WO2022141069A1 - 复合集流体及其制备方法以及电化学装置 - Google Patents

复合集流体及其制备方法以及电化学装置 Download PDF

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WO2022141069A1
WO2022141069A1 PCT/CN2020/140909 CN2020140909W WO2022141069A1 WO 2022141069 A1 WO2022141069 A1 WO 2022141069A1 CN 2020140909 W CN2020140909 W CN 2020140909W WO 2022141069 A1 WO2022141069 A1 WO 2022141069A1
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current collector
composite current
polymer film
metal layer
layer
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French (fr)
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杨晓兵
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • the present application relates to the field of electrochemistry, in particular to a composite current collector and a preparation method thereof and an electrochemical device.
  • the current collector runs through the entire processing process of electrochemical devices (such as lithium-ion batteries) and serves the entire life cycle of electrochemical devices. It is the carrier of active materials in electrochemical devices and provides channels for electron transport. component.
  • the current collector is closely related to the energy density of the cell, and the energy density of the cell can be increased by reducing the thickness of the current collector.
  • the composite current collector obtained by arranging the conductive layer on the surface of the low-density polymer film can effectively reduce the density of the lithium ion battery current collector and improve the weight energy density of the lithium ion battery.
  • the adhesion between the conductive layer and the polymer film is low, and the conductive layer on the surface of the composite current collector falls off during the processing of the pole piece and the life cycle of the lithium-ion battery, which seriously affects the cycle life and high-temperature storage performance of the lithium-ion battery.
  • the purpose of the present application is to provide a composite current collector, a preparation method thereof, and an electrochemical device.
  • the energy density of the electrochemical device can be increased, and the cycle performance and high temperature storage performance of the electrochemical device can be improved.
  • the present application provides a composite current collector comprising a polymer film layer and a metal layer disposed on at least one side of the polymer film layer, wherein the polymer film layer and the metal layer are The ionic bond structure [M + COO - ] is combined, where M is a metal element in the metal layer.
  • the metal element in the metal layer includes at least one of aluminum, copper, nickel, iron, titanium, silver, gold, cobalt, chromium, molybdenum, or tungsten.
  • the thickness of the metal layer is 100 nm to 5000 nm.
  • the thickness of the polymer film layer is 2 ⁇ m to 36 ⁇ m.
  • carboxyl groups are grafted on the surface of the polymer film layer.
  • the present application provides a method for preparing the composite current collector of the present application, comprising the steps of: disposing a metal layer on a polymer film substrate grafted with carboxyl groups to obtain a composite current collector.
  • the preparation method of the composite current collector includes the steps of: a. performing oxygen plasma or corona treatment on the polymer film to generate hydroxyl groups carrying active hydrogen atoms; b. The film is coated or impregnated with an acid anhydride solution to cause a carboxylation reaction; c. After the carboxylation reaction, the solvent in the acid anhydride solution is evaporated to obtain a polymer film matrix grafted with carboxyl groups; d. A metal layer is deposited on the material film substrate to obtain a composite current collector.
  • the polymer film material includes polyethylene, polypropylene, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate At least one of p-phenylenediamine, polyimide, polycarbonate, polyether ether ketone, polyoxymethylene, poly-p-phenylene sulfide, poly-p-phenylene oxide, polyvinyl chloride, polyamide or polytetrafluoroethylene.
  • the acid anhydride includes at least one of phthalic anhydride, maleic anhydride, or polyolefin-grafted maleic anhydride.
  • the present application provides an electrochemical device comprising the composite current collector of the present application.
  • the present application at least includes the following beneficial effects: the ionic bond structure of the composite current collector of the present application can improve the adhesion between the metal layer and the polymer layer, improve the phenomenon of delamination and shedding of the composite current collector, and simultaneously When applied to an electrochemical device, the energy density of the electrochemical device can be increased, and the cycle performance and high-temperature storage performance of the electrochemical device can be improved.
  • FIG. 1 is a partial cross-sectional structural schematic diagram of a composite current collector according to a specific embodiment of the present application, wherein,
  • FIG. 2 is a schematic diagram of steps for preparing a composite current collector according to a specific embodiment of the present application.
  • FIG. 3 is a schematic diagram of an infrared spectrum of the PET film of Example 1 of the application after carboxyl groups are grafted.
  • FIG. 4 is a schematic diagram of an infrared spectrum of the PET film of Example 2 of the application after carboxyl groups are grafted.
  • Example 5 is a schematic diagram of an infrared spectrum of the PET film of Example 3 of the present application after carboxyl groups are grafted.
  • Figure 5a is a schematic diagram of the infrared spectrum of the PET film.
  • Figure 5b is the infrared spectrum of the acid anhydride grafted layer.
  • FIG. 6 is a schematic diagram of the infrared spectrum of the PET film of Example 4 of the application after carboxyl groups are grafted.
  • FIG. 7 is a schematic diagram of an infrared spectrum of the PET film of Example 5 of the present application after carboxyl groups are grafted.
  • FIG. 8 is a schematic diagram of an infrared spectrum of the PET film of Example 6 of the application after carboxyl groups are grafted.
  • FIG. 9 is a schematic diagram of an infrared spectrum of the PET film of Comparative Example 1 of the present application.
  • FIG. 10 is a schematic diagram of the infrared spectrum of the PET film of Comparative Example 2 of the present application after being coated with acrylate.
  • FIG. 11 is a schematic diagram of the infrared spectrum of the PET film of Comparative Example 3 of the present application after being coated with polyacrylic acid.
  • the composite current collector of the present application the preparation method thereof, and the electrochemical device will be described in detail below.
  • the composite current collector of the present application comprises a polymer film layer and a metal layer disposed on at least one side of the polymer film layer, wherein the polymer film layer and the metal layer are in an ionic bond structure [M + COO ⁇ ] combined, wherein M is a metal element in the metal layer.
  • the ionic bond [M + COO - ] structure can enhance the adhesion between the polymer film and the metal layer, and the adhesion between the metal layer and the polymer film layer can reach more than 5N/15mm, which can significantly improve the delamination of the composite current collector. Phenomenon.
  • the composite current collector includes upper and lower metal layers and an intermediate polymer film layer.
  • the metal element in the metal layer includes at least one of aluminum, copper, nickel, iron, titanium, silver, gold, cobalt, chromium, molybdenum, or tungsten.
  • the thickness of the metal layer of the composite current collector is 100 nm to 5000 nm.
  • the thickness of the polymer film layer is 2 ⁇ m to 36 ⁇ m.
  • the polymer film layer is grafted with carboxyl groups. In some embodiments, the surface of the polymer film layer is grafted with carboxyl groups.
  • the method for preparing a composite current collector as described above in the present application comprises the steps of: disposing a metal layer on a polymer film substrate grafted with carboxyl groups to obtain a composite current collector.
  • the polymer film substrate grafted with carboxyl groups can form an ionic bond with the metal layer by chemical deposition, so combining the polymer film layer and the metal layer can enhance the adhesion between the polymer film and the metal layer, improve the Delamination of composite current collectors.
  • the surface of the polymer film can be carboxylated by the method of chemically grafting acid anhydride as a polymer film matrix (among the derivatives of carboxylic acid, the acid anhydride is second only to acid chloride in activity, and has a strong reactivity), After that, metal atoms are deposited on the substrate, and ionic bonds can be generated between the carboxyl group and the metal to enhance the adhesion between the film layer and the metal layer.
  • the method for preparing the composite current collector described in the present application is shown in FIG. 2 .
  • the method for preparing the aforementioned composite current collector comprises the steps of: a. performing oxygen plasma or corona treatment on the polymer film to generate hydroxyl groups carrying active hydrogen atoms; b. The polymer film is coated or impregnated with an acid anhydride solution to cause a carboxylation reaction; c. After the carboxylation reaction, the solvent in the acid anhydride solution is evaporated to obtain a polymer film matrix grafted with carboxyl groups; d. A metal layer is deposited on the polymer film substrate to obtain a composite current collector.
  • the material of the polymer film comprises polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyethylene terephthalate (PEN), Polyparaphenylene terephthalamide (PPTA), polyimide (PI), polycarbonate (PC), polyether ether ketone (PEEK), polyoxymethylene (POM), polyparaphenylene sulfide (PPS) ), at least one of polyparaphenylene ether (PPO), polyvinyl chloride (PVC), polyamide (PA), or polytetrafluoroethylene (PTFE).
  • PE polyethylene
  • PP polypropylene
  • PET polyethylene terephthalate
  • PEN polyethylene terephthalate
  • PPTA Polyparaphenylene terephthalamide
  • PI polyimide
  • PC polycarbonate
  • PEEK polyether ether ketone
  • POM polyoxymethylene
  • PPS polyparaphenylene sulfide
  • PPO polyparaphenylene sul
  • the treatment of the polymer film is preferably an O2 plasma treatment.
  • the surface of the polymer treated by O2 plasma will generate hydroxyl groups carrying active hydrogen atoms.
  • the hydroxyl groups react with the acid anhydrides to form carboxyl groups by ring-opening.
  • the acid anhydride comprises phthalic anhydride (PA), maleic anhydride (MAH), or polyolefins (including high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP)) Graft at least one of maleic anhydride (PO-g-MAH).
  • the synthesis method of polyolefin grafting maleic anhydride comprises melt grafting, solution grafting, solid phase grafting, and suspension grafting.
  • the solvent of the acid anhydride solution comprises at least one of cyclohexane, toluene, xylene, ethyl acetate, butyl acetate, or butanone.
  • the solid content of the acid anhydride in the acid anhydride solution is 0.2% to 2% based on the total mass of the acid anhydride solution.
  • the reaction temperature of the hydroxyl group and the acid anhydride in the polymer film is 80 to 150°C.
  • reaction time of the hydroxyl group and the acid anhydride in the polymer film is 1 to 30 min.
  • step b can be step b': mixing the acid anhydride solution, the epoxy resin and/or the isocyanate solution A mixed solution is formed, and then the mixed solution is deposited on the polymer film of step a, so that the hydroxyl group of the polymer reacts with the acid anhydride to form a carboxyl group by ring-opening.
  • the solids content of the epoxy resin and/or isocyanate is 20% to 65% based on the total mass of the epoxy resin and/or isocyanate solution.
  • the acid anhydride solution, the epoxy resin and/or the isocyanate solution are mixed in a mass ratio of 100:0.32 to 100:4.16.
  • the evaporation temperature of the solvent is not particularly limited as long as the solvent can be completely evaporated. In some embodiments, the evaporation temperature of the solvent is 60°C to 140°C.
  • the metal layer deposition method includes magnetron sputtering, crucible boat evaporation coating method, and electron beam evaporation coating method.
  • the metal layer is deposited to a thickness of 100 nm to 5000 nm.
  • the electrochemical device of the present application is, for example, a primary battery, a secondary battery, a capacitor, and the like.
  • the secondary battery is, for example, a lithium secondary battery, and the lithium secondary battery includes, but is not limited to, a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
  • the electrochemical device includes a positive electrode sheet, a negative electrode sheet, a separator, and an electrolyte.
  • the positive electrode sheet includes a conductive agent, a binder, a positive electrode active material layer, and a composite current collector as previously described herein.
  • the aforementioned composite current collector of the present application includes a polymer film layer and a metal layer disposed on at least one side of the polymer film layer. Compared with a pure metal current collector of the same thickness, the density is lower. The aforementioned composite current collector of the application is lower in weight, and therefore, when the composite current collector of the present application is applied to an electrochemical device, its energy density can be improved.
  • the positive electrode current collector as aluminum as an example, its density is 2.7g/cm 3
  • the composite current collector prepared by the method for preparing a composite current collector mentioned above in this application for example, 1 ⁇ m Al+ 8 ⁇ m PET film layer (its density is 1.4 g/cm 3 ) + 1 ⁇ m Al
  • the weight of the current collector will be reduced to 61.5% of the original. Therefore, the composite current collector of the present application has the advantage that the energy density of the electrochemical device can be improved.
  • the polymer film was subjected to corona treatment, the maleic anhydride grafted polypropylene solution with a solid content of 15 wt% was coated on the surface of the PET film, and the solvent was evaporated by drying at 100 °C, and then the maleic anhydride grafted polypropylene solution was coated.
  • the PET film was placed in the vacuum chamber of the crucible boat type vacuum evaporation aluminizer, the vacuum chamber was sealed, the air pressure of the vacuum aluminizer was pumped to 10 -3 Pa, the temperature of the crucible boat was adjusted to 1200-1500 °C, and the aluminum plating was started. After the thickness of the aluminum layer reached 200 nm, the aluminum plating was stopped, and the composite current collector 1 was obtained.
  • the PET film was subjected to corona treatment, the maleic anhydride grafted polypropylene solution with a solid content of 15 wt% was coated on the surface of the PET film, and the solvent was evaporated by drying at 100 °C, and then the maleic anhydride grafted polypropylene solution was coated.
  • the PET film is placed in the vacuum chamber of the crucible boat type vacuum evaporation aluminizer, the vacuum chamber is sealed, the air pressure of the vacuum aluminizer is pumped to 10 -3 Pa, the temperature of the crucible boat is adjusted to 1200-1500°C, and the aluminum plating is started. After the layer thickness reached 500 nm, the aluminum plating was stopped, and the composite current collector 2 was obtained.
  • the PET film was subjected to corona treatment, the maleic anhydride grafted polypropylene solution with a solid content of 15 wt% was coated on the surface of the PET film, and the solvent was evaporated by drying at 100 °C, and then the maleic anhydride grafted polypropylene solution was coated.
  • the PET film is placed in the vacuum chamber of the crucible boat type vacuum evaporation aluminizer, the vacuum chamber is sealed, the air pressure of the vacuum aluminizer is pumped to 10 -3 Pa, the temperature of the crucible boat is adjusted to 1200-1500°C, and the aluminum plating is started. After the layer thickness reached 800 nm, the aluminum plating was stopped, and the composite current collector 3 was obtained.
  • the PET film is subjected to corona treatment, and the maleic anhydride grafted polypropylene solution with a solid content of 15 wt % and an epoxy resin solution with a solid content of 10 wt % are mixed in a weight ratio of 9:1 and then coated on the surface of the PET film, Use 100 °C to dry and evaporate the solvent, then place the PET film in the vacuum chamber of the crucible boat vacuum evaporation aluminizer, seal the vacuum chamber, pump the vacuum aluminizer to 10 -3 Pa, and adjust the crucible boat temperature to 1200 At ⁇ 1500° C., aluminum plating is started, and after the thickness of the aluminum layer reaches 500 nm, aluminum plating is stopped to obtain composite current collector 4 .
  • the PET film is subjected to corona treatment, and the maleic anhydride grafted polypropylene solution with a solid content of 15 wt % and an epoxy resin solution with a solid content of 10 wt % are mixed in a weight ratio of 7:3 and then coated on the surface of the PET film, Use 100 °C to dry and evaporate the solvent, then place the PET film in the vacuum chamber of the crucible boat vacuum evaporation aluminizer, seal the vacuum chamber, pump the vacuum aluminizer to 10 -3 Pa, and adjust the crucible boat temperature to 1200 At ⁇ 1500° C., aluminum plating is started, and after the thickness of the aluminum layer reaches 500 nm, aluminum plating is stopped to obtain composite current collector 5 .
  • the PET film was subjected to corona treatment, and the maleic anhydride grafted polypropylene solution with a solid content of 15 wt % and an isocyanate solution with a solid content of 10 wt % were mixed in a weight ratio of 7:3 and coated on the surface of the PET film, using 100 °C dry and evaporate the solvent, then place the PET film in the vacuum chamber of the crucible boat vacuum evaporation aluminizer, seal the vacuum chamber, pump the pressure of the vacuum aluminizer to 10 -3 Pa, and adjust the temperature of the crucible boat to 1200-1500 °C, the aluminum plating is started, and after the thickness of the aluminum layer reaches 500 nm, the aluminum plating is stopped, and the composite current collector 6 is obtained.
  • the corona-treated PET film was placed in the vacuum chamber of the crucible boat type vacuum evaporation aluminizer, the vacuum chamber was sealed, the air pressure of the vacuum aluminizer was pumped to 10 -3 Pa, and the temperature of the crucible boat was adjusted to 1200-1500°C, The aluminum plating was started, and after the thickness of the aluminum layer reached 500 nm, the aluminum plating was stopped, and the comparative composite current collector 1 was obtained.
  • the corona-treated PET film After the surface of the corona-treated PET film is coated with acrylate, it is placed in the vacuum chamber of the crucible boat type vacuum evaporation aluminizer, the vacuum chamber is sealed, the air pressure of the vacuum aluminizer is pumped to 10 -3 Pa, and the temperature of the crucible boat is lowered. The temperature was adjusted to 1200-1500° C., and aluminum plating was started. After the thickness of the aluminum layer reached 500 nm, aluminum plating was stopped, and a comparative composite current collector 2 was obtained.
  • the corona-treated PET film After the surface of the corona-treated PET film is coated with polyacrylic acid, it is placed in the vacuum chamber of a crucible boat type vacuum evaporation aluminizer, the vacuum chamber is sealed, the pressure of the vacuum aluminizer is pumped to 10 -3 Pa, and the temperature of the crucible boat is lowered. The temperature was adjusted to 1200-1500° C., and aluminum plating was started. After the thickness of the aluminum layer reached 500 nm, aluminum plating was stopped, and a comparative composite current collector 3 was obtained.
  • sample test prompt interface When the sample test prompt interface appears, open the upper cover of the test box, take a film sample of moderate thickness and lay it on the sample holder, and scan the sample.
  • EAA ethylene acrylic acid copolymer
  • the hot-pressing conditions are: temperature 85 °C, pressure 0.7MPa, time 30s.
  • the hot-pressing conditions are: temperature 85°C, pressure 0.7MPa, time 45s.
  • test results of carboxyl groups in the polymers of Examples 1-6 and Comparative Examples 1-3 are shown in Figures 3-8 and 9-11, respectively.
  • Table 1 shows the test results of the adhesive force of the current collectors of Examples 1-6 and Comparative Examples 1-3.
  • Example 3 referring to Figures 5, 5a, and 5b, the acid anhydride graft layer exhibited a characteristic vibration peak of acid anhydride at 1785 cm -1 ( Figure 5b), and after the graft layer was coated on the PET layer, it was attributed to acid anhydride
  • the vibration peak of PET disappears, the hydroxyl group of PET disappears at about 3430 cm -1 ( Figure 5a), and the vibration of the carboxyl group appears at 1706 cm -1 ( Figure 5), which indicates that the hydroxyl group on the surface of the PET film layer and the acid anhydride in the acid anhydride grafted layer disappear.
  • a reaction occurs to form a new functional carboxyl group.
  • the adhesion between the metal layer and the polymer layer in the composite current collector of the present application is significantly improved, and the delamination phenomenon of the composite current collector can be significantly improved. Therefore, when the composite current collector described in the present application is applied to an electrochemical device, the cycle performance and high temperature storage performance of the electrochemical device can be improved.

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Abstract

本申请提供了一种复合集流体及其制备方法以及电化学装置。复合集流体包括聚合物膜层以及设置在聚合物膜层至少一面上的金属层，其中，所述聚合物膜层和所述金属层以离子键结构[M +COO -]结合，其中，M为金属层中的金属元素。制备复合集流体的方法包括步骤：在接枝有羧基的聚合物膜基体上设置金属层，得到复合集流体。电化学装置包括所述复合集流体。本申请的复合集流体的离子键结构可以提高金属层与聚合物层的粘接力，改善复合集流体分层、脱落的现象，同时其应用于电化学装置时可以提高电化学装置的能量密度，并且改善电化学装置的循环性能与高温存储性能。

Description

复合集流体及其制备方法以及电化学装置 技术领域
本申请涉及电化学领域，具体涉及一种复合集流体及其制备方法以及电化学装置。
背景技术
集流体贯穿了电化学装置(例如锂离子电池)全部的加工过程以及服务于电化学装置的整个生命周期，是电化学装置中活性材料的载体并为电子传输提供通道，是电化学装置中重要组成部分。集流体与电芯的能量密度密切相关，可以通过降低集流体厚度的方式提高电芯的能量密度。然而由于金属材料的特性(如断裂延伸率低)，当集流体厚度降低至一定水平后，集流体易发生断裂，破损等不良现象，造成原材料浪费、产能降低等问题。
在低密度的聚合物薄膜表面通过设置导电层得到的复合集流体可以有效降低锂离子电池集流体的密度，提升锂离子电池的重量能量密度。然而导电层与聚合物薄膜之间的附着力低，在极片加工与锂离子电池生命周期中存在复合集流体表层导电层脱落等现象，严重影响锂离子电池的循环寿命与高温存储性能。
发明内容
鉴于背景技术中存在的问题，本申请的目的在于提供一种复合集流体及其制备方法以及电化学装置，所述复合集流体可以改善复合集流体分层、脱落的现象，同时其应用于电化学装置时可以提高电化学装置的能量密度，并且改善电化学装置的循环性能与高温存储性能。
在一些实施例中，本申请提供了一种复合集流体，其包括聚合物膜层以及设置在聚合物膜层至少一面上的金属层，其中，所述聚合物膜层和所述金属层以离子键结构[M +COO -]结合，其中，M为金属层中的金属元素。
在一些实施例中，所述金属层中的金属元素包括铝、铜、镍、铁、钛、 银、金、钴、铬、钼或钨中的至少一种。
在一些实施例中，所述金属层的厚度为100nm至5000nm。
在一些实施例中，所述聚合物膜层的厚度为2μm至36μm。
在一些实施例中，所述聚合物膜层表面接枝有羧基。
在一些实施例中，本申请提供了一种制备本申请的复合集流体的方法，包括步骤：在接枝有羧基的聚合物膜基体上设置金属层，得到复合集流体。
在一些实施例中，所述复合集流体的制备方法包括步骤：a.对聚合物膜进行氧气等离子体或电晕处理，使其产生携带活性氢原子的羟基；b.将步骤a的聚合物膜涂覆或浸渍酸酐溶液，使发生羧基化反应；c.羧基化反应完后，将酸酐溶液中的溶剂蒸发，得到接枝有羧基的聚合物膜基体；d.在接枝有羧基的聚合物膜基体上沉积金属层，得到复合集流体。
在一些实施例中，在步骤a中，所述聚合物膜材料包括聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、聚对萘二甲酸乙二醇酯、聚对苯二甲酰对苯二胺、聚酰亚胺、聚碳酸酯、聚醚醚酮、聚甲醛、聚对苯硫醚、聚对苯醚、聚氯乙烯、聚酰胺或聚四氟乙烯中的至少一种。
在一些实施例中，在步骤b中，所述酸酐包括邻苯二甲酸酐、马来酸酐或聚烯烃接枝马来酸酐中的至少一种。
在一些实施例中，本申请提供了一种电化学装置，其包括本申请的复合集流体。
相比于现有技术，本申请至少包括如下有益效果：本申请的复合集流体的离子键结构可以提高金属层与聚合物层的粘接力，改善复合集流体分层、脱落的现象，同时其应用于电化学装置时可以提高电化学装置的能量密度，并且改善电化学装置的循环性能与高温存储性能。
附图说明
下面结合附图和具体实施例，对本申请的复合集流体进行详细说明。
图1为本申请的一具体实施例的复合集流体的局部剖视结构示意图，其中，
1-第一金属层；
2-第一酸酐接枝层；
3-聚合物膜层；
4-第二酸酐接枝层；
5-第二金属层。
图2为本申请的一具体实施例的制备复合集流体的步骤示意图。
图3为本申请的实施例1的PET膜接枝羧基后的红外光谱示意图。
图4为本申请的实施例2的PET膜接枝羧基后的红外光谱示意图。
图5为本申请的实施例3的PET膜接枝羧基后的红外光谱示意图。
图5a为PET膜的红外光谱示意图。
图5b为酸酐接枝层的红外谱图。
图6为本申请的实施例4的PET膜接枝羧基后的红外光谱示意图。
图7为本申请的实施例5的PET膜接枝羧基后的红外光谱示意图。
图8为本申请的实施例6的PET膜接枝羧基后的红外光谱示意图。
图9为本申请的对比例1的PET膜的红外光谱示意图。
图10为本申请的对比例2的PET膜涂覆丙烯酸酯后的红外光谱示意图。
图11为本申请的对比例3的PET膜涂覆聚丙烯酸后的红外光谱示意图。
具体实施方式
应理解的是，所公开的实施例仅是本申请的示例，本申请可以以各种形式实施，因此，本申请的具体细节不应被解释为限制，而是仅作为权利要求的基础且作为表示性的基础用于教导本领域普通技术人员以各种方式实施本申请。
在本申请的说明中，除非另有定义，未明确说明的专业术语、专业用词均与本领域技术人员通常理解的含义相同，且为本领域技术人员的公知常识，未明确说明的方法均为本领域技术人员公知的常规方法。
下面详细说明本申请的复合集流体及其制备方法以及电化学装置。
[复合集流体]
首先说明本申请的复合集流体。
在一些实施例中，本申请的复合集流体包含聚合物膜层以及设置在聚合物膜层至少一面上的金属层，其中，聚合物膜层和金属层以离子键结构 [M +COO -]结合，其中，M为金属层中的金属元素。
离子键[M +COO -]结构可以增强聚合物薄膜与金属层的粘接力，可使金属层与聚合物膜层间的附着力达5N/15mm以上，能够显著改善复合集流体的分层现象。
在一些实施例中，如图1所示，复合集流体包含上下两层金属层以及中间的聚合物膜层。
在一些实施例中，金属层中的金属元素包括铝、铜、镍、铁、钛、银、金、钴、铬、钼或钨中的至少一种。
在一些实施例中，复合集流体的金属层的厚度为100nm至5000nm。
在一些实施例中，聚合物膜层的厚度为2μm至36μm。
在一些实施例中，聚合物膜层接枝有羧基。在一些实施例中，聚合物膜层的表面接枝有羧基。
[复合集流体的制备方法]
其次说明本申请的复合集流体的制备方法。
在一些实施例中，制备本申请前述的复合集流体的方法包含步骤：在接枝有羧基的聚合物膜基体上设置金属层，得到复合集流体。
接枝有羧基的聚合物膜基体可与通过化学沉积的金属层之间形成离子键，因此将聚合物膜层和金属层结合在一起，可以增强聚合物膜与金属层的粘接力，改善复合集流体的分层现象。
在本申请中，可在聚合物膜表面通过化学接枝酸酐的方法使其羧基化作为聚合物膜基体(在羧酸的衍生物中，酸酐的活性仅次于酰氯，反应能力很强)，之后在此基体上沉积金属原子，羧基与金属之间可以产生离子键作用而增强膜层与金属层的粘接力。
在一些实施例中，制备本申请前述的复合集流体的方法如图2所示。
在一些实施例中，制备本申请前述的复合集流体的方法包含步骤：a.对聚合物膜进行氧气等离子体或电晕处理，使其产生携带活性氢原子的羟基；b.将步骤a的聚合物膜涂覆或浸渍酸酐溶液，使发生羧基化反应；c.羧基化反应完后，将酸酐溶液中的溶剂蒸发，得到接枝有羧基的聚合物膜基体；d.在接枝有羧基的聚合物膜基体上沉积金属层，得到复合集流体。
<步骤a>
在一些实施例中，聚合物膜的材料包含聚乙烯(PE)、聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对萘二甲酸乙二醇酯(PEN)、聚对苯二甲酰对苯二胺(PPTA)、聚酰亚胺(PI)、聚碳酸酯(PC)、聚醚醚酮(PEEK)、聚甲醛(POM)、聚对苯硫醚(PPS)、聚对苯醚(PPO)、聚氯乙烯(PVC)、聚酰胺(PA)或聚四氟乙烯(PTFE)中的至少一种。
在一些实施例中，对聚合物膜的处理优选为O 2等离子体处理。经过O 2等离子体处理的聚合物表面会产生携带活性氢原子的羟基，此时在高温下涂覆或浸渍含有酸酐的溶液，羟基与酸酐反应，从而开环形成羧基。
<步骤b>
在一些实施例中，酸酐包含邻苯二甲酸酐(PA)、马来酸酐(MAH)或聚烯烃(包含高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)、聚丙烯(PP))接枝马来酸酐(PO-g-MAH)中的至少一种。在一些实施例中，聚烯烃接枝马来酸酐的合成方法包含熔融接枝、溶液接枝、固相接枝、悬浮接枝。
在一些实施例中，酸酐溶液的溶剂包含环己烷、甲苯、二甲苯、乙酸乙酯、乙酸丁酯或丁酮中的至少一种。
在一些实施例中，以酸酐溶液的总质量计，酸酐溶液中酸酐的固含量为0.2％至2％。
在一些实施例中，聚合物膜中的羟基与酸酐的反应温度为80至150℃。
在一些实施例中，聚合物膜中的羟基与酸酐的反应时间为1至30min。
<步骤bˊ>
由于环氧树脂和/或异氰酸酯可以与酸酐固化交联，提高酸酐主体树脂的内聚力，因此，在一些实施例中，步骤b可为步骤bˊ：将酸酐溶液、环氧树脂和/或异氰酸酯溶液混合形成混合溶液，之后将混合溶液沉积于步骤a的聚合物膜，使得聚合物的羟基与酸酐反应，开环形成羧基。
在一些实施例中，以环氧树脂和/或异氰酸酯溶液的总质量计，环氧树脂和/或异氰酸酯的固含量为20％至65％。
在一些实施例中，酸酐溶液、环氧树脂和/或异氰酸酯溶液混合的质量比为100:0.32至100:4.16。
<步骤c>
溶剂的蒸发温度不受具体限制，只要能够将溶剂蒸发完全即可。在一些实施例中，溶剂的蒸发温度为60℃至140℃。
<步骤d>
在一些实施例中，金属层沉积的方法包含磁控溅射法、坩埚舟蒸发镀膜法、电子束蒸发镀膜法。
在一些实施例中，金属层的沉积厚度为100nm至5000nm。
[电化学装置]
最后说明本申请的电化学装置。
本申请的电化学装置例如为一次电池、二次电池、电容器等。二次电池例如为锂二次电池，锂二次电池包含但不限于锂金属二次电池、锂离子二次电池、锂聚合物二次电池或锂离子聚合物二次电池。
在一些实施例中，电化学装置包含正极片、负极片、隔离膜以及电解液。
在一些实施例中，正极片包括导电剂、粘接剂、正极活性材料层以及本申请前述的复合集流体。
本申请前述的复合集流体包含聚合物膜层以及设置在聚合物膜层至少一面上的金属层，相对于同等厚度的纯金属集流体而言，密度更小，在相同的电池能量下由于本申请前述的复合集流体重量更低，因此，当本申请的复合集流体应用于电化学装置时，可以改善其能量密度。以正极集流体为铝为例，其密度为2.7g/cm 3，当将10μm厚度的铝集流体替换为由本申请前述的制备复合集流体的方法制备得到的复合集流体时，例如1μm Al+8μm PET膜层(其密度为1.4g/cm 3)+1μm Al，集流体重量将减轻至原来的61.5％。因此，本申请的复合集流体具有可以提升电化学装置的能量密度的优势。
下面结合实施例，进一步阐述本申请。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。除有特别说明，示例中用到的各种试剂、原料均为可以从市场上购买的商品或者可以通过公知的方法制得的产品。
实施例1
将聚合物膜进行电晕处理，将固含量为15wt％的马来酸酐接枝聚丙烯溶液涂覆于PET膜表面，使用100℃干燥蒸发溶剂，随后将涂覆了马来酸酐接枝聚丙烯的PET膜置于坩埚舟式真空蒸发镀铝机真空室，将真空室密封，将真空镀铝机气压抽至10 -3Pa，将坩埚舟温度调节至1200～1500℃，开始镀铝，待铝层厚度达到200nm后，停止镀铝，得到复合集流体1。
实施例2
将PET膜进行电晕处理，将固含量为15wt％的马来酸酐接枝聚丙烯溶液涂覆于PET膜表面，使用100℃干燥蒸发溶剂，随后将涂覆了马来酸酐接枝聚丙烯的PET膜置于坩埚舟式真空蒸发镀铝机真空室，将真空室密封，将真空镀铝机气压抽至10 -3Pa，将坩埚舟温度调节至1200～1500℃，开始镀铝，待铝层厚度达到500nm后，停止镀铝，得到复合集流体2。
实施例3
将PET膜进行电晕处理，将固含量为15wt％的马来酸酐接枝聚丙烯溶液涂覆于PET膜表面，使用100℃干燥蒸发溶剂，随后将涂覆了马来酸酐接枝聚丙烯的PET膜置于坩埚舟式真空蒸发镀铝机真空室，将真空室密封，将真空镀铝机气压抽至10 -3Pa，将坩埚舟温度调节至1200～1500℃，开始镀铝，待铝层厚度达到800nm后，停止镀铝，得到复合集流体3。
实施例4
将PET膜进行电晕处理，将固含量为15wt％的马来酸酐接枝聚丙烯溶液与固含量为10wt％的环氧树脂溶液按照9:1的重量比混合后涂覆于PET膜表面，使用100℃干燥蒸发溶剂，随后将此PET膜置于坩埚舟式真空蒸发镀铝机真空室，将真空室密封，将真空镀铝机气压抽至10 -3Pa，将坩埚舟温度调节至1200～1500℃，开始镀铝，待铝层厚度达到500nm后，停止镀铝，得到复合集流体4。
实施例5
将PET膜进行电晕处理，将固含量为15wt％的马来酸酐接枝聚丙烯溶液 与固含量为10wt％的环氧树脂溶液按照7:3的重量比混合后涂覆于PET膜表面，使用100℃干燥蒸发溶剂，随后将此PET膜置于坩埚舟式真空蒸发镀铝机真空室，将真空室密封，将真空镀铝机气压抽至10 -3Pa，将坩埚舟温度调节至1200～1500℃，开始镀铝，待铝层厚度达到500nm后，停止镀铝，得到复合集流体5。
实施例6
将PET膜进行电晕处理，将固含量为15wt％的马来酸酐接枝聚丙烯溶液与固含量为10wt％的异氰酸酯溶液按照7:3的重量比混合后涂覆于PET膜表面，使用100℃干燥蒸发溶剂，随后将此PET膜置于坩埚舟式真空蒸发镀铝机真空室，将真空室密封，将真空镀铝机气压抽至10 -3Pa，将坩埚舟温度调节至1200～1500℃，开始镀铝，待铝层厚度达到500nm后，停止镀铝，得到复合集流体6。
对比例1
将经过电晕处理的PET膜置于坩埚舟式真空蒸发镀铝机真空室，将真空室密封，将真空镀铝机气压抽至10 -3Pa，将坩埚舟温度调节至1200-1500℃，开始镀铝，待铝层厚度达到500nm后，停止镀铝，得到对比复合集流体1。
对比例2
将经过电晕处理的PET膜表面涂覆丙烯酸酯后，置于坩埚舟式真空蒸发镀铝机真空室，将真空室密封，将真空镀铝机气压抽至10 -3Pa，将坩埚舟温度调节至1200～1500℃，开始镀铝，待铝层厚度达到500nm后，停止镀铝，得到对比复合集流体2。
对比例3
将经过电晕处理的PET膜表面涂覆聚丙烯酸后，置于坩埚舟式真空蒸发镀铝机真空室，将真空室密封，将真空镀铝机气压抽至10 -3Pa，将坩埚舟温度调节至1200～1500℃，开始镀铝，待铝层厚度达到500nm后，停止镀铝，得到对比复合集流体3。
接下来说明实施例1-6的聚合物中羧基的测试过程。
利用Nicolet iS10红外光谱仪对实施例1-6中的聚合物进行羧基测试：
①参数设置：在OMINC软件主界面下点击Collect，打开Experiment Setup，设定扫描次数为32，分辨率为4cm -1，扫描范围为4000-600cm -1。
②背景扣除：在Collect中选择collect background，进行空气背景扫描。每次在扫描样品图谱之前均需扣除背景。
③样品测试：待出现样品测试提示界面时，打开测试箱上盖，取厚度适中的薄膜样品平铺在样品架，进行样品扫描，此时所得谱图即为已扣除背景的样品图谱。
最后说明对比例1-3的集流体的粘接力的测试过程。
粘接力测试的具体步骤为：
①将厚度约80μm的EAA(乙烯丙烯酸共聚物)热熔胶与12μm的PET薄膜经LCP200-A2008N型热压机热压，热压条件为：温度85℃，压力0.7MPa，时间30s。
②将集流体裁切为2cm×10cm规格的样条，并使用无水乙醇润湿的无尘纸擦拭干净。
③将经过热压复合的EAA表层的离型纸剥掉，并将粘接面与裁切好的集流体正对放置，且使用热压机热压，热压条件为：温度85℃，压力0.7MPa，时间45s。
④将双面胶贴在长度为125±1mm、宽度为50±1mm、厚度为1.5-2mm的钢板上并剥掉离型纸，将步骤③制备好的复合样品中的集流体侧贴在双面胶上。使用美工刀及直尺将测试样裁切成长为80mm、宽为15mm规格的待测样。
⑤开启INSTRON 3365型电子万能试验机，选择180°剥离测试项准备测试：将样品自由端对折180°，并从实验板上剥开粘合面约25mm，把样品自由端和实验板分别夹在上、下夹持器上且传感器恰好不受力，夹持时剥离面与拉力机力线保持一致。
⑥按控制面板上试验键开始测试，测试行程完成后，拉力试验机上夹头 将回位，在上夹头回位到位时，将试验板从下夹头上取出。每次测试至少取三个数据，以均值表示样品的粘接力。
实施例1-6和对比例1-3的聚合物中羧基的测试结果分别如图3-8、9-11所示。实施例1-6和对比例1-3的集流体的粘接力的测试结果如表1所示。
表1
样品名称 粘接力(N/15mm)
复合集流体1 5.8
复合集流体2 5.1
复合集流体3 5.3
复合集流体4 5.5
复合集流体5 5.3
复合集流体6 5.4
对比复合集流体1 2.0
对比复合集流体2 2.8
对比复合集流体3 2.6
在实施例3中，参见图5、5a、5b，酸酐接枝层在1785cm -1处表现出酸酐的特征振动峰(图5b)，当接枝层涂覆在PET层上之后，归属于酸酐的振动峰消失，PET在3430cm -1左右的羟基消失(图5a)，而在1706cm -1处出现羧基的振动(图5)，这表明PET膜层表面的羟基与酸酐接枝层中的酸酐发生反应形成新的官能团羧基。
通过图3-4、6-8可以看出，在这些光谱图中都出现了归属羧基的羰基振动峰，在2800-3000cm -1波数处出现了归属羧基的峰值较宽的羟基振动峰，这与实施例3的结果相同。因此，在实施例1-2、4-6中，羧基也已经成功接枝到了PET聚合物中。
而图9-10中却没有出现图3-8中的归属羧基的振动峰。从图11中可以看出，在1699cm -1处出现了羧基特征峰，但是这是对比例3中的聚丙烯酸中固有的羧基，但由于聚丙烯酸与PET基底无明显的相互作用，因此涂层与PET的附着力较差，进而对比复合集流体3的粘接力也较差。
从表1中粘接力的测试数据可以看出，实施例1-6的粘接力明显优于对比例1-2。实施例的剥离强度均在5N/15mm以上，而对比例1-3的剥离强度则在3.5N/15mm以下。
由此可见，本申请的复合集流体中的金属层与聚合物层的粘接力得到显 著提高，可以显著改善复合集流体的分层现象。因此，当本申请所述的复合集流体应用到电化学装置中时，可以改善电化学装置的循环性能与高温存储性能。
以上所述，仅是本申请的示例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均在本申请技术方案的范围内。

Claims (10)

  1. 一种复合集流体，包括聚合物膜层以及设置在聚合物膜层至少一面上的金属层，其中，
    所述聚合物膜层和所述金属层以离子键结构[M +COO -]结合，其中，M为金属层中的金属元素。
  2. 根据权利要求1所述的复合集流体，其中，所述金属层中的金属元素包括铝、铜、镍、铁、钛、银、金、钴、铬、钼或钨中的至少一种。
  3. 根据权利要求1所述的复合集流体，其中，所述金属层的厚度为100nm至5000nm。
  4. 根据权利要求1所述的复合集流体，其中，所述聚合物膜层的厚度为2μm至36μm。
  5. 根据权利要求1所述的复合集流体，其中，所述聚合物膜层表面接枝有羧基。
  6. 一种复合集流体的制备方法，用于制备根据权利要求1-5任一项所述的复合集流体，其中，包括步骤：在接枝有羧基的聚合物膜基体上设置金属层，得到复合集流体。
  7. 根据权利要求6所述的复合集流体的制备方法，其中，包括步骤：
    a.对聚合物膜进行氧气等离子体或电晕处理，使其产生携带活性氢原子的羟基；
    b.将步骤a的聚合物膜涂覆或浸渍酸酐溶液，使发生羧基化反应；
    c.所述羧基化反应完后，将所述酸酐溶液中的溶剂蒸发，得到带有羧基的聚合物膜基体；
    d.在带有羧基的聚合物膜基体上沉积金属层，得到复合集流体。
  8. 根据权利要求7所述的复合集流体的制备方法，其中，在所述步骤a中，所述聚合物膜材料包括聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、聚对萘二甲酸乙二醇酯、聚对苯二甲酰对苯二胺、聚酰亚胺、聚碳酸酯、聚醚醚酮、聚甲醛、聚对苯硫醚、聚对苯醚、聚氯乙烯、聚酰胺或聚四氟乙烯中的至少一种。
  9. 根据权利要求7所述的复合集流体的制备方法，其中，在所述步骤b中，所述酸酐包括邻苯二甲酸酐、马来酸酐或聚烯烃接枝马来酸酐中的至少一种。
  10. 一种电化学装置，包括根据权利要求1-5中任一项所述的复合集流体。
PCT/CN2020/140909 2020-12-29 2020-12-29 复合集流体及其制备方法以及电化学装置 Ceased WO2022141069A1 (zh)

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CN115498193A (zh) * 2022-09-23 2022-12-20 杭州允腾科技有限公司 一种新型复合集电体及其制备方法
CN116031412A (zh) * 2023-02-27 2023-04-28 华中科技大学 一种记忆性复合集流体及其制备方法
CN116314841A (zh) * 2023-03-28 2023-06-23 南通迈威电子材料有限公司 一种多层复合集流体
CN117888065A (zh) * 2023-12-29 2024-04-16 江苏华旺新材料有限公司 一种复合铜膜蒸镀工艺
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CN118380588A (zh) * 2024-03-18 2024-07-23 中科兴业(无锡)高新材料有限公司 基于聚芳硫醚树脂的复合集流体、锂离子电池及制备方法
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CN119581567A (zh) * 2024-12-02 2025-03-07 四川普利司德高分子新材料有限公司 一种高性能复合集流体及其制备方法
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