coating has good corrosion resistance, barrier properties, high thermal decomposition temperature and excellent thermal stability, when it is subjected to local heat and sudden mechanical shock, the polyurea will be transformed into a glassy state and absorb part of the energy, thus helping the polymer film to resist the erosion of the electrolyte and the high temperature environment. In summary, the modified current collector base film provided by the present invention has excellent mechanical properties, thermal stability and bonding force, is not easy to be damaged in the subsequent preparation process of the composite current collector, can promote the promotion and application of the composite current collector, and the battery prepared based on this has excellent physical and chemical properties and safety performance.
作为本发明一种优选的技术方案，所述改性聚脲涂层的制备方法包括以下步骤：As a preferred technical solution of the present invention, the preparation method of the modified polyurea coating comprises the following steps:
(a)将异氰酸酯、聚醚多元醇和活性剂混合，反应后得到A组分，所述A组分包括含-NCO的预聚物；(a) mixing isocyanate, polyether polyol and activator to obtain component A after reaction, wherein component A includes a prepolymer containing -NCO;
(b)将端氨基聚醚、胺扩链剂、功能性填料和助剂混合，得到B组分；(b) mixing the amino-terminated polyether, the amine chain extender, the functional filler and the additive to obtain component B;
(c)将所述A组分和B组分混合，然后喷涂到所述聚合物膜上，形成改性聚脲涂层。(c) mixing the A component and the B component, and then spraying them onto the polymer film to form a modified polyurea coating.
作为本发明一种优选的技术方案，所述改性聚脲涂层的单面厚度为50-500nm，例如可以是50nm、100nm、200nm、300nm、400nm或500nm等，优选为50-200nm。As a preferred technical solution of the present invention, the single-sided thickness of the modified polyurea coating is 50-500 nm, for example, it can be 50 nm, 100 nm, 200 nm, 300 nm, 400 nm or 500 nm, etc., preferably 50-200 nm.
本发明中，若改性聚脲涂层的单面厚度过薄，则效果不明显；若改性聚脲涂层的单面厚度过厚，则容易造成厚度不均匀，且阻碍电化学性能。In the present invention, if the thickness of one side of the modified polyurea coating is too thin, the effect is not obvious; if the thickness of one side of the modified polyurea coating is too thick, it is easy to cause uneven thickness and hinder the electrochemical performance.
优选地，所述聚合物膜的材料包括聚对苯二甲酸乙二醇酯(PET)、聚丙烯(PP)、聚对苯二甲酸丁二醇酯(PBT)、聚萘二甲酸乙二醇酯(PEN)、聚乙烯(PE)、聚丙乙烯、聚氯乙烯(PVC)、聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚苯硫醚(PPS)、聚苯醚(PPO)、聚苯乙烯(PS)或聚酰亚胺(PI)中的任意一种或至少两种的组合。Preferably, the material of the polymer film includes any one or a combination of at least two of polyethylene terephthalate (PET), polypropylene (PP), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyethylene (PE), polypropylene, polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyphenylene sulfide (PPS), polyphenylene oxide (PPO), polystyrene (PS) or polyimide (PI).
优选地，所述聚合物膜的厚度为1-10μm，例如可以是1μm、3μm、5μm、7μm、8μm或10μm等。Preferably, the polymer film has a thickness of 1-10 μm, for example, 1 μm, 3 μm, 5 μm, 7 μm, 8 μm or 10 μm.
本发明中，考虑到复合集流体的应用要求，同时兼顾制备工艺的难度和成本的高低，优选聚合物膜的厚度为1-10μm。In the present invention, considering the application requirements of the composite current collector and the difficulty and cost of the preparation process, the thickness of the polymer film is preferably 1-10 μm.
第二方面，本发明提供一种如第一方面所述的改性集流体基膜的制备方法，所述制备方法包括以下步骤：In a second aspect, the present invention provides a method for preparing the modified current collector base film as described in the first aspect, the preparation method comprising the following steps:
将改性聚脲材料涂覆在聚合物膜的至少一侧表面上，得到所述改性集流体基膜。The modified polyurea material is coated on at least one surface of the polymer film to obtain the modified current collector base film.
作为本发明一种优选的技术方案，所述涂覆的方法包括喷涂法、刷涂法或辊涂法中的任意一种或至少两种的组合。As a preferred technical solution of the present invention, the coating method includes any one of spraying, brushing or roller coating, or a combination of at least two of them.
作为本发明一种优选的技术方案，所述改性聚脲材料的制备方法包括以下步骤：As a preferred technical solution of the present invention, the preparation method of the modified polyurea material comprises the following steps:
(a)将异氰酸酯、聚醚多元醇和活性剂混合，反应后得到A组分，所述A组分包括含-NCO的预聚物；(a) mixing isocyanate, polyether polyol and activator to obtain component A after reaction, wherein component A includes a prepolymer containing -NCO;
(b)将端氨基聚醚、胺扩链剂、功能性填料和助剂混合，得到B组分；(b) mixing the amino-terminated polyether, the amine chain extender, the functional filler and the additive to obtain component B;
(c)将所述A组分和B组分混合，得到所述改性聚脲材料。(c) mixing the component A and the component B to obtain the modified polyurea material.
本发明中，使用一定质量比的长碳链二胺和脂环族二胺组成的胺扩链剂替代芳香族扩链剂，可以有效提高聚脲材料的力学性能，因此改性聚脲材料随着刚度和强度的增加，破坏应变是降低的，改性聚脲材料具有较高的应变率敏感性，同时在高应变速率等情况下可呈现出玻璃态，可在高应变速率下吸收能量，因此具有更好的力学性能，从而可以避免在集流体的制备过程中产生缺陷。In the present invention, an amine chain extender composed of a long carbon chain diamine and an alicyclic diamine in a certain mass ratio is used to replace the aromatic chain extender, which can effectively improve the mechanical properties of the polyurea material. Therefore, as the stiffness and strength of the modified polyurea material increase, the failure strain is reduced. The modified polyurea material has a high strain rate sensitivity and can present a glassy state under high strain rate conditions. It can absorb energy at high strain rates and thus has better mechanical properties, thereby avoiding defects in the preparation process of the current collector.
作为本发明一种优选的技术方案，步骤(a)所述异氰酸酯包括2,4-二甲基癸二异氰酸酯、2,2–二甲基癸二异氰酸酯、2,2,4-三甲基癸二异氰酸酯或2,4,6-三甲基癸二异氰酸酯单体中的任意一种或至少两种的组合。As a preferred technical solution of the present invention, the isocyanate in step (a) includes any one of 2,4-dimethyldecane diisocyanate, 2,2-dimethyldecane diisocyanate, 2,2,4-trimethyldecane diisocyanate or 2,4,6-trimethyldecane diisocyanate monomers, or a combination of at least two thereof.
优选地，步骤(a)所述聚醚多元醇包括丙二醇聚醚、丁二醇聚醚、己二醇聚醚、聚氧化丙烯二醇、聚氧化丙烯三醇或聚四氢呋喃醚二醇中的任意一种或至少两种的组合。Preferably, the polyether polyol in step (a) comprises any one of propylene glycol polyether, butylene glycol polyether, hexanediol polyether, polyoxypropylene glycol, polyoxypropylene triol or polytetramethylene glycol, or a combination of at least two thereof.
优选地，步骤(a)所述活性剂包括聚醚碳酸酯、烯丙基缩水甘油醚或亚烷基碳酸酯中的任意一种或至少两种的组合。Preferably, the active agent in step (a) comprises any one of polyether carbonate, allyl glycidyl ether or alkylene carbonate, or a combination of at least two thereof.
优选地，步骤(a)所述异氰酸酯、聚醚多元醇和活性剂的质量比为(40-55):(44-55):(1-5)，其中，异氰酸酯的选择范围“40-55”例如可以是40、45、50或55等，聚醚多元醇的选择范围“44-55”例如可以是44、50或55等，活性剂的选择范围“1-5”例如可以是1、2、3、4或5等。Preferably, the mass ratio of the isocyanate, the polyether polyol and the activator in step (a) is (40-55):(44-55):(1-5), wherein the selection range of the isocyanate "40-55" can be, for example, 40, 45, 50 or 55, etc., the selection range of the polyether polyol "44-55" can be, for example, 44, 50 or 55, etc., and the selection range of the activator "1-5" can be, for example, 1, 2, 3, 4 or 5, etc.
作为本发明一种优选的技术方案，步骤(b)所述端氨基聚醚为氨基封端的聚环氧烷烃化合物。As a preferred technical solution of the present invention, the amino-terminated polyether in step (b) is an amino-terminated polyalkylene oxide compound.
优选地，所述氨基封端的聚环氧烷烃化合物包括D-230(CAS号：9046-10-0)、D-2000(CAS：9046-10-0)、T-403(CAS：39423-51-3)、T-5000(CAS：64852-22-8)、ZD-1200(CAS：100-1000-11)、ZD-140(CAS：9040-10-0)、ZD-123(CAS：9046-10-0)、ZT-143(CAS：39423-51-3)或ZT-1500(CAS：64852-22-8)中的任意一种或至少两种的组合。Preferably, the amino-terminated polyalkylene oxide compound includes any one of D-230 (CAS No.: 9046-10-0), D-2000 (CAS: 9046-10-0), T-403 (CAS: 39423-51-3), T-5000 (CAS: 64852-22-8), ZD-1200 (CAS: 100-1000-11), ZD-140 (CAS: 9040-10-0), ZD-123 (CAS: 9046-10-0), ZT-143 (CAS: 39423-51-3) or ZT-1500 (CAS: 64852-22-8) or a combination of at least two thereof.
优选地，步骤(b)所述胺扩链剂包括长碳链二胺和脂环族二胺。Preferably, the amine chain extender in step (b) comprises long carbon chain diamine and alicyclic diamine.
优选地，所述长碳链二胺为碳原子数大于等于10的直链二胺，碳原子数例如可以是10、11、12、13、14、15、18、20、22、25、28、30、33、35、38或40等，优选为碳原子数在C12-C30区间内的直链二胺。Preferably, the long carbon chain diamine is a straight chain diamine having a carbon number greater than or equal to 10, for example, 10, 11, 12, 13, 14, 15, 18, 20, 22, 25, 28, 30, 33, 35, 38 or 40, preferably a straight chain diamine with a carbon number in the range of C12-C30.
优选地，所述长碳链二胺包括癸二胺、十一烷二胺、十二烷二胺、十三烷二胺或十四烷二胺中的任意一种或至少两种的组合。Preferably, the long carbon chain diamine includes any one of decanediamine, undecanediamine, dodecanediamine, tridecanediamine or tetradecanediamine, or a combination of at least two thereof.
优选地，所述脂环族二胺包括分子量小于300的脂环族二胺。Preferably, the alicyclic diamine includes an alicyclic diamine having a molecular weight of less than 300.
本发明中，使用分子量小于300的脂环族二胺代替少量芳香族扩链剂，可以有效提高聚脲材料的力学性能。In the present invention, the alicyclic diamine with a molecular weight less than 300 is used to replace a small amount of aromatic chain extender, which can effectively improve the mechanical properties of the polyurea material.
优选地，所述分子量小于300的脂环族二胺包括3,3二甲基-4,4-二环乙基甲烷二胺、异佛尔酮二胺或4,4'-二氨基二环己基甲烷中的任意一种或至少两种的组合。Preferably, the alicyclic diamine with a molecular weight less than 300 includes any one of 3,3-dimethyl-4,4-dicycloethylmethanediamine, isophoronediamine or 4,4'-diaminodicyclohexylmethane, or a combination of at least two thereof.
优选地，所述长碳链二胺和脂环族二胺的质量比为1:(0.2-2.5)，例如可以是1:0.2、1:0.3、1:0.4、1:0.5、1:0.6、1:0.7、1:0.8、1:0.9、1:1、1:2、1:4、1:6、1:8、1:2或1:2.5等。Preferably, the mass ratio of the long carbon chain diamine to the alicyclic diamine is 1:(0.2-2.5), for example, it can be 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:2, 1:4, 1:6, 1:8, 1:2 or 1:2.5, etc.
本发明中，若长碳链二胺和脂环族二胺的质量比过小或过大均会导致聚脲材料的力学性能的提高达不到最佳效果。In the present invention, if the mass ratio of the long carbon chain diamine to the alicyclic diamine is too small or too large, the mechanical properties of the polyurea material cannot be improved to the best effect.
优选地，步骤(b)所述功能性填料包括阻燃剂、亲水性化合物、增塑剂、增粘剂或胶粘剂中的任意一种或至少两种的组合。Preferably, the functional filler in step (b) comprises any one of a flame retardant, a hydrophilic compound, a plasticizer, a tackifier or an adhesive, or a combination of at least two thereof.
本发明中，利用阻燃剂进行改性，可以提高聚脲涂层的热分解温度，获得优异的热稳定性，受到外界火源攻击时，能够有效地阻止、延缓或终止火焰的传播；利用亲水性化合物进行改性，可以改善聚合物膜的极性，使其变得亲水，从而与导电层间接触更紧密，增加粘结力；利用增塑剂、增粘剂或胶粘剂进行改性，可以提升力学性能，使不同化合物间结合更紧密。In the present invention, the thermal decomposition temperature of the polyurea coating can be increased by using a flame retardant for modification, thereby obtaining excellent thermal stability, and being able to effectively prevent, delay or terminate the spread of flames when attacked by an external fire source; the polarity of the polymer film can be improved by using a hydrophilic compound for modification, thereby making it hydrophilic, thereby making it in closer contact with the conductive layer and increasing the bonding force; the mechanical properties can be improved by using a plasticizer, a tackifier or an adhesive for modification, thereby making different compounds more closely bonded.
优选地，所述阻燃剂包括聚乙烯基倍半硅氧烷、次磷酸铝或石墨中的任意一种或至少两种的组合。Preferably, the flame retardant includes any one of polyvinyl silsesquioxane, aluminum hypophosphite or graphite, or a combination of at least two thereof.
优选地，所述亲水性化合物中的亲水基团包括羧基、磺酸基、氨基、胺基、羟基、酰胺基或醚键中的任意一种或至少两种的组合。示例性的，例如可以是氨化聚丙烯PP-g-NH2和2,2-二羟甲基丙酸的组合等。Preferably, the hydrophilic group in the hydrophilic compound includes any one or a combination of at least two of a carboxyl group, a sulfonic acid group, an amino group, an amine group, a hydroxyl group, an amide group or an ether bond. For example, it may be a combination of ammoniated polypropylene PP-g-NH2 and 2,2-dimethylol propionic acid.
优选地，所述增塑剂包括邻苯二甲酸二辛酯、环氧十八酸异辛酯、马来酸二甲酯、已二酸二异辛酯、磷酸三甲苯酯或偏苯三酸三(2-乙基)己酯中的任意一种或至少两种的组合。Preferably, the plasticizer includes any one of dioctyl phthalate, isooctyl epoxy octadecanoate, dimethyl maleate, diisooctyl adipate, tricresyl phosphate or tri(2-ethyl)hexyl trimellitate, or a combination of at least two thereof.
优选地，所述增粘剂包括萜烯树脂、特级松香、氢化C5石油树脂或共聚石油树脂中的任意一种或至少两种的组合。Preferably, the tackifier includes any one of terpene resin, special rosin, hydrogenated C5 petroleum resin or copolymerized petroleum resin, or a combination of at least two thereof.
优选地，所述胶粘剂包括硅烷偶联剂、丙烯酸、环氧树脂、氯化聚丙烯或氨化聚丙烯中的任意一种或至少两种的组合。Preferably, the adhesive comprises any one of silane coupling agent, acrylic acid, epoxy resin, chlorinated polypropylene or ammoniated polypropylene, or a combination of at least two thereof.
需要说明的是，本发明对助剂的种类不进行限定，示例性的，例如可以是相容剂、分散剂或催化剂等物质，其中相容剂例如可以是SBS(苯乙烯-丁二烯-苯乙烯三嵌段共聚物)、SEBS((以聚苯乙烯为末端段,以聚丁二烯加氢得到的乙烯-丁烯共聚物为中间弹性嵌段的线性三嵌段共聚物)或SIS(苯乙烯-异戊二烯-苯乙烯三嵌段共聚物)等，分散剂例如可以是丙酮、甲乙酮或甲苯等，催化剂例如可以是二月桂酸二丁基锡等。It should be noted that the present invention does not limit the types of auxiliary agents. Exemplary agents include compatibilizers, dispersants, catalysts, and the like. The compatibilizer may be, for example, SBS (styrene-butadiene-styrene triblock copolymer), SEBS (a linear triblock copolymer with polystyrene as the terminal segment and ethylene-butylene copolymer obtained by hydrogenating polybutadiene as the middle elastic block), or SIS (styrene-isoprene-styrene triblock copolymer), etc. The dispersant may be, for example, acetone, methyl ethyl ketone or toluene, etc., and the catalyst may be, for example, dibutyltin dilaurate, etc.
优选地，步骤(b)所述端氨基聚醚、胺扩链剂、功能性填料和助剂的质量比为(40-60):(20-35):(0-20):(0-5)，其中，端氨基聚醚的选择范围“40-60”例如可以是40、45、50、55或60等，胺扩链剂的选择范围“20-35”例如可以是20、25、30或35等，功能性填料的选择范围“0-20”例如可以是5、10、15或20等，助剂的选择范围“0-5”例如可以是0、1、2、3、4或5等。Preferably, the mass ratio of the amino-terminated polyether, the amine chain extender, the functional filler and the auxiliary agent in step (b) is (40-60):(20-35):(0-20):(0-5), wherein the selection range of the amino-terminated polyether "40-60" can be, for example, 40, 45, 50, 55 or 60, etc., the selection range of the amine chain extender "20-35" can be, for example, 20, 25, 30 or 35, etc., the selection range of the functional filler "0-20" can be, for example, 5, 10, 15 or 20, etc., and the selection range of the auxiliary agent "0-5" can be, for example, 0, 1, 2, 3, 4 or 5, etc.
本发明中，若胺扩链剂的用量过少，则扩链不充分，聚氨酯分子硬段含量下降，强度、耐热性以及耐溶剂性等性能降低，若胺扩链剂的用量过多，则造成预聚物与扩链剂团聚，进而导致产物不均匀。In the present invention, if the amount of the amine chain extender is too small, the chain extension is insufficient, the hard segment content of the polyurethane molecule decreases, and the strength, heat resistance and solvent resistance and other properties are reduced. If the amount of the amine chain extender is too large, the prepolymer and the chain extender will agglomerate, resulting in an uneven product.
本发明中，若功能性填料的用量过多，则性能无法进一步提升且会造成团聚。In the present invention, if the amount of the functional filler is too much, the performance cannot be further improved and agglomeration may occur.
作为本发明一种优选的技术方案，所述制备方法包括以下步骤：As a preferred technical solution of the present invention, the preparation method comprises the following steps:
(1)将聚醚多元醇加入反应釜中，在90-120℃(例如可以是90℃、100℃、110℃或120℃等)的负压(例如可以是-0.05MPa等)下脱水0.5-2h(例如可以是0.5h、1h、1.5h或2h等)，然后加入活性剂继续脱水，直至聚醚多元醇的含水量≤0.05％，随后降温至40-60℃(例如可以是40℃、50℃或60℃等)加入异氰酸酯，然后升温至80-90℃(例如可以是80℃、85℃或90等)，恒温2-3h(例如可以是2h、2.5h或3h等)，得到含-NCO质量分数为13-16％(例如可以是13％、14％、15％或16％等)的预聚体，然后真空脱水，制得A组分；(1) adding a polyether polyol into a reaction kettle, dehydrating the polyether polyol at 90-120° C. (for example, 90° C., 100° C., 110° C. or 120° C.) under negative pressure (for example, −0.05 MPa, etc.) for 0.5-2 h (for example, 0.5 h, 1 h, 1.5 h or 2 h, etc.), then adding an active agent to continue dehydrating the polyether polyol until the water content of the polyether polyol is ≤ 0.05%, then cooling the polyether polyol to 40-60° C. (for example, 40° C., 50° C. or 60° C.), adding isocyanate, then heating the polyether polyol to 80-90° C. (for example, 80° C., 85° C. or 90° C.), maintaining the temperature for 2-3 h (for example, 2 h, 2.5 h or 3 h, etc.), obtaining a prepolymer having an -NCO mass fraction of 13-16% (for example, 13%, 14%, 15% or 16%, etc.), and then vacuum dehydrating the prepolymer to obtain component A;
其中，异氰酸酯、聚醚多元醇和活性剂的质量比为(40-55):(44-55):(1-5)；Wherein, the mass ratio of isocyanate, polyether polyol and activator is (40-55):(44-55):(1-5);
将端氨基聚醚、胺扩链剂、功能性填料和助剂依次加入并在高速分散机中，分散30-60min(例如可以是30min、40min、50min或60min等)，然后在40-60℃下干燥，得到B组分；Add the amino-terminated polyether, amine chain extender, functional filler and auxiliary agent in sequence and disperse in a high-speed disperser for 30-60 minutes (for example, 30 minutes, 40 minutes, 50 minutes or 60 minutes, etc.), and then dry at 40-60° C. to obtain component B;
其中，端氨基聚醚、胺扩链剂、功能性填料和助剂的质量比为(40-60):(20-35):(0-20):(0-5)；Wherein, the mass ratio of the amino-terminated polyether, the amine chain extender, the functional filler and the auxiliary agent is (40-60):(20-35):(0-20):(0-5);
(2)将所述A组分和B组分按照1:1的体积比混合，得到改性聚脲材料；(2) mixing the component A and the component B in a volume ratio of 1:1 to obtain a modified polyurea material;
(3)将所述改性聚脲材料喷涂在聚合物膜的至少一侧表面上，得到改性集流体基膜。(3) Spraying the modified polyurea material onto at least one surface of a polymer film to obtain a modified current collector base film.
第三方面，本发明提供一种复合集流体，所述复合集流体包括如第一方面所述的改性集流体基膜或如第二方面所述的制备方法制得的改性集流体基膜，以及设置在所述改性集流体基膜至少一侧表面上的导电层。In a third aspect, the present invention provides a composite current collector, comprising the modified current collector base film as described in the first aspect or the modified current collector base film prepared by the preparation method as described in the second aspect, and a conductive layer arranged on at least one side surface of the modified current collector base film.
作为本发明一种优选的技术方案，所述导电层的厚度为500-2000nm，例如可以是500nm、1000nm、1500nm或2000nm等，优选为800-1200nm。As a preferred technical solution of the present invention, the thickness of the conductive layer is 500-2000 nm, for example, it can be 500 nm, 1000 nm, 1500 nm or 2000 nm, etc., preferably 800-1200 nm.
本发明中，导电层太薄，导电性较差；太厚，则制备的复合集流体太厚重，不利于提升电池的能量密度。考虑到导电性并兼顾能量密度的提升，优选厚度为800-1200nm。In the present invention, if the conductive layer is too thin, the conductivity is poor; if it is too thick, the prepared composite current collector is too heavy, which is not conducive to improving the energy density of the battery. Considering the conductivity and the improvement of energy density, the preferred thickness is 800-1200nm.
优选地，所述导电层的制备方法包括物理气相沉积法、电镀法或化学镀法中的任意一种或至少两种的组合。Preferably, the preparation method of the conductive layer includes any one of physical vapor deposition, electroplating or chemical plating, or a combination of at least two of them.
优选地，所述物理气相沉积法包括蒸镀法和/或磁控溅射法。Preferably, the physical vapor deposition method includes evaporation and/or magnetron sputtering.
优选地，所述电镀法中，制备导电层的具体参数包括：电流强度为20000-50000A，例如可以是20000A、30000A、40000A或50000A等，电流密度为5000-10000A/m2，例如可以是5000A/m2、6000A/m2、7000A/m2、8000A/m2、9000A/m2或10000A/m2等，铜离子的浓度为65-100g/L，例如可以是65g/L、75g/L、85g/L、95g/L或100g/L等，电解液中氢离子的浓度为90-110g/L，例如可以是90g/L、95g/L、100g/L、105g/L或110g/L等。Preferably, in the electroplating method, specific parameters for preparing the conductive layer include: current intensity of 20000-50000A, such as 20000A, 30000A, 40000A or 50000A, etc., current density of 5000-10000A/m2 , such as 5000A/m2 , 6000A/m2 , 7000A/m2 , 8000A/m2 , 9000A/m2 or 10000A/m2 , the concentration of copper ions is 65-100 g/L, for example, it can be 65 g/L, 75 g/L, 85 g/L, 95 g/L or 100 g/L, and the concentration of hydrogen ions in the electrolyte is 90-110 g/L, for example, it can be 90 g/L, 95 g/L, 100 g/L, 105 g/L or 110 g/L, etc.
优选地，所述磁控溅射法中，制备导电层的具体参数包括：功率为2-20KW，例如可以是2KW、5KW、10KW、15KW或20KW等，真空舱体的真空度≤0.1Pa，例如可以是0.1Pa、0.05Pa或0.01Pa等，气源的流量为20-500mL/min，例如可以是20mL/min、50mL/min、100mL/min、200mL/min或500mL/min等，每次镀膜时间为0.1-120s，例如可以是0.1s、1s、10s、50s、100s或120s等。Preferably, in the magnetron sputtering method, specific parameters for preparing the conductive layer include: a power of 2-20KW, for example, 2KW, 5KW, 10KW, 15KW or 20KW, etc., a vacuum degree of the vacuum chamber ≤0.1Pa, for example, 0.1Pa, 0.05Pa or 0.01Pa, etc., a flow rate of the gas source of 20-500mL/min, for example, 20mL/min, 50mL/min, 100mL/min, 200mL/min or 500mL/min, etc., and a coating time of 0.1-120s, for example, 0.1s, 1s, 10s, 50s, 100s or 120s, etc.
优选地，所述导电层和所述改性集流体基膜之间还设置有粘结层，所述粘结层的材料包括氧化铝、氧化硅、氧化钛、单质镍、单质铬、单质钛、镍铬合金、镍铬铜合金或硅铝合金中的任意一种或至少两种的组合。Preferably, a bonding layer is also provided between the conductive layer and the modified current collector base film, and the material of the bonding layer includes any one of aluminum oxide, silicon oxide, titanium oxide, elemental nickel, elemental chromium, elemental titanium, nickel-chromium alloy, nickel-chromium-copper alloy or silicon-aluminum alloy, or a combination of at least two thereof.
优选地，相邻所述导电层和粘结层之间的粘结力为100-900N/m，例如可以是100N/m、300N/m、500N/m、700N/m或900N/m等。Preferably, the bonding force between adjacent conductive layers and bonding layers is 100-900 N/m, for example, 100 N/m, 300 N/m, 500 N/m, 700 N/m or 900 N/m.
本发明中，粘结层与导电层的粘结力会影响复合集流体变形过程中导电层与聚合物膜之间的相对运动，从而影响导电层的变形裂变行为，进而影响其对电池安全性能提升的效果。In the present invention, the bonding force between the bonding layer and the conductive layer will affect the relative movement between the conductive layer and the polymer film during the deformation of the composite current collector, thereby affecting the deformation and fission behavior of the conductive layer, and further affecting its effect on improving the safety performance of the battery.
优选地，所述导电层远离改性集流体基膜的一侧表面上设置有保护层，所述保护层的材料包括单质镍、单质铬、镍基合金、铜基合金、氧化铝、氧化镍、氧化铬、氧化钴、铬酸铜、亚铬酸铜、石墨、炭黑、碳纳米量子点、碳纳米管、碳纳米纤维或石墨烯中的任意一种或至少两种的组合。Preferably, a protective layer is provided on the surface of the conductive layer away from the modified current collector base film, and the material of the protective layer includes any one of elemental nickel, elemental chromium, nickel-based alloy, copper-based alloy, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, copper chromate, copper chromite, graphite, carbon black, carbon nano-quantum dots, carbon nanotubes, carbon nanofibers or graphene, or a combination of at least two of them.
需要说明的是，当聚合物膜的两侧表面上均设置有保护层时，两侧保护层的材料可以一致也可以不一致，厚度可以一致也可以不一致。It should be noted that when protective layers are provided on both sides of the polymer film, the materials of the protective layers on both sides may be consistent or inconsistent, and the thicknesses may be consistent or inconsistent.
本发明中，设置保护层的作用是防止导电层被化学腐蚀或物理损坏。In the present invention, the protective layer is provided to prevent the conductive layer from being chemically corroded or physically damaged.
优选地，所述保护层的厚度为10-100nm，例如可以是10nm、30nm、50nm、70nm或90nm等，优选为20-80nm。Preferably, the thickness of the protective layer is 10-100 nm, for example, 10 nm, 30 nm, 50 nm, 70 nm or 90 nm, etc., preferably 20-80 nm.
优选地，所述保护层的厚度≤导电层的厚度的十分之一。Preferably, the thickness of the protective layer is ≤ one tenth of the thickness of the conductive layer.
优选地，所述保护层的制备方法包括物理气相沉积法、化学气相沉积法、原位成型法或涂布法中的任意一种或至少两种的组合。Preferably, the preparation method of the protective layer includes any one of physical vapor deposition, chemical vapor deposition, in-situ forming or coating, or a combination of at least two of them.
第四方面，本发明提供一种锂离子电池，所述锂离子电池的电极极片中包括如第三方面所述的复合集流体，或包括基于第一方面所述的改性集流体基膜制成的复合集流体。In a fourth aspect, the present invention provides a lithium-ion battery, wherein the electrode plate of the lithium-ion battery includes the composite current collector as described in the third aspect, or includes a composite current collector made based on the modified current collector base film described in the first aspect.
本发明所述的数值范围不仅包括上述例举的点值，还包括没有例举出的上述数值范围之间的任意的点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。The numerical range described in the present invention not only includes the point values listed above, but also includes any point values between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the range.
相对于现有技术，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明采用改性聚脲涂层对聚合物膜进行改性，可以改善聚合物膜的极性，使其与导电层的接触更加紧密，增加粘结力，并且改性后的聚脲涂层具有优异的刚度、强度、高应变速率敏感性和优异的力学性能，避免在集流体的制备过程中产生缺陷，其次，由于改性聚脲涂层具有良好的防腐性能和阻隔性能，因此有助于聚合物膜抵御电解液的侵蚀。最后，改性聚脲涂层具有高热分解温度和优异的热稳定性，可抵御高温环境。综上，本发明提供的改性集流体基膜具有优异的力学性能、热稳定性和粘结力，在后续复合集流体的制备过程中不易产生损伤，可促进复合集流体的推广和应用，基于此制备的电池具有优异的物化性能及安全性能。The present invention uses a modified polyurea coating to modify the polymer film, which can improve the polarity of the polymer film, make it more closely contacted with the conductive layer, increase the bonding force, and the modified polyurea coating has excellent stiffness, strength, high strain rate sensitivity and excellent mechanical properties, avoiding defects in the preparation process of the current collector. Secondly, since the modified polyurea coating has good corrosion resistance and barrier properties, it helps the polymer film to resist the erosion of the electrolyte. Finally, the modified polyurea coating has a high thermal decomposition temperature and excellent thermal stability, and can withstand high temperature environments. In summary, the modified current collector base film provided by the present invention has excellent mechanical properties, thermal stability and bonding force, is not easy to be damaged in the subsequent preparation process of the composite current collector, can promote the promotion and application of the composite current collector, and the battery prepared based on this has excellent physical and chemical properties and safety performance.
具体实施方式DETAILED DESCRIPTION
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only used to help understand the present invention and should not be regarded as specific limitations of the present invention.
实施例1Example 1
本实施例提供了一种改性集流体基膜，所述改性集流体基膜包括聚合物膜，以及设置在所述聚合物两侧表面上的改性聚脲涂层；This embodiment provides a modified current collector base film, the modified current collector base film comprising a polymer film and a modified polyurea coating disposed on both side surfaces of the polymer;
所述改性聚脲涂层的单面厚度为100nm；The single-sided thickness of the modified polyurea coating is 100 nm;
所述聚合物膜的材料为PP，厚度为4.5μm。The polymer film is made of PP and has a thickness of 4.5 μm.
本实施例还提供了上述改性集流体基膜的制备方法，所述制备方法包括以下步骤：This embodiment also provides a method for preparing the modified current collector base film, the preparation method comprising the following steps:
(1)将丙二醇聚醚PPG2000加入反应釜中，在100℃、-0.05MPa下脱水1h，然后加入亚烷基碳酸酯继续脱水，直至丙二醇聚醚PPG2000的含水量≤0.05％，随后降温至50℃加入2,4-二甲基癸二异氰酸酯，然后升温至80℃，恒温2h，得到含-NCO质量分数为15％的预聚体，然后真空脱水，制得A组分；(1) Add propylene glycol polyether PPG2000 into a reaction kettle, dehydrate at 100° C. and −0.05 MPa for 1 h, then add alkylene carbonate to continue dehydration until the water content of propylene glycol polyether PPG2000 is ≤0.05%, then cool to 50° C. and add 2,4-dimethyldecane diisocyanate, then heat to 80° C. and keep the temperature constant for 2 h to obtain a prepolymer containing 15% of -NCO by mass, and then vacuum dehydrate to obtain component A;
其中，2,4-二甲基癸二异氰酸酯、丙二醇聚醚PPG2000和亚烷基碳酸酯的质量比为50:46:4；Among them, the mass ratio of 2,4-dimethyldecane diisocyanate, propylene glycol polyether PPG2000 and alkylene carbonate is 50:46:4;
将55％聚醚胺D-2000、20％十二烷二胺、5％异佛尔酮二胺、15％次磷酸铝、1％SBS和4％丙酮依次加入并在高速分散机中，分散45min后，于60℃下烘干，得到B组分；55% polyetheramine D-2000, 20% dodecanediamine, 5% isophoronediamine, 15% aluminum hypophosphite, 1% SBS and 4% acetone were added in sequence and dispersed in a high-speed disperser for 45 minutes, and then dried at 60°C to obtain component B;
其中，聚醚胺D-2000、胺扩链剂(包括十二烷二胺和异佛尔酮二胺)、次磷酸铝和助剂(SBS和丙酮)的质量比为55:25:15:5；The mass ratio of polyetheramine D-2000, amine chain extender (including dodecanediamine and isophoronediamine), aluminum hypophosphite and additives (SBS and acetone) is 55:25:15:5;
(2)将所述A组分和B组分装入喷涂机，按照体积比1:1喷涂在所述聚合物膜的两侧表面上，得到改性集流体基膜。(2) The component A and the component B are loaded into a sprayer and sprayed on both sides of the polymer film in a volume ratio of 1:1 to obtain a modified current collector base film.
本实施例还提供了一种复合集流体，所述复合集流体包括如上所述的改性集流体基膜；This embodiment also provides a composite current collector, the composite current collector comprising the modified current collector base film as described above;
粘结层，所述粘结层设置在所述改性集流体基膜的两侧表面上，材料为镍铬合金，单面厚度为5nm；A bonding layer, which is disposed on both sides of the modified current collector base film and is made of nickel-chromium alloy with a single-side thickness of 5 nm;
铜层，所述铜层沿着远离所述改性集流体基膜的方向设置在所述粘结层的表面上，单面厚度为900nm；A copper layer, wherein the copper layer is disposed on the surface of the bonding layer in a direction away from the modified current collector base film, and has a single-side thickness of 900 nm;
保护层，所述保护层沿着远离所述改性集流体基膜的方向设置在所述铜层的表面上，材料为氧化铬，单面厚度均为20nm。A protective layer is arranged on the surface of the copper layer in a direction away from the modified current collector base film, the material of the protective layer is chromium oxide, and the thickness of a single side is 20 nm.
本实施例还提供了上述复合集流体的制备方法，所述制备方法包括以下步骤：This embodiment also provides a method for preparing the composite current collector, which comprises the following steps:
(Ⅰ)将改性集流体基膜置于磁控溅射机内，以镍铬合金靶为靶材，在膜的两面各沉积一层5nm的粘结层，具体工艺条件为：以镍铬靶(纯度：99.99％)为靶材，功率为4.0KW，氩气流量为50mL/min，镀膜真空度为0.08Pa，镀膜时间为1s，镀膜过程中主辊的温度为10℃；(I) The modified current collector substrate film is placed in a magnetron sputtering machine, and a 5 nm bonding layer is deposited on both sides of the film using a nickel-chromium alloy target as the target material. The specific process conditions are: using a nickel-chromium target (purity: 99.99%) as the target material, the power is 4.0 KW, the argon flow rate is 50 mL/min, the coating vacuum is 0.08 Pa, the coating time is 1 s, and the temperature of the main roller during the coating process is 10°C;
(Ⅱ)将上述制备出的表面含有粘结层的复合膜置于磁控溅射机内，在膜的两面各沉积制备一层厚度为900nm的铜层，制备条件为：以铜靶(纯度：99.99％)为靶材，功率为12.0KW，氩气流量为70mL/min，镀膜真空度为0.1Pa，镀膜时间为100s，镀膜过程中主辊的冷却温度为-5℃；(II) The composite film with the bonding layer prepared above was placed in a magnetron sputtering machine, and a copper layer with a thickness of 900 nm was deposited on both sides of the film. The preparation conditions were: a copper target (purity: 99.99%) was used as the target material, the power was 12.0 KW, the argon gas flow rate was 70 mL/min, the coating vacuum was 0.1 Pa, the coating time was 100 s, and the cooling temperature of the main roller during the coating process was -5°C;
(Ⅲ)将上述制备出包含粘结层及铜层的复合膜置于0.5g/L铬酐水溶液(25℃)中浸泡处理20s，处理完成后再通过纯水槽进行清洗，清洗完成后，置于60℃烘箱内进行烘干，即制备出所述复合集流体。(III) The composite film comprising the bonding layer and the copper layer prepared above is immersed in a 0.5 g/L chromic anhydride aqueous solution (25° C.) for 20 seconds, and then washed with a pure water tank. After washing, it is placed in an oven at 60° C. for drying to prepare the composite current collector.
实施例2Example 2
本实施例与实施例1的不同之处为，所述胺扩链剂替换为17％十二烷二胺和8％异佛尔酮二胺的组合。The difference between this embodiment and embodiment 1 is that the amine chain extender is replaced by a combination of 17% dodecanediamine and 8% isophoronediamine.
其余制备方法和参数与实施例1保持一致。The rest of the preparation methods and parameters were the same as those in Example 1.
实施例3Example 3
本实施例与实施例1的不同之处为，所述胺扩链剂替换为15％十二烷二胺和10％异佛尔酮二胺的组合。The difference between this embodiment and embodiment 1 is that the amine chain extender is replaced by a combination of 15% dodecanediamine and 10% isophoronediamine.
其余制备方法和参数与实施例1保持一致。The rest of the preparation methods and parameters were the same as those in Example 1.
实施例4Example 4
本实施例与实施例1的不同之处为，所述胺扩链剂替换为8％十二烷二胺和17％异佛尔酮二胺的组合。The difference between this embodiment and embodiment 1 is that the amine chain extender is replaced by a combination of 8% dodecanediamine and 17% isophoronediamine.
其余制备方法和参数与实施例1保持一致。The rest of the preparation methods and parameters were the same as those in Example 1.
实施例5Example 5
本实施例与实施例1的不同之处为，所述胺扩链剂替换为22％十二烷二胺和3％异佛尔酮二胺的组合。The difference between this embodiment and embodiment 1 is that the amine chain extender is replaced by a combination of 22% dodecanediamine and 3% isophoronediamine.
其余制备方法和参数与实施例1保持一致。The rest of the preparation methods and parameters were the same as those in Example 1.
实施例6Example 6
本实施例与实施例1的不同之处为，所述胺扩链剂替换为5％十二烷二胺和20％异佛尔酮二胺的组合。The difference between this embodiment and embodiment 1 is that the amine chain extender is replaced by a combination of 5% dodecanediamine and 20% isophoronediamine.
其余制备方法和参数与实施例1保持一致。The rest of the preparation methods and parameters were the same as those in Example 1.
实施例7Example 7
本实施例与实施例3的不同之处为，所述次磷酸铝替换为马来酸二甲酯。The difference between this embodiment and embodiment 3 is that the aluminum hypophosphite is replaced by dimethyl maleate.
其余制备方法和参数与实施例3保持一致。The rest of the preparation methods and parameters were the same as those in Example 3.
实施例8Example 8
本实施例与实施例3的不同之处为，所述次磷酸铝替换为5％硅烷偶联剂KH-570和15％特级松香的组合。The difference between this embodiment and embodiment 3 is that the aluminum hypophosphite is replaced by a combination of 5% silane coupling agent KH-570 and 15% special grade rosin.
其余制备方法和参数与实施例3保持一致。The rest of the preparation methods and parameters were the same as those in Example 3.
实施例9Embodiment 9
本实施例与实施例3的不同之处为，所述次磷酸铝和助剂的组合替换为3％的氨化聚丙烯PP-g-NH2、16％的2,2-二羟甲基丙酸和1％二月桂酸二丁基锡的组合。The difference between this embodiment and embodiment 3 is that the combination of aluminum hypophosphite and the auxiliary agent is replaced by a combination of 3% ammoniated polypropylene PP-g-NH2 , 16% 2,2-dihydroxymethylpropionic acid and 1% dibutyltin dilaurate.
其余制备方法和参数与实施例3保持一致。The rest of the preparation methods and parameters were the same as those in Example 3.
实施例10Example 10
本实施例与实施例3的不同之处为，步骤(1)所述胺扩链剂替换为3,3'-二氯-4,4'-二氨基苯基甲烷。The difference between this embodiment and embodiment 3 is that the amine chain extender in step (1) is replaced by 3,3'-dichloro-4,4'-diaminophenylmethane.
其余制备方法和参数与实施例3保持一致。The rest of the preparation methods and parameters were the same as those in Example 3.
实施例11Embodiment 11
本实施例与实施例3的不同之处为，改性聚脲涂层的单面厚度为30nm。The difference between this embodiment and embodiment 3 is that the single-side thickness of the modified polyurea coating is 30 nm.
其余制备方法和参数与实施例3保持一致。The rest of the preparation methods and parameters were the same as those in Example 3.
实施例12Example 12
本实施例与实施例3的不同之处为，改性聚脲涂层的单面厚度为200nm。The difference between this embodiment and embodiment 3 is that the single-side thickness of the modified polyurea coating is 200 nm.
其余制备方法和参数与实施例3保持一致。The rest of the preparation methods and parameters were the same as those in Example 3.
对比例1Comparative Example 1
本对比例与实施例1的不同之处为，改性集流体基膜替换为纯的PP膜，即不对PP膜进行改性。The difference between this comparative example and Example 1 is that the modified current collector base film is replaced by a pure PP film, that is, the PP film is not modified.
其余制备方法和参数与实施例1保持一致。The rest of the preparation methods and parameters were the same as those in Example 1.
对比例2Comparative Example 2
本对比例与实施例1的不同之处为，步骤(1)中不添加次磷酸铝，即不对聚脲涂层进行改性。The difference between this comparative example and Example 1 is that aluminum hypophosphite is not added in step (1), that is, the polyurea coating is not modified.
其余制备方法和参数与实施例1保持一致。The rest of the preparation methods and parameters were the same as those in Example 1.
性能测试Performance Testing
一、对上述实施例和对比例制备的复合集流体进行粘结力、拉伸强度和断裂伸长率进行测试：1. The bonding force, tensile strength and elongation at break of the composite current collectors prepared in the above examples and comparative examples were tested:
1)粘结力：将复合集流体样品裁取宽为24mm、长度为300mm的试样，将裁取试样的一端胶粘面对折，形成约12mm长的折叠层；将试样的另一端粘贴在钢板的一端，并用胶粘带压滚机以600mm/min的速度滚压两次；置于电子剥离试验机中，设置试验速度为300mm/min、试样宽度为24mm；设备自动记录剥离过程中的力值，并依此报告试样的剥离强度。1) Adhesion: Cut the composite current collector sample into a sample with a width of 24 mm and a length of 300 mm, fold the adhesive surface of one end of the cut sample to form a folded layer of about 12 mm long; stick the other end of the sample to one end of the steel plate, and roll it twice with an adhesive tape roller at a speed of 600 mm/min; place it in an electronic peeling tester, set the test speed to 300 mm/min and the sample width to 24 mm; the equipment automatically records the force value during the peeling process and reports the peel strength of the sample accordingly.
2)拉伸强度：按照标准GB/T 1040.3-2006对上述制备的复合集流体的拉伸强度进行测试。2) Tensile strength: The tensile strength of the composite current collector prepared above was tested according to standard GB/T 1040.3-2006.
3)断裂伸长率：按照标准GB/T 1040.3-2006对上述制备的复合集流体的断裂伸长率进行测试。3) Elongation at break: The elongation at break of the composite current collector prepared above was tested according to the standard GB/T 1040.3-2006.
二、基于上述复合集流体制备锂离子电池，然后进行安全性能测试。2. Prepare a lithium-ion battery based on the above composite current collector and then conduct a safety performance test.
1)电池制备：对于正极，正极集流体采用传统铝箔(厚度为13μm)，正极材料采用LiNi0.6Mn0.2Co0.2O2(NCM622)；对于负极：负极集流体采用本发明制备的复合集流体，负极电极材料采用人造石墨；对于隔膜，采用氧化铝陶瓷涂覆聚乙烯隔膜(厚度为25μm)；对于电解液，采用1mol·L-1LiPF6的碳酸酯溶液，碳酸酯包括质量比为1:1:1的碳酸丙烯酯、碳酸乙烯酯和碳酸甲乙酯；利用上述材料，按照相关流程组装锂离子电池；1) Battery preparation: for the positive electrode, the positive electrode current collector adopts traditional aluminum foil (thickness of 13 μm), and the positive electrode material adopts LiNi0.6 Mn0.2 Co0.2 O2 (NCM622); for the negative electrode: the negative electrode current collector adopts the composite current collector prepared by the present invention, and the negative electrode material adopts artificial graphite; for the diaphragm, an alumina ceramic coated polyethylene diaphragm (thickness of 25 μm) is adopted; for the electrolyte, a carbonate solution of 1 mol·L-1 LiPF6 is adopted, and the carbonate comprises propylene carbonate, ethylene carbonate and ethyl methyl carbonate in a mass ratio of 1:1:1; the above materials are used to assemble a lithium ion battery according to the relevant process;
2)安全性能测试：采用针刺实验验证电池的安全性能，具体如下：将上述制备的电池置于针刺实验装置中，其中刺针的直径为3mm，针刺速度为10mm/s，采样间隔为100ms，采样时间为15min。若安全性能合格，则电池应不爆炸、不起火、不冒烟，以100个电池为测试样本。2) Safety performance test: The safety performance of the battery is verified by a needle puncture test, as follows: the battery prepared above is placed in a needle puncture test device, where the diameter of the needle is 3mm, the puncture speed is 10mm/s, the sampling interval is 100ms, and the sampling time is 15min. If the safety performance is qualified, the battery should not explode, catch fire, or smoke, and 100 batteries are used as test samples.
上述测试结果如表1所示。The above test results are shown in Table 1.
表1Table 1
分析：analyze:
由上表可知，本发明采用改性聚脲涂层对聚合物膜进行改性，改性聚脲涂层具有优异的刚度、强度、高应变速率敏感性和优异的力学性能，因此制备得到的改性集流体基膜具有优异的力学性能、热稳定性和粘结力，且在后续复合集流体的制备过程中不易产生损伤。基于此制备的电池具有优异的物化性能及安全性能。As can be seen from the above table, the present invention uses a modified polyurea coating to modify the polymer film, and the modified polyurea coating has excellent stiffness, strength, high strain rate sensitivity and excellent mechanical properties, so the prepared modified current collector base film has excellent mechanical properties, thermal stability and adhesion, and is not easy to be damaged during the subsequent preparation process of the composite current collector. The battery prepared based on this has excellent physical and chemical properties and safety performance.
由实施例1与实施例5-6可知，长碳链二胺和脂环族二胺的质量比过大或过大均会导致聚脲材料的力学性能的提高达不到最佳效果，电池的安全性能减弱。It can be seen from Example 1 and Examples 5-6 that if the mass ratio of the long carbon chain diamine to the alicyclic diamine is too large or too large, the mechanical properties of the polyurea material cannot be improved to the best effect, and the safety performance of the battery is weakened.
由实施例1与实施例10可知，若将步骤(1)所述胺扩链剂替换为芳香族扩链剂3,3'-二氯-4,4'-二氨基苯基甲烷，则聚脲材料的力学性能得不到显著提升，且在集流体的制备过程中易产生缺陷。It can be seen from Examples 1 and 10 that if the amine chain extender in step (1) is replaced with the aromatic chain extender 3,3'-dichloro-4,4'-diaminophenylmethane, the mechanical properties of the polyurea material cannot be significantly improved, and defects are easily generated during the preparation of the current collector.
由实施例1与实施例11-12可知，若改性聚脲涂层的单面厚度过小，则对集流体基膜的改性效果不明显；若改性聚脲涂层的单面厚度较大，虽然会使得集流体性能提升，但提升幅度小，且易造成厚度不均匀，成本增大。It can be seen from Example 1 and Examples 11-12 that if the single-sided thickness of the modified polyurea coating is too small, the modification effect on the current collector base film is not obvious; if the single-sided thickness of the modified polyurea coating is larger, although the current collector performance will be improved, the improvement is small, and it is easy to cause uneven thickness and increase costs.
由实施例1与对比例1可知，若不对PP膜进行改性，则集流体基膜的力学性能得不到改善，稳定性差，在遭受应力或化学试剂等伤害时，更易出现低性能或是缺陷，从而对复合集流体的物化性能造成影响。It can be seen from Example 1 and Comparative Example 1 that if the PP film is not modified, the mechanical properties of the current collector base film cannot be improved, the stability is poor, and when subjected to damage such as stress or chemical reagents, it is more likely to have low performance or defects, thereby affecting the physical and chemical properties of the composite current collector.
由实施例1与对比例2可知，若不对聚脲涂层进行改性，由于其应变速率敏感性和力学性能不如改性聚脲涂层，因此对集流体基膜的性能改善幅度小，达不到最佳效果。It can be seen from Example 1 and Comparative Example 2 that if the polyurea coating is not modified, since its strain rate sensitivity and mechanical properties are not as good as those of the modified polyurea coating, the performance improvement of the current collector base film is small and the optimal effect cannot be achieved.
申请人声明，本发明通过上述实施例来说明本发明的技术方案，但本发明并不局限于上述实施例，即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。The applicant declares that the present invention illustrates the technical solution of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
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| CN202410869756.3ACN118610475A (en) | 2024-06-28 | 2024-06-28 | A modified current collector base film and its preparation method and application |
| Application Number | Priority Date | Filing Date | Title |
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| CN202410869756.3ACN118610475A (en) | 2024-06-28 | 2024-06-28 | A modified current collector base film and its preparation method and application |
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|---|---|---|---|---|
| US5578372A (en)* | 1990-10-09 | 1996-11-26 | Daicel Chemical Industries, Ltd. | Heat-weldable composite films and method of production thereof |
| US5759695A (en)* | 1997-06-05 | 1998-06-02 | Huntsman Petrochemical Corporation | Polyurea elastomer systems with improved adhesion to substrates |
| CN113801552A (en)* | 2021-10-18 | 2021-12-17 | 成都托展新材料股份有限公司 | Modified polyurea composition, preparation method and application thereof |
| CN114085330A (en)* | 2021-11-18 | 2022-02-25 | 广州集泰化工股份有限公司 | Modified acrylic emulsion and preparation method thereof |
| CN116632253A (en)* | 2023-05-08 | 2023-08-22 | 华中科技大学 | A functional collector and its preparation method and application |
| CN118039920A (en)* | 2024-02-20 | 2024-05-14 | 江阴纳力新材料科技有限公司 | Composite current collector and preparation method and application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5578372A (en)* | 1990-10-09 | 1996-11-26 | Daicel Chemical Industries, Ltd. | Heat-weldable composite films and method of production thereof |
| US5759695A (en)* | 1997-06-05 | 1998-06-02 | Huntsman Petrochemical Corporation | Polyurea elastomer systems with improved adhesion to substrates |
| CN113801552A (en)* | 2021-10-18 | 2021-12-17 | 成都托展新材料股份有限公司 | Modified polyurea composition, preparation method and application thereof |
| CN114085330A (en)* | 2021-11-18 | 2022-02-25 | 广州集泰化工股份有限公司 | Modified acrylic emulsion and preparation method thereof |
| CN116632253A (en)* | 2023-05-08 | 2023-08-22 | 华中科技大学 | A functional collector and its preparation method and application |
| CN118039920A (en)* | 2024-02-20 | 2024-05-14 | 江阴纳力新材料科技有限公司 | Composite current collector and preparation method and application thereof |
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