WO2019157845A1 - Liquid-additive-free, separator-free all-solid-state lithium-ion dual-electric-layer supercapacitor and preparation method therefor - Google Patents

Liquid-additive-free, separator-free all-solid-state lithium-ion dual-electric-layer supercapacitor and preparation method therefor Download PDF

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WO2019157845A1
WO2019157845A1 PCT/CN2018/116354 CN2018116354W WO2019157845A1 WO 2019157845 A1 WO2019157845 A1 WO 2019157845A1 CN 2018116354 W CN2018116354 W CN 2018116354W WO 2019157845 A1 WO2019157845 A1 WO 2019157845A1
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solid
layer
polymer electrolyte
supercapacitor
electrode sheet
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PCT/CN2018/116354
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French (fr)
Chinese (zh)
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黄宝陵
赤骋
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香港科技大学深圳研究院
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Publication of WO2019157845A1 publication Critical patent/WO2019157845A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention belongs to the technical field of energy storage devices, and particularly relates to an all-solid lithium ion electric double layer super capacitor without liquid additive and without diaphragm and a preparation method thereof.
  • supercapacitors are widely used in many applications requiring fast charge and discharge energy and long cycle life, such as automobiles, trains, and renewable energy storage.
  • supercapacitors with high energy density, long life and high safety have become research hotspots.
  • Conventional commercial supercapacitors use water or other liquid electrolytes. Although these liquid electrolytes have high ionic conductivity and high power density, traditional liquid supercapacitors face many problems, such as electrolyte leakage, which can corrode the electrodes, resulting in loss of performance, even The leakage of liquid electrolyte may cause safety hazards such as fire.
  • the liquid electrolyte has a smaller voltage window that limits the energy density and requires high sealing, complicating manufacturing.
  • solid polymer electrolytes have good mechanical properties, no leakage, thereby improving safety and packaging efficiency, and are widely considered as a substitute for liquid electrolytes.
  • a colloidal electrolyte mainly composed of PVA-H 2 SO 4 and PVA-H 3 PO 4 is usually used.
  • such a gel electrolyte has a small operating voltage window (1.0 V), which limits the energy density (5-10 Wh kg -1 ).
  • Lithium-ion polymer electrolytes have a high voltage window, but conventional solid-state lithium ion polymer electrolyte materials have poor ion conductivity ( ⁇ 10 -5 S cm -1 at room temperature).
  • An organic-inorganic hybrid polymer electrolyte can be obtained by filling an inorganic nanomaterial or a nano-lithium ion conductor to a polymer electrolyte, and has a high ionic conductivity (>10 -5 S cm -1 at room temperature). Therefore, such an organic-inorganic hybrid polymer electrolyte is expected to improve the performance of a solid supercapacitor.
  • the same assembly structure as the liquid supercapacitor is mainly used, that is, an electrode-solid electrolyte-electrode sandwich structure.
  • this solid-solid direct contact structure results in high contact resistance and reduces the performance of solid supercapacitors.
  • conventional solid supercapacitors still require additional diaphragms (US8947853B2; US7612985B2), resulting in complex manufacturing procedures and high costs.
  • the conductivity of a solid electrolyte suitable for a solid supercapacitor needs to be higher than 10 -4 S cm -1 at least at room temperature. Therefore, the preparation of an all-solid supercapacitor based on lithium ion high conductivity polymer can avoid the above problems and has very important practical significance.
  • the object of the present invention is to provide an all-solid-state lithium ion electric double layer supercapacitor without liquid additive and without a diaphragm, which solves the technical problem that the prior art manufacturing process is too complicated and has high cost; and solves the existing gel Shape or quasi-solid supercapacitors have safety hazards and cannot be used on a large scale.
  • the solid polymer electrolyte layer in the middle portion and the outer nanocomposite electrode symmetrically disposed on the top surface and the bottom surface of the solid polymer electrolyte layer;
  • the external nanocomposite electrode includes an adhesive layer and a composite electrode which are sequentially disposed from the inside to the outside a sheet and a flexible conductive substrate layer, and a packaging layer is disposed outside the nanocomposite electrode.
  • the solid polymer electrolyte layer is made of a polymer electrolyte composite material, which is a composite structure in which a nano-ion conductive material is combined with a solid polymer electrolyte, and the solid polymer electrolyte includes a polyvinylidene fluoride copolymer, a LiBOB, a LiODFB, a LiBFMB, and a LiBFMB derivative, the polyvinylidene fluoride copolymer including PVDF-TrFE, PVDF-TFE, and PVDF-HFP; the nano-ion conductive material including a nanometer size Inorganic ceramic filler and ionic conductor filler, including but not limited to BaTiO 3 , SiO 2 or TiO 2 , the weight ratio of the nano-ion conductive material in the polymer electrolyte composite is 0 to 10 wt.% by weight In the range.
  • the adhesive layer is made of a copolymerizable polymer material having ion conductivity or a solid polymer electrolyte.
  • the composite electrode sheet is composed of a composite material comprising a continuous conductive frame formed of a solid ion conductive polymer and a low-dimensional conductive capacitive material, the solid ion conductive polymer being a solid polymer electrolyte layer
  • the shape structure of the low-dimensional conductive capacitive material comprises a zero-dimensional particle structure, a one-dimensional nanotube structure and/or a two-dimensional layer structure
  • the low-dimensional conductive capacitive material comprises a carbon material
  • the carbon includes graphene, carbon nanotubes and activated carbon
  • the weight ratio of low-dimensional conductive and capacitive materials in the composite electrode sheet is 80-90. Weight range of wt.%.
  • the flexible conductive substrate layer comprises a carbon-based fabric, a metal mesh and/or a conductive polymer layer, the carbon-based fabric, the metal mesh and the conductive polymer are coated with a metal material.
  • the packaging layer is used to protect and seal the supercapacitor, and the packaging layer is a flexible insulating plastic polymer film or an aluminum plastic packaging film.
  • the top surface and the bottom surface of the supercapacitor are symmetrically provided with openings, the openings are filled with an adhesive, and a plurality of supercapacitors are filled in the openings of adjacent supercapacitors by an adhesive to adjacent supercapacitors The adhesive is fixed to form a tandem solid double-layer supercapacitor.
  • a method for preparing an all-solid lithium ion electric double layer supercapacitor without liquid additive and without a membrane characterized in that the method comprises the following methods:
  • S1 preparing a solid polymer electrolyte layer: first dissolving the copolymer of the polymer chain in an organic solvent, and then adding a lithium-based compound salt to the above solution, and setting the mass ratio to 10
  • the wt.% ⁇ 50 wt.% solution, the inorganic nanoparticles can continue to be doped into the solution, stirred for a sufficient time in an inert gas atmosphere, and finally a solid polymer electrolyte layer is obtained by a solution casting process;
  • S2 preparing a composite electrode sheet: mixing a 1D, 2D inorganic carbon material and a solid ion conductive polymer into an organic solvent, and uniformly stirring at a certain temperature, the electrode slurry is prepared, and the electrode slurry is prepared. Uniformly coated on a flexible conductive substrate layer composed of conductive graphite paper by a coating method, and sufficiently dried at a high temperature to obtain a flexible conductive substrate layer covered with a composite electrode sheet;
  • a layer of the composition thereby obtaining a multilayer structure of the flexible conductive substrate layer-composite electrode sheet-adhesive layer, and sandwiching the solid polymer electrolyte layer prepared in step S1 on two identical flexible conductive substrate layers-composite electrode sheets-bonding Press between the agent layers and at a temperature of 80-200 ° C to obtain a flexible conductive substrate layer - composite electrode sheet - adhesive layer - solid polymer electrolyte layer - adhesive layer - composite electrode sheet - flexible
  • the multilayer structure of the conductive substrate layer is packaged using a packaging layer.
  • an all-solid lithium ion electric double layer supercapacitor without liquid additive and without a separator is prepared.
  • the method includes the following steps: the step S1 specifically includes the following steps:
  • a copolymer of polyvinylidene fluoride is dissolved in dimethylformamide, and then a borate-based lithium salt is added, and a solution of a copolymer of different weight ratio of polyvinylidene fluoride/borate-based lithium salt is disposed.
  • a solid polymer electrolyte layer of a copolymer of vinyl fluoride/borate-based lithium salt having a thickness of about 10 to 100 ⁇ m.
  • the step S2 specifically comprises the steps of mixing activated carbon, graphene oxide, multi-walled carbon nanotubes and a solid polymer electrolyte, wherein the weight ratio of activated carbon is 20 to 30 wt.%, and the weight of graphene oxide The ratio is 15 to 25 wt.%, the weight ratio of the multi-walled carbon nanotubes is 35 to 35 wt.%, and the weight ratio of the solid polymer electrolyte is 10 to 20 wt.%.
  • the composite electrode sheet was obtained by coating on the surface of a flexible conductive substrate layer composed of graphite paper, followed by placing in a vacuum drying oven and drying at a temperature of 100 ° C for more than 24 hours.
  • the solid polymer electrolyte layer of the present invention comprises a copolymer, a lithium-based compound and an inorganic nano-filler material, and the lithium-based compound is a borate group anion having a large ionic radius, which acts as a solid plasticizer to help The crystallinity of the polymer electrolyte is lowered and the ion mobility is improved to enhance the ionic conductivity of the polymer electrolyte.
  • the adhesive layer 40 in the present invention is used to help improve contact and increase the adhesion between the composite electrode sheet 30 and the solid polymer electrolyte layer 50, avoiding direct contact of solids and solids between the electrode and the electrolyte.
  • the adhesive layer 40 has good adhesion and is fully compatible with the electrolyte and the electrode, which can bring about good contact and reduce the contact resistance between the electrolyte and the electrode.
  • the present invention provides anionic and inorganic nanofillers using large ionic radius borate groups to increase the ionic conductivity of solid polymer electrolytes.
  • the solid polymer electrolyte can operate at voltages above 1.8V, providing 1 dimension/ 2D/Polymer Electrolyte Composite Electrode Material to enhance the transport of ions on the surface of the electrode material and reduce contact resistance.
  • the ion conductive adhesive layer helps to improve the contact between the electrode active material and the solid polymer electrolyte and increase the affinity.
  • Solid supercapacitors have high specific capacity, energy density and stable cycle life. The process requires simple process, low cost and easy scale production. The invention is equally applicable to the development of flexible solid state supercapacitors.
  • FIG. 1 is a schematic structural view of an all-solid lithium ion electric double layer supercapacitor without a liquid additive and without a separator;
  • Figure 2 is a flow chart of the preparation of the present invention
  • FIG. 3 is a schematic view showing a serial connection structure of a series solid double-layer supercapacitor according to the present invention.
  • Figure 4 is a comparison of the results of the impedance of the adhesive layer and the adhesive-free layer in the solid supercapacitor of the present invention.
  • Figure 5 is a CV curve of the solid supercapacitor of the present invention having a voltage range of 0-1.8V;
  • FIG. 6 is a graph showing a test curve and a coulombic efficiency curve of a constant current charging method of 00 volts for a solid supercapacitor having a voltage range of 0-1.8 V of the present invention.
  • 2-stage capacitor 3-series solid double-layer supercapacitor; 4-external connector; 70-binder; 60-opening; 50-solid polymer electrolyte layer; 40-adhesive layer; 30-composite electrode sheet 20-flexible conductive substrate layer and 10-pack layer.
  • the solid polymer electrolyte layer 50 located at the middle portion and the outer electrode and the package portion symmetrically disposed on the top and bottom surfaces of the solid polymer electrolyte layer 50 are included; the external electrode and the package portion are sequentially disposed from the inside to the outside.
  • the solid polymer electrolyte layer 50 is made of a polymer electrolyte composite material, which is a composite structure of a nano-ion conductive material and a solid polymer electrolyte, and the solid polymer electrolyte is a polyvinylidene fluoride copolymer.
  • the material is made of or prepared from a solid polymer electrolyte; the flexible conductive substrate layer 20 comprises a carbon-based fabric, a metal mesh, and/or a conductive polymer layer, and the carbon-based fabric, the metal mesh, and the conductive polymer are coated with a metal. material.
  • the composite electrode sheet 30 is a continuous conductive frame formed of a solid ion conductive polymer and a low-dimensional conductive capacitive material.
  • the solid ion conductive polymer is the same material as the solid polymer electrolyte 50, and the shape structure of the low-dimensional conductive capacitive material includes Zero-dimensional particle structure, one-dimensional nanotube structure and/or two-dimensional layer structure, low-dimensional conductive and capacitive materials include carbon materials, and carbon materials include graphene, carbon nanotubes and activated carbon.
  • the packaging layer 10 is used to protect and seal the supercapacitor, and the packaging layer 10 is a flexible insulating plastic polymer film or an aluminum plastic packaging film. An opening 60 is symmetrically disposed on the top and bottom surfaces of the supercapacitor.
  • the opening 60 is filled with an adhesive 70.
  • the supercapacitor opening 60 is connected to an external adhesive wire, and the opening 60 is connected to an external adhesive wire.
  • a stage capacitor 2 having two external connectors is obtained, and a plurality of supercapacitors are filled in the opening 60 of the adjacent supercapacitor by the adhesive 70 to bond the adjacent supercapacitors to form a tandem solid double Layer supercapacitor 3.
  • a method for preparing an all-solid lithium ion electric double layer supercapacitor without liquid additive and without a diaphragm, as shown in FIG. 2, comprises the following methods:
  • S1 preparing a solid polymer electrolyte layer 50: first dissolving a copolymer of a polymer chain in an organic solvent, and then adding a lithium-based compound salt to the above solution, and setting a mass ratio of 10 wt% to 50 The wt% solution, the inorganic nanoparticles can continue to be doped into the solution, stirred in an inert gas atmosphere for a sufficient time, and finally the solution casting process is used to obtain a solid polymer electrolyte layer 50;
  • the method comprises the steps of: first dissolving a copolymer of polyvinylidene fluoride in dimethylformamide, then adding a borate-based lithium salt, and disposing a copolymer of different mass ratios of polyvinylidene fluoride/borate group; A solution of lithium salt is mixed in an argon atmosphere at a temperature of 60-90 ° C to form a homogeneous solution, and the mixed solution is dropped into a flat surface dish and placed in a vacuum drying oven at 80 ° - 100 ° C for more than 48 h. a solid polymer electrolyte layer 50 of a copolymer of polyvinylidene fluoride/borate-based lithium salt, having a thickness of about 50-100 Um.
  • S2 preparing composite electrode sheet 30: mixing 1D, 2D inorganic carbon material and solid ion conductive polymer into organic solvent, and fully stirring at a certain temperature, the electrode slurry is prepared, and the electrode slurry is prepared.
  • the material is uniformly coated on the flexible conductive substrate layer 20 composed of conductive graphite paper, and dried at a high temperature to obtain a flexible conductive substrate layer 20 covered with the composite electrode sheet 30;
  • the method comprises the following steps: mixing a mixture of activated carbon, graphene oxide, multi-walled carbon nanotubes and a solid polymer electrolyte, wherein the weight ratio of the activated carbon is 20 to 30 wt.%, and the weight ratio of graphene oxide is 15 to 25 wt.%.
  • the weight ratio of the multi-walled carbon nanotubes is 35 to 35 wt.%, and the weight ratio of the solid polymer electrolyte is 10 to 20 wt.%.
  • the mixture is ball-milled at 300 rpm for 3 hours to obtain an electrode slurry, which is then coated on graphite paper.
  • the surface of the flexible conductive substrate layer 20 is then placed in a vacuum drying oven and dried at a temperature of 100 ° C for more than 24 hours to obtain a composite electrode sheet 30.
  • the two steps S2 are used to prepare the flexible conductive substrate layer 20 covered with the composite electrode sheet 30, and the ion conductive copolymer slurry is deposited on the surface of the composite electrode sheet 30, and baked in a vacuum environment for a certain period of time.
  • the adhesive layer 40 is formed to obtain a multilayer structure of the flexible conductive substrate layer 20 - the composite electrode sheet 30 - the adhesive layer 40, and the solid polymer electrolyte layer 50 prepared in the step S1 is sandwiched between two identical flexible conductive groups
  • the bottom layer 20 - the composite electrode sheet 30 - the adhesive layer 40 is pressed at a temperature of 120 ° C to obtain a flexible conductive base layer 20 - a composite electrode sheet 30 - an adhesive layer 40 - a solid polymer electrolyte layer 50 -
  • the adhesive layer 40 - the composite electrode sheet 30 - the flexible conductive base layer 20 is encapsulated using the packaging layer 10.
  • an all-solid lithium ion electric double layer supercapacitor without a liquid additive and without a separator is prepared.
  • This embodiment is based on an activated carbon, a graphene oxide, a carbon nanotube composite material doped with a polymer electrolyte as a symmetric electrode, and an all-solid supercapacitor-1 composed of a copolymer of polyvinylidene fluoride as an electrolyte.
  • the specific steps are as follows: :
  • Solid polymer electrolyte layer 50 First, a copolymer of polyvinylidene fluoride is dissolved in dimethylformamide, and then a borate-based lithium salt is added to configure a copolymer of different mass ratio of polyvinylidene fluoride/boric acid. A solution of a base lithium salt is mixed at 60-90 ° C in an argon atmosphere to form a homogeneous solution. The mixed solution is dropped into a flat surface dish and placed in a vacuum drying oven at 80°-100° C. for more than 48 hours to obtain a polymer electrolyte of a polyvinylidene fluoride copolymer/borate-based lithium salt. About 50-100 Um.
  • Preparation of composite electrode sheet 30 a slurry of activated carbon, graphene oxide, multi-walled carbon nanotubes and a polymer solid electrolyte was ball-milled at 300 rpm for 3 hours to obtain an electrode slurry, which was then coated on the surface of the current collector, wherein The four components are 20 ⁇ 30 wt.%, 15 ⁇ 25 wt.%, 35 ⁇ 35 wt.% and 10 ⁇ 20 wt.%, and then placed in a vacuum drying oven and dried at 100 °C.
  • the electrode sheet can be obtained, the active material mass is about 1-5mg cm -2 , the current collector is graphite paper, the ion conductive polymer solution is spin-coated on the surface of the electrode, and dried under vacuum to form an adhesive layer.
  • the all-solid supercapacitor is a composite of a flexible conductive base layer 20 (graphite carbon paper current collector 20), a composite layer 30 coated with an adhesive layer, a solid polymer electrolyte layer 50: coated with an adhesive layer 40.
  • the electrode sheets 30 and the graphite carbon paper current collectors are sequentially sealed by 20, and the solid supercapacitors are sealed in the packaging layer 10 by using a lamination method.
  • Various tests were performed on all solid state supercapacitors to confirm their performance over a wide range of voltages and stability. The test results are shown in Figures 4, 5 and 6. As shown in FIG.
  • the all-solid supercapacitor containing the adhesive layer 40 has a charge transfer resistance of about 60-80 ⁇ cm-2, which greatly reduces the impedance compared to the ultracapacitor 200 without the adhesive layer 40. 220 ⁇ cm -2 . In addition, it has a high specific capacity of 240-260 F g -1 , a high energy density of 22-30 Wh Kg -1 and excellent cycle stability.

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Abstract

Disclosed are a liquid-additive-free, separator-free, all-solid-state lithium-ion double-electric-layer supercapacitor and a preparation method therefor. The supercapacitor comprises a solid polymer electrolyte layer located in a middle portion, and external electrodes and packaging portions symmetrically disposed on the top and bottom surfaces of the solid polymer electrolyte layer. The external electrode and the packaging portion comprise an adhesive layer, an electrode sheet, a flexible conductive base layer and a packaging layer, which are sequentially disposed from the inside to the outside. The adhesive layer and nanocomposite electrode in the present invention are used for helping to improve contact and enhancing the adhesion between the electrode sheet and the solid polymer electrolyte layer, thereby avoiding direct solid-solid contact between between the electrodes and an electrolyte. In addition, the adhesive layer has good adhesion and is fully compatible with the electrolyte and the electrodes, and same can bring about good contact and reduce the contact resistance between the electrolyte and the electrodes.

Description

一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器及其制备方法All-solid lithium ion electric double layer super capacitor without liquid additive and without diaphragm and preparation method thereof 技术领域Technical field
本发明属于储能器件技术领域，具体涉及一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器及其制备方法。The invention belongs to the technical field of energy storage devices, and particularly relates to an all-solid lithium ion electric double layer super capacitor without liquid additive and without diaphragm and a preparation method thereof.
背景技术Background technique
作为新能源储能器件之一的超级电容器，在诸多要求快速充放电能和长循环使用寿命的应用中被广泛采用，例如汽车、火车以及可再生发电储能等领域。特别是近年来，随着电动汽车市场的快速发展，高能量密度、长寿命、高安全性的超级电容器成为研究热点。传统商业的超级电容器使用水系或者其他液体的电解液。虽然这些液态的电解液具有较高的离子导电率和较高的功率密度等特点，但是，传统的液态超级电容器面临着诸多问题，比如电解液的泄露会腐蚀电极，进而导致性能的损失，甚至，液态电解液的泄露会造成失火等安全隐患。此外，液态电解液具有较小的电压窗口限制了能量密度，并且密封要求高，使得制造复杂化。As one of the new energy storage devices, supercapacitors are widely used in many applications requiring fast charge and discharge energy and long cycle life, such as automobiles, trains, and renewable energy storage. Especially in recent years, with the rapid development of the electric vehicle market, supercapacitors with high energy density, long life and high safety have become research hotspots. Conventional commercial supercapacitors use water or other liquid electrolytes. Although these liquid electrolytes have high ionic conductivity and high power density, traditional liquid supercapacitors face many problems, such as electrolyte leakage, which can corrode the electrodes, resulting in loss of performance, even The leakage of liquid electrolyte may cause safety hazards such as fire. In addition, the liquid electrolyte has a smaller voltage window that limits the energy density and requires high sealing, complicating manufacturing.
相比之下，固态聚合物电解质具有良好的机械性能、无泄漏，从而提升安全性和包装效率，被广泛地认为是液体电解质的替代物。当前，在超级电容器中，通常使用以PVA-H 2SO 4, PVA-H 3PO 4为主的胶体电解质。但是此类凝胶状电解质的工作电压窗口较小（1.0V）, 限制了能量密度 （5-10 Wh kg -1）。锂离子聚合物电解质具有较高的电压窗口，但是，传统的固态锂离子聚合物电解质材料的离子导电性能差（室温下<10 -5 S cm -1）。虽然可以通过添加液态塑化剂提升导电性，但是此方法会同时降低机械性能，仍会发生泄露现象且会造成与电极界面的兼容性不稳定，从而导致循环性能变差。这些凝胶状或者准固态类超级电容器存在安全隐患，限制了其的大规模使用。通过将无机纳米材料或者纳米锂离子导体填充至聚合物电解质可得到有机-无机复合高分子电解质，具有较高的离子电导率（室温下>10 -5 S cm -1）。因此，此类有机-无机复合高分子电解质被期望可以提升固态超级电容器的性能。但是，仍然存在较多问题。例如：现有公开的固态超级电容器的专利中，主要采用了和液态超级电容器相同的组装结构，即：电极-固态电解质-电极三明治结构。然而，这种固体-固体直接接触结构导致高接触电阻，降低了固态超级电容器的性能。此外，传统的固态超级电容器仍然需要额外的隔膜（US8947853B2; US7612985B2），导致复杂的制造程序和高成本。此外，从实用角度考虑，适用于固态超级电容器的固态电解质的电导率需要至少在室温下高于10 -4 S cm -1。因此，制备出一种基于锂离子高导聚合物的全固态超级电容器可以规避以上问题，具有非常重要的现实意义。 In contrast, solid polymer electrolytes have good mechanical properties, no leakage, thereby improving safety and packaging efficiency, and are widely considered as a substitute for liquid electrolytes. Currently, in supercapacitors, a colloidal electrolyte mainly composed of PVA-H 2 SO 4 and PVA-H 3 PO 4 is usually used. However, such a gel electrolyte has a small operating voltage window (1.0 V), which limits the energy density (5-10 Wh kg -1 ). Lithium-ion polymer electrolytes have a high voltage window, but conventional solid-state lithium ion polymer electrolyte materials have poor ion conductivity (<10 -5 S cm -1 at room temperature). Although the conductivity can be improved by adding a liquid plasticizer, this method simultaneously reduces the mechanical properties, and leakage still occurs and the compatibility with the electrode interface is unstable, resulting in poor cycle performance. These gel-like or quasi-solid supercapacitors have safety hazards that limit their large-scale use. An organic-inorganic hybrid polymer electrolyte can be obtained by filling an inorganic nanomaterial or a nano-lithium ion conductor to a polymer electrolyte, and has a high ionic conductivity (>10 -5 S cm -1 at room temperature). Therefore, such an organic-inorganic hybrid polymer electrolyte is expected to improve the performance of a solid supercapacitor. However, there are still many problems. For example, in the patent of the existing disclosed solid supercapacitor, the same assembly structure as the liquid supercapacitor is mainly used, that is, an electrode-solid electrolyte-electrode sandwich structure. However, this solid-solid direct contact structure results in high contact resistance and reduces the performance of solid supercapacitors. In addition, conventional solid supercapacitors still require additional diaphragms (US8947853B2; US7612985B2), resulting in complex manufacturing procedures and high costs. Furthermore, from a practical standpoint, the conductivity of a solid electrolyte suitable for a solid supercapacitor needs to be higher than 10 -4 S cm -1 at least at room temperature. Therefore, the preparation of an all-solid supercapacitor based on lithium ion high conductivity polymer can avoid the above problems and has very important practical significance.
技术问题technical problem
本发明的目的是提供一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器，要解决现有技术制造程序过于复杂，且成本较高的技术问题；并解决现有的凝胶状或者准固态类超级电容器存在安全隐患，不能大规模使用的问题。The object of the present invention is to provide an all-solid-state lithium ion electric double layer supercapacitor without liquid additive and without a diaphragm, which solves the technical problem that the prior art manufacturing process is too complicated and has high cost; and solves the existing gel Shape or quasi-solid supercapacitors have safety hazards and cannot be used on a large scale.
技术解决方案Technical solution
一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器，其特征在于：An all-solid lithium ion electric double layer supercapacitor without liquid additive and without diaphragm, characterized in that:
包括位于中部的固态聚合物电解质层和对称设置在固态聚合物电解质层顶面和底面的外部纳米复合电极；所述外部纳米复合电极包括由内而外顺次设置的粘合剂层、复合电极片和柔性导电基底层，所述纳米复合电极外侧设有包装层。The solid polymer electrolyte layer in the middle portion and the outer nanocomposite electrode symmetrically disposed on the top surface and the bottom surface of the solid polymer electrolyte layer; the external nanocomposite electrode includes an adhesive layer and a composite electrode which are sequentially disposed from the inside to the outside a sheet and a flexible conductive substrate layer, and a packaging layer is disposed outside the nanocomposite electrode.
进一步优选地，所述固态聚合物电解质层由聚合物电解质复合材料制成，所述聚合物电解质复合材料为纳米离子导电性材料与固态聚合物电解质复合的复合结构，所述固态聚合物电解质包括聚偏氟乙烯基共聚物、LiBOB、LiODFB、LiBFMB和LiBFMB衍生物，所述聚偏氟乙烯基共聚物包括PVDF-TrFE、PVDF-TFE和PVDF-HFP；所述纳米离子导电性材料包括纳米尺寸的无机陶瓷填料和离子导体填料，所述无机陶瓷填料包括但不限于BaTiO 3、SiO 2或TiO 2，纳米离子导电性材料在聚合物电解质复合材料中的重量比在0至10 wt.% 重量的范围内。 Further preferably, the solid polymer electrolyte layer is made of a polymer electrolyte composite material, which is a composite structure in which a nano-ion conductive material is combined with a solid polymer electrolyte, and the solid polymer electrolyte includes a polyvinylidene fluoride copolymer, a LiBOB, a LiODFB, a LiBFMB, and a LiBFMB derivative, the polyvinylidene fluoride copolymer including PVDF-TrFE, PVDF-TFE, and PVDF-HFP; the nano-ion conductive material including a nanometer size Inorganic ceramic filler and ionic conductor filler, including but not limited to BaTiO 3 , SiO 2 or TiO 2 , the weight ratio of the nano-ion conductive material in the polymer electrolyte composite is 0 to 10 wt.% by weight In the range.
进一步地，所述粘合剂层由具有离子导电性的共聚聚合物材料制成或由固态聚合物电解质制备而成。Further, the adhesive layer is made of a copolymerizable polymer material having ion conductivity or a solid polymer electrolyte.
进一步地，所述复合电极片由复合材料组成，所述复合材料由固态离子导电聚合物和低维导电电容性材料形成的连续导电框架，所述固态离子导电聚合物是和固态聚合物电解质层相同的材料，所述低维导电电容性材料的形状结构包括零维颗粒结构、一维纳米管结构和/或二维层状结构，所述低维导电电容性材料包括碳材料，所述碳材料包括石墨烯、碳纳米管和活性碳，低维导电电容性材料在复合电极片中的重量比在80~90 wt.% 的重量范围内。Further, the composite electrode sheet is composed of a composite material comprising a continuous conductive frame formed of a solid ion conductive polymer and a low-dimensional conductive capacitive material, the solid ion conductive polymer being a solid polymer electrolyte layer The same material, the shape structure of the low-dimensional conductive capacitive material comprises a zero-dimensional particle structure, a one-dimensional nanotube structure and/or a two-dimensional layer structure, the low-dimensional conductive capacitive material comprises a carbon material, the carbon The material includes graphene, carbon nanotubes and activated carbon, and the weight ratio of low-dimensional conductive and capacitive materials in the composite electrode sheet is 80-90. Weight range of wt.%.
进一步地，所述柔性导电基底层包括碳基织物、金属网和/或导电聚合物层，所述碳基织物、金属网和导电聚合物上均涂覆有金属材料。Further, the flexible conductive substrate layer comprises a carbon-based fabric, a metal mesh and/or a conductive polymer layer, the carbon-based fabric, the metal mesh and the conductive polymer are coated with a metal material.
此外，所述包装层用于保护和密封超级电容器，包装层为柔性绝缘塑料聚合物膜或铝塑料包装膜。Furthermore, the packaging layer is used to protect and seal the supercapacitor, and the packaging layer is a flexible insulating plastic polymer film or an aluminum plastic packaging film.
更加优选地，所述超级电容器顶面和底面上对称设有开口，所述开口内填充有粘合剂，若干个超级电容器通过粘合剂填充在相邻超级电容器的开口内将相邻超级电容器粘合固定形成串联固态双层超级电容器。More preferably, the top surface and the bottom surface of the supercapacitor are symmetrically provided with openings, the openings are filled with an adhesive, and a plurality of supercapacitors are filled in the openings of adjacent supercapacitors by an adhesive to adjacent supercapacitors The adhesive is fixed to form a tandem solid double-layer supercapacitor.
一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器的制备方法，其特征在于，包括以下方法：A method for preparing an all-solid lithium ion electric double layer supercapacitor without liquid additive and without a membrane, characterized in that the method comprises the following methods:
S1、制备固态聚合物电解质层：首先将高分子链的共聚物溶解在有机溶剂中，然后将锂基化合物盐加入上述溶液中，配置质量比为10 wt.%~50 wt.%溶液，无机纳米颗粒可继续掺杂至溶液中，在惰性气体的氛围中搅拌充足时间, 最后采用溶液铸膜法工艺得到固态聚合物电解质层；S1: preparing a solid polymer electrolyte layer: first dissolving the copolymer of the polymer chain in an organic solvent, and then adding a lithium-based compound salt to the above solution, and setting the mass ratio to 10 The wt.%~50 wt.% solution, the inorganic nanoparticles can continue to be doped into the solution, stirred for a sufficient time in an inert gas atmosphere, and finally a solid polymer electrolyte layer is obtained by a solution casting process;
S2、制备复合电极片：将1维、2维的无机碳材料和固态离子导电聚合物混合后加入有机溶剂中，并在一定温度下充分搅拌均匀后，电极浆料制备完成，将电极浆料用涂布方法均匀涂在由导电石墨纸组成的柔性导电基底层上，高温充分烘干后得到覆盖有复合电极片的柔性导电基底层；S2: preparing a composite electrode sheet: mixing a 1D, 2D inorganic carbon material and a solid ion conductive polymer into an organic solvent, and uniformly stirring at a certain temperature, the electrode slurry is prepared, and the electrode slurry is prepared. Uniformly coated on a flexible conductive substrate layer composed of conductive graphite paper by a coating method, and sufficiently dried at a high temperature to obtain a flexible conductive substrate layer covered with a composite electrode sheet;
S3、组装：选取两片步骤S2制备完成覆盖有复合电极片的柔性导电基底层，在复合电极片的表面上沉积离子导电共聚聚合物浆料，在真空环境中烘烤一定的时间形成粘合剂层，从而获得柔性导电基底层-复合电极片-粘合剂层的多层结构，将步骤S1制备的固态聚合物电解质层夹在两个相同的柔性导电基底层-复合电极片-粘合剂层之间，并在80-200 ℃的温度下进行压制得到顺次为柔性导电基底层-复合电极片-粘合剂层-固态聚合物电解质层-粘合剂层-复合电极片-柔性导电基底层的多层结构，并使用包装层封装，至此，一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器制备完成。S3, assembly: two steps S2 are selected to complete the flexible conductive substrate layer covered with the composite electrode sheet, and the ion conductive copolymer polymer slurry is deposited on the surface of the composite electrode sheet, and baked in a vacuum environment for a certain time to form a bond. a layer of the composition, thereby obtaining a multilayer structure of the flexible conductive substrate layer-composite electrode sheet-adhesive layer, and sandwiching the solid polymer electrolyte layer prepared in step S1 on two identical flexible conductive substrate layers-composite electrode sheets-bonding Press between the agent layers and at a temperature of 80-200 ° C to obtain a flexible conductive substrate layer - composite electrode sheet - adhesive layer - solid polymer electrolyte layer - adhesive layer - composite electrode sheet - flexible The multilayer structure of the conductive substrate layer is packaged using a packaging layer. Thus, an all-solid lithium ion electric double layer supercapacitor without liquid additive and without a separator is prepared.
进一步优选地，包括以下方法：所述步骤S1具体包括以下步骤：Further preferably, the method includes the following steps: the step S1 specifically includes the following steps:
首先将聚偏二氟乙烯的共聚物溶解在二甲基甲酰胺中，然后加入硼酸盐基锂盐，配置不同质量比聚偏二氟乙烯的共聚物/硼酸盐基锂盐的溶液，在温度为60-90℃的氩气环境中混合以形成均匀溶液，将混合溶液滴落至平整的表面皿中，在真空干燥箱80°-100°C中放置超过48h后，得到聚偏二氟乙烯的共聚物/硼酸盐基锂盐的固态聚合物电解质层，厚度约10-100 μm。First, a copolymer of polyvinylidene fluoride is dissolved in dimethylformamide, and then a borate-based lithium salt is added, and a solution of a copolymer of different weight ratio of polyvinylidene fluoride/borate-based lithium salt is disposed. Mixing in an argon atmosphere at a temperature of 60-90 ° C to form a homogeneous solution, dropping the mixed solution into a flat surface dish, and placing it in a vacuum drying oven at 80 ° - 100 ° C for more than 48 h to obtain a polydisperse A solid polymer electrolyte layer of a copolymer of vinyl fluoride/borate-based lithium salt having a thickness of about 10 to 100 μm.
更加优选地，所述步骤S2具体包括以下步骤：将活性炭、氧化石墨烯、多壁碳纳米管和固态聚合物电解质混合的浆料，其中活性炭重量比为20~30wt.%，氧化石墨烯重量比为15〜25wt.％，多壁碳纳米管重量比35〜35wt.％，固态聚合物电解质重量比10〜20wt.％，混匀后以300转的速度球磨3h，得到电极浆料，然后涂布在由石墨纸组成的柔性导电基底层表面，之后放置在真空干燥箱中，在100°C温度下干燥超过24h，即可得到复合电极片。More preferably, the step S2 specifically comprises the steps of mixing activated carbon, graphene oxide, multi-walled carbon nanotubes and a solid polymer electrolyte, wherein the weight ratio of activated carbon is 20 to 30 wt.%, and the weight of graphene oxide The ratio is 15 to 25 wt.%, the weight ratio of the multi-walled carbon nanotubes is 35 to 35 wt.%, and the weight ratio of the solid polymer electrolyte is 10 to 20 wt.%. After mixing, the mixture is ball-milled at 300 rpm for 3 hours to obtain an electrode slurry, and then The composite electrode sheet was obtained by coating on the surface of a flexible conductive substrate layer composed of graphite paper, followed by placing in a vacuum drying oven and drying at a temperature of 100 ° C for more than 24 hours.
有益效果Beneficial effect
本发明中的固态聚合物电解质层中包含了共聚物，锂基化合物和无机纳米填充材料，锂基化合物是一种含有较大离子半径的硼酸盐基团阴离子，作为固态增塑剂，帮助降低聚合物电解质的结晶度并改善离子迁移率，增强聚合物电解质的离子电导率。The solid polymer electrolyte layer of the present invention comprises a copolymer, a lithium-based compound and an inorganic nano-filler material, and the lithium-based compound is a borate group anion having a large ionic radius, which acts as a solid plasticizer to help The crystallinity of the polymer electrolyte is lowered and the ion mobility is improved to enhance the ionic conductivity of the polymer electrolyte.
本发明中的粘合剂层40用于帮助改善接触并增加复合电极片30和固态聚合物电解质层50之间的粘合性，避免了电极和电解质之间的固体与固体的直接接触。此外，粘合剂层40具有良好的粘合性并且与电解质与电极完全兼容，其可以带来良好的接触并降低电解质与电极之间的接触电阻。The adhesive layer 40 in the present invention is used to help improve contact and increase the adhesion between the composite electrode sheet 30 and the solid polymer electrolyte layer 50, avoiding direct contact of solids and solids between the electrode and the electrolyte. In addition, the adhesive layer 40 has good adhesion and is fully compatible with the electrolyte and the electrode, which can bring about good contact and reduce the contact resistance between the electrolyte and the electrode.
本发明提供了使用大离子半径硼酸盐基团的阴离子和无机纳米填料来提高固态聚合物电解质的离子电导率，固态聚合物电解质能够在高于1.8V的电压下工作，提供了1维/2维/聚合物电解质复合电极材料以增强离子在电极材料表面的传输并降低接触电阻，离子传导粘合层以帮助改善电极活性材料与固体聚合物电解质之间的接触并增加亲和力，组装后的固态超级电容器具有高比容量、能量密度及稳定的循环寿命的性能，工艺所需流程简单，成本低，易于规模化生产。本发明同样适用于发展柔性固态超级电容器。The present invention provides anionic and inorganic nanofillers using large ionic radius borate groups to increase the ionic conductivity of solid polymer electrolytes. The solid polymer electrolyte can operate at voltages above 1.8V, providing 1 dimension/ 2D/Polymer Electrolyte Composite Electrode Material to enhance the transport of ions on the surface of the electrode material and reduce contact resistance. The ion conductive adhesive layer helps to improve the contact between the electrode active material and the solid polymer electrolyte and increase the affinity. Solid supercapacitors have high specific capacity, energy density and stable cycle life. The process requires simple process, low cost and easy scale production. The invention is equally applicable to the development of flexible solid state supercapacitors.
附图说明DRAWINGS
图1为本发明一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器的结构示意图；1 is a schematic structural view of an all-solid lithium ion electric double layer supercapacitor without a liquid additive and without a separator;
图2为本发明的制备流程图；Figure 2 is a flow chart of the preparation of the present invention;
图3为本发明涉及的串联固态双层超级电容器串接结构示意图；3 is a schematic view showing a serial connection structure of a series solid double-layer supercapacitor according to the present invention;
图4本发明的固态超级电容器中含有粘合剂层和无粘合剂层阻抗结果的比较；Figure 4 is a comparison of the results of the impedance of the adhesive layer and the adhesive-free layer in the solid supercapacitor of the present invention;
图5是本发明的固态超级电容器电压范围为0-1.8V的CV曲线；Figure 5 is a CV curve of the solid supercapacitor of the present invention having a voltage range of 0-1.8V;
图6是本发明的固态超级电容器电压范围为0-1.8V的恒流充电法20000圈测试曲线和库仑效率曲线图。6 is a graph showing a test curve and a coulombic efficiency curve of a constant current charging method of 00 volts for a solid supercapacitor having a voltage range of 0-1.8 V of the present invention.
具体实施方式的附图标号说明：DESCRIPTION OF THE PREFERRED EMBODIMENTS
2-级电容器；3-串联固态双层超级电容器；4-外部连接器；70-粘合剂；60-开口；50-固态聚合物电解质层；40-粘合剂层；30-复合电极片；20-柔性导电基底层和；10-包装层。2-stage capacitor; 3-series solid double-layer supercapacitor; 4-external connector; 70-binder; 60-opening; 50-solid polymer electrolyte layer; 40-adhesive layer; 30-composite electrode sheet 20-flexible conductive substrate layer and 10-pack layer.
本发明的实施方式Embodiments of the invention
为了对本发明的技术特征、目的和效果有更加清楚的理解，现对照附图详细说明本发明的具体实施方式。显然，所描述的实施例仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。For a better understanding of the technical features, objects and effects of the present invention, the embodiments of the present invention are described in detail with reference to the accompanying drawings. It is apparent that the described embodiments are only a part of the embodiments of the invention, and not all of the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention.
一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器，其特征在于：An all-solid lithium ion electric double layer supercapacitor without liquid additive and without diaphragm, characterized in that:
如图2所示，包括位于中部的固态聚合物电解质层50和对称设置在固态聚合物电解质层50顶面和底面的外部电极和包装部；外部电极和包装部包括由内而外顺次设置的粘合剂层40、复合电极片30、柔性导电基底层20和包装层10。As shown in FIG. 2, the solid polymer electrolyte layer 50 located at the middle portion and the outer electrode and the package portion symmetrically disposed on the top and bottom surfaces of the solid polymer electrolyte layer 50 are included; the external electrode and the package portion are sequentially disposed from the inside to the outside. The adhesive layer 40, the composite electrode sheet 30, the flexible conductive substrate layer 20, and the packaging layer 10.
固态聚合物电解质层50由聚合物电解质复合材料制成，聚合物电解质复合材料制成为纳米离子导电性材料与固态聚合物电解质复合的复合结构，固态聚合物电解质为聚偏氟乙烯基共聚物、LiBOB、LiODFB、LiBFMB和LiBFMB衍生物，聚偏氟乙烯基共聚物包括PVDF-TrFE、PVDF-TFE和PVDF-HFP；纳米离子导电性材料包括纳米尺寸的无机陶瓷填料或离子导体填料，无机陶瓷填料为BaTiO 3、SiO 2或TiO 2，纳米尺寸的无机陶瓷填料在聚合物电解质复合材料中的重量比在0至10wt.% 重量的范围内；粘合剂层40由具有离子导电性的共聚聚合物材料制成或由固态聚合物电解质制备而成；柔性导电基底层20包括碳基织物、金属网和/或导电聚合物层，碳基织物、金属网和导电聚合物上均涂覆有金属材料。 The solid polymer electrolyte layer 50 is made of a polymer electrolyte composite material, which is a composite structure of a nano-ion conductive material and a solid polymer electrolyte, and the solid polymer electrolyte is a polyvinylidene fluoride copolymer. LiBOB, LiODFB, LiBFMB and LiBFMB derivatives, polyvinylidene fluoride copolymers including PVDF-TrFE, PVDF-TFE and PVDF-HFP; nano-ion conductive materials including nano-sized inorganic ceramic fillers or ionic conductor fillers, inorganic ceramic fillers For BaTiO 3 , SiO 2 or TiO 2 , the weight ratio of the nano-sized inorganic ceramic filler in the polymer electrolyte composite is in the range of 0 to 10 wt.% by weight; the adhesive layer 40 is copolymerized by ion conductivity. The material is made of or prepared from a solid polymer electrolyte; the flexible conductive substrate layer 20 comprises a carbon-based fabric, a metal mesh, and/or a conductive polymer layer, and the carbon-based fabric, the metal mesh, and the conductive polymer are coated with a metal. material.
复合电极片30是由固态离子导电聚合物和低维导电电容性材料形成的连续导电框架，固态离子导电聚合物是与固态聚合物电解质50相同的材料，低维导电电容性材料的形状结构包括零维颗粒结构、一维纳米管结构和/或二维层状结构，低维导电电容性材料包括碳材料，碳材料包括石墨烯、碳纳米管和活性碳。包装层10用于保护和密封超级电容器，包装层10为柔性绝缘塑料聚合物膜或铝塑料包装膜。超级电容器顶面和底面上对称设有开口60，开口60内填充有粘合剂70，如图3所示，超级电容器开口60与外部粘合剂导线连接，开口60与外部粘合剂导线连接后形成外部连接器4，获得具有两个外部连接器的级电容器2，若干个超级电容器通过粘合剂70填充在相邻超级电容器的开口60内将相邻超级电容器粘合固定形成串联固态双层超级电容器3。The composite electrode sheet 30 is a continuous conductive frame formed of a solid ion conductive polymer and a low-dimensional conductive capacitive material. The solid ion conductive polymer is the same material as the solid polymer electrolyte 50, and the shape structure of the low-dimensional conductive capacitive material includes Zero-dimensional particle structure, one-dimensional nanotube structure and/or two-dimensional layer structure, low-dimensional conductive and capacitive materials include carbon materials, and carbon materials include graphene, carbon nanotubes and activated carbon. The packaging layer 10 is used to protect and seal the supercapacitor, and the packaging layer 10 is a flexible insulating plastic polymer film or an aluminum plastic packaging film. An opening 60 is symmetrically disposed on the top and bottom surfaces of the supercapacitor. The opening 60 is filled with an adhesive 70. As shown in FIG. 3, the supercapacitor opening 60 is connected to an external adhesive wire, and the opening 60 is connected to an external adhesive wire. After forming the external connector 4, a stage capacitor 2 having two external connectors is obtained, and a plurality of supercapacitors are filled in the opening 60 of the adjacent supercapacitor by the adhesive 70 to bond the adjacent supercapacitors to form a tandem solid double Layer supercapacitor 3.
一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器的制备方法，如图2所示，包括以下方法：A method for preparing an all-solid lithium ion electric double layer supercapacitor without liquid additive and without a diaphragm, as shown in FIG. 2, comprises the following methods:
S1、制备固态聚合物电解质层50：首先将高分子链的共聚物溶解在有机溶剂中，然后将锂基化合物盐加入上述溶液中，配置质量比为10wt%~50 wt %溶液，无机纳米颗粒可继续掺杂至溶液中，在惰性气体的氛围中搅拌充足时间, 最后采用溶液铸膜法工艺得到固态聚合物电解质层50；S1: preparing a solid polymer electrolyte layer 50: first dissolving a copolymer of a polymer chain in an organic solvent, and then adding a lithium-based compound salt to the above solution, and setting a mass ratio of 10 wt% to 50 The wt% solution, the inorganic nanoparticles can continue to be doped into the solution, stirred in an inert gas atmosphere for a sufficient time, and finally the solution casting process is used to obtain a solid polymer electrolyte layer 50;
具体包括以下步骤：首先将聚偏二氟乙烯的共聚物溶解在二甲基甲酰胺中，然后加入硼酸盐基锂盐，配置不同质量比聚偏二氟乙烯的共聚物/硼酸盐基锂盐的溶液，在温度为60-90℃的氩气环境中混合以形成均匀溶液，将混合溶液滴落至平整的表面皿中，在真空干燥箱80°-100°C中放置超过48h后，得到聚偏二氟乙烯的共聚物/硼酸盐基锂盐的固态聚合物电解质层50，厚度约50-100 um。Specifically, the method comprises the steps of: first dissolving a copolymer of polyvinylidene fluoride in dimethylformamide, then adding a borate-based lithium salt, and disposing a copolymer of different mass ratios of polyvinylidene fluoride/borate group; A solution of lithium salt is mixed in an argon atmosphere at a temperature of 60-90 ° C to form a homogeneous solution, and the mixed solution is dropped into a flat surface dish and placed in a vacuum drying oven at 80 ° - 100 ° C for more than 48 h. a solid polymer electrolyte layer 50 of a copolymer of polyvinylidene fluoride/borate-based lithium salt, having a thickness of about 50-100 Um.
S2、制备复合电极片30：将1维、2维的无机碳材料和固态离子导电聚合物混合后加入有机溶剂中，并在一定温度下充分搅拌均匀后，电极浆料制备完成，将电极浆料用涂布方法均匀涂在由导电石墨纸组成的柔性导电基底层20上，高温充分烘干后得到覆盖有复合电极片30的柔性导电基底层20；S2, preparing composite electrode sheet 30: mixing 1D, 2D inorganic carbon material and solid ion conductive polymer into organic solvent, and fully stirring at a certain temperature, the electrode slurry is prepared, and the electrode slurry is prepared. The material is uniformly coated on the flexible conductive substrate layer 20 composed of conductive graphite paper, and dried at a high temperature to obtain a flexible conductive substrate layer 20 covered with the composite electrode sheet 30;
具体包括以下步骤：将活性炭、氧化石墨烯、多壁碳纳米管和固态聚合物电解质混合的浆料，其中活性炭重量比为20~30wt.%，氧化石墨烯重量比为15〜25wt.％，多壁碳纳米管重量比35〜35wt.％，固态聚合物电解质重量比10〜20wt.％，混匀后以300转的速度球磨3h，得到电极浆料，然后涂布在由石墨纸组成的柔性导电基底层20表面，之后放置在真空干燥箱中，在100°C温度下干燥超过24h，即可得到复合电极片30。Specifically, the method comprises the following steps: mixing a mixture of activated carbon, graphene oxide, multi-walled carbon nanotubes and a solid polymer electrolyte, wherein the weight ratio of the activated carbon is 20 to 30 wt.%, and the weight ratio of graphene oxide is 15 to 25 wt.%. The weight ratio of the multi-walled carbon nanotubes is 35 to 35 wt.%, and the weight ratio of the solid polymer electrolyte is 10 to 20 wt.%. After mixing, the mixture is ball-milled at 300 rpm for 3 hours to obtain an electrode slurry, which is then coated on graphite paper. The surface of the flexible conductive substrate layer 20 is then placed in a vacuum drying oven and dried at a temperature of 100 ° C for more than 24 hours to obtain a composite electrode sheet 30.
S3、组装：选取两片步骤S2制备完成覆盖有复合电极片30的柔性导电基底层20，在复合电极片30的表面上沉积离子导电共聚聚合物浆料，在真空环境中烘烤一定的时间形成粘合剂层40，从而获得柔性导电基底层20-复合电极片30-粘合剂层40的多层结构，将步骤S1制备的固态聚合物电解质层50夹在两个相同的柔性导电基底层20-复合电极片30-粘合剂层40之间，并在120℃的温度下进行压制得到柔性导电基底层20-复合电极片30-粘合剂层40-固态聚合物电解质层50-粘合剂层40-复合电极片30-柔性导电基底层20，并使用包装层10封装，至此，一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器制备完成。S3. Assembly: The two steps S2 are used to prepare the flexible conductive substrate layer 20 covered with the composite electrode sheet 30, and the ion conductive copolymer slurry is deposited on the surface of the composite electrode sheet 30, and baked in a vacuum environment for a certain period of time. The adhesive layer 40 is formed to obtain a multilayer structure of the flexible conductive substrate layer 20 - the composite electrode sheet 30 - the adhesive layer 40, and the solid polymer electrolyte layer 50 prepared in the step S1 is sandwiched between two identical flexible conductive groups The bottom layer 20 - the composite electrode sheet 30 - the adhesive layer 40 is pressed at a temperature of 120 ° C to obtain a flexible conductive base layer 20 - a composite electrode sheet 30 - an adhesive layer 40 - a solid polymer electrolyte layer 50 - The adhesive layer 40 - the composite electrode sheet 30 - the flexible conductive base layer 20 is encapsulated using the packaging layer 10. Thus, an all-solid lithium ion electric double layer supercapacitor without a liquid additive and without a separator is prepared.
实施例1：Example 1:
本实施例是基于以聚合物电解质掺杂的活性炭、氧化石墨烯、碳纳米管复合材料作为对称电极，以聚偏二氟乙烯的共聚物为电解质组成的全固态超级电容器-1，具体步骤如下：This embodiment is based on an activated carbon, a graphene oxide, a carbon nanotube composite material doped with a polymer electrolyte as a symmetric electrode, and an all-solid supercapacitor-1 composed of a copolymer of polyvinylidene fluoride as an electrolyte. The specific steps are as follows: :
固态聚合物电解质层50：首先将聚偏二氟乙烯的共聚物溶解在二甲基甲酰胺中，然后加入硼酸盐基锂盐, 配置不同质量比聚偏二氟乙烯的共聚物/硼酸盐基锂盐的溶液，在氩气环境中60-90℃混合以形成均匀溶液。将混合溶液滴落至平整的表面皿中，在真空干燥箱80°-100°C中放置超过48h后，得到聚偏二氟乙烯的共聚物/硼酸盐基锂盐的聚合物电解质，厚度约50-100 um。Solid polymer electrolyte layer 50: First, a copolymer of polyvinylidene fluoride is dissolved in dimethylformamide, and then a borate-based lithium salt is added to configure a copolymer of different mass ratio of polyvinylidene fluoride/boric acid. A solution of a base lithium salt is mixed at 60-90 ° C in an argon atmosphere to form a homogeneous solution. The mixed solution is dropped into a flat surface dish and placed in a vacuum drying oven at 80°-100° C. for more than 48 hours to obtain a polymer electrolyte of a polyvinylidene fluoride copolymer/borate-based lithium salt. About 50-100 Um.
复合电极片30的制备：将活性炭, 氧化石墨烯，多壁碳纳米管与聚合物固体电解质的浆料，以300转的速度球磨3h，得到电极浆料，然后涂布在集流体表面，其中四种成分的分别为20~30 wt.%，15〜25 wt.％，35〜35 wt.％和10〜20 wt.％，之后放置在真空干燥箱中，在100°C温度下干燥超过24h，即可得到电极片，活性物质量约为1-5mg cm -2, 集流体为石墨纸，将离子导电聚合物溶液旋涂在电极表面上，真空干燥后形成粘合剂层。 Preparation of composite electrode sheet 30: a slurry of activated carbon, graphene oxide, multi-walled carbon nanotubes and a polymer solid electrolyte was ball-milled at 300 rpm for 3 hours to obtain an electrode slurry, which was then coated on the surface of the current collector, wherein The four components are 20~30 wt.%, 15~25 wt.%, 35~35 wt.% and 10~20 wt.%, and then placed in a vacuum drying oven and dried at 100 °C. 24h, the electrode sheet can be obtained, the active material mass is about 1-5mg cm -2 , the current collector is graphite paper, the ion conductive polymer solution is spin-coated on the surface of the electrode, and dried under vacuum to form an adhesive layer.
全固态超级电容器是将柔性导电基底层20（石墨碳纸集流体20）、涂覆有粘合剂层的复合电极片30、固态聚合物电解质层50：涂覆有粘合剂层40的复合电极片30、石墨碳纸集流体的20顺序密封，通过使用层压法，将固态超级电容器密封在包装层10内。对全固态超级电容器的进行各种测试以确认其在大范围电压以及稳定性方面的性能，测试结果见图4、图5和图6。如图4所示，含有粘合层40的全固态超级电容器的电荷传递电阻约为60-80 Ωcm-2，极大的减小了阻抗相比于不含粘合层40的超级电容器200-220 Ωcm -2。此外，它具有240-260 F g -1的高质量比容量，22-30 Wh Kg -1的高能量密度和优异的循环稳定性。 The all-solid supercapacitor is a composite of a flexible conductive base layer 20 (graphite carbon paper current collector 20), a composite layer 30 coated with an adhesive layer, a solid polymer electrolyte layer 50: coated with an adhesive layer 40. The electrode sheets 30 and the graphite carbon paper current collectors are sequentially sealed by 20, and the solid supercapacitors are sealed in the packaging layer 10 by using a lamination method. Various tests were performed on all solid state supercapacitors to confirm their performance over a wide range of voltages and stability. The test results are shown in Figures 4, 5 and 6. As shown in FIG. 4, the all-solid supercapacitor containing the adhesive layer 40 has a charge transfer resistance of about 60-80 Ωcm-2, which greatly reduces the impedance compared to the ultracapacitor 200 without the adhesive layer 40. 220 Ωcm -2 . In addition, it has a high specific capacity of 240-260 F g -1 , a high energy density of 22-30 Wh Kg -1 and excellent cycle stability.
上面结合附图对本发明的实施例进行了描述，但是本发明并不局限于上述的具体实施方式，上述的具体实施方式仅仅是示意性的，而不是限制性的，本领域的普通技术人员在本发明的启示下，在不脱离本发明宗旨和权利要求所保护的范围情况下，还可做出很多形式，这些均属于本发明的保护之内。The embodiments of the present invention have been described above with reference to the drawings, but the present invention is not limited to the specific embodiments described above, and the specific embodiments described above are merely illustrative and not restrictive, and those skilled in the art In the light of the present invention, many forms may be made without departing from the spirit and scope of the invention as claimed.

Claims (10)

  1. 一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器，其特征在于：An all-solid lithium ion electric double layer supercapacitor without liquid additive and without diaphragm, characterized in that:
    包括位于中部的固态聚合物电解质层（50）和对称设置在固态聚合物电解质层（50）顶面和底面的外部纳米复合电极；所述外部纳米复合电极包括由内而外顺次设置的粘合剂层（40）、复合电极片（30）和柔性导电基底层（20），所述纳米复合电极外侧设有包装层（10）。The solid polymer electrolyte layer (50) located at the middle portion and the outer nanocomposite electrode symmetrically disposed on the top surface and the bottom surface of the solid polymer electrolyte layer (50); the external nanocomposite electrode includes a viscosity set sequentially from the inside to the outside A mixture layer (40), a composite electrode sheet (30) and a flexible conductive substrate layer (20), and a packaging layer (10) is disposed outside the nanocomposite electrode.
  2. 如权利要求1所述的一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器，其特征在于：所述固态聚合物电解质层（50）由聚合物电解质复合材料制成，所述聚合物电解质复合材料为纳米离子导电性材料与固态聚合物电解质复合的复合结构，所述固态聚合物电解质包括聚偏氟乙烯基共聚物、LiBOB、LiODFB、LiBFMB和LiBFMB衍生物，所述聚偏氟乙烯基共聚物包括PVDF-TrFE、PVDF-TFE和PVDF-HFP；所述纳米离子导电性材料包括纳米尺寸的无机陶瓷填料和离子导体填料，所述无机陶瓷填料包括但不限于BaTiO 3、SiO 2或TiO 2，纳米离子导电性材料在聚合物电解质复合材料中的重量比在0至10 wt.% 重量的范围内。 The all-solid-state lithium ion electric double layer supercapacitor without liquid additive and without a separator according to claim 1, wherein the solid polymer electrolyte layer (50) is made of a polymer electrolyte composite material. The polymer electrolyte composite material is a composite structure of a nano-ion conductive material composited with a solid polymer electrolyte, which comprises a polyvinylidene fluoride copolymer, LiBOB, LiODFB, LiBFMB and LiBFMB derivatives, the poly The vinylidene fluoride copolymer comprises PVDF-TrFE, PVDF-TFE and PVDF-HFP; the nano-ion conductive material comprises a nano-sized inorganic ceramic filler and an ionic conductor filler, including but not limited to BaTiO 3 , The weight ratio of SiO 2 or TiO 2 , nano-ion conductive material in the polymer electrolyte composite is in the range of 0 to 10 wt.% by weight.
  3. 如权利要求2所述的一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器，其特征在于：所述粘合剂层（40）由具有离子导电性的共聚聚合物材料制成或由固态聚合物电解质制备而成。A liquid-free additive, diaphragmless all-solid-state lithium ion electric double layer supercapacitor according to claim 2, wherein said adhesive layer (40) is made of a copolymerized polymer material having ion conductivity. Made or prepared from a solid polymer electrolyte.
  4. 如权利要求2所述的一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器，其特征在于：所述复合电极片（30）由复合材料组成，所述复合材料由固态离子导电聚合物和低维导电电容性材料形成的连续导电框架，所述固态离子导电聚合物是和固态聚合物电解质层（50）相同的材料，所述低维导电电容性材料的形状结构包括零维颗粒结构、一维纳米管结构和/或二维层状结构，所述低维导电电容性材料包括碳材料，所述碳材料包括石墨烯、碳纳米管和活性碳，低维导电电容性材料在复合电极片（30）中的重量比在80~90 wt.% 的重量范围内。A liquid-free additive, diaphragmless all-solid-state lithium ion electric double layer supercapacitor according to claim 2, wherein said composite electrode sheet (30) is composed of a composite material, said composite material being composed of solid ions a continuous conductive frame formed of a conductive polymer and a low-dimensional conductive capacitive material, the solid ion conductive polymer being the same material as the solid polymer electrolyte layer (50), the shape structure of the low-dimensional conductive capacitive material including zero Dimensional particle structure, one-dimensional nanotube structure and/or two-dimensional layered structure, the low-dimensional conductive capacitive material comprises carbon material, including graphene, carbon nanotubes and activated carbon, low-dimensional conductive capacitance The weight ratio of the material in the composite electrode sheet (30) is between 80 and 90 Weight range of wt.%.
  5. 如权利要求1所述的一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器，其特征在于：所述柔性导电基底层（20）包括碳基织物、金属网和/或导电聚合物层，所述碳基织物、金属网和导电聚合物上均涂覆有金属材料。A liquid-free additive, diaphragmless all-solid-state lithium ion electric double layer supercapacitor according to claim 1, wherein said flexible conductive substrate layer (20) comprises a carbon-based fabric, a metal mesh and/or a conductive material. A polymer layer coated with a metal material on the carbon-based fabric, the metal mesh, and the conductive polymer.
  6. 如权利要求2所述的一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器，其特征在于：所述包装层（10）用于保护和密封超级电容器，包装层（10）为柔性绝缘塑料聚合物膜或铝塑料包装膜。A liquid-free additive, diaphragmless all-solid-state lithium ion electric double layer supercapacitor according to claim 2, wherein said packaging layer (10) is used for protecting and sealing a supercapacitor, packaging layer (10) It is a flexible insulating plastic polymer film or aluminum plastic packaging film.
  7. 如权利要求1所述的一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器，其特征在于：所述超级电容器顶面和底面上对称设有开口（60），所述开口（60）内填充有粘合剂（70），若干个超级电容器通过粘合剂（70）填充在相邻超级电容器的开口（60）内将相邻超级电容器粘合固定形成串联固态双层超级电容器。An all-solid-state lithium ion electric double layer supercapacitor without a liquid additive and a separator according to claim 1, wherein an opening (60) is symmetrically disposed on a top surface and a bottom surface of the super capacitor, (60) is filled with an adhesive (70), and a plurality of supercapacitors are filled in an opening (60) of an adjacent supercapacitor by an adhesive (70) to bond adjacent supercapacitors to form a tandem solid double layer super Capacitor.
  8. 如权利要求1~8任意一项所述的一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器的制备方法，其特征在于，包括以下方法：The method for preparing a solid-state lithium ion electric double layer supercapacitor without a liquid additive and without a separator according to any one of claims 1 to 8, characterized in that the method comprises the following methods:
    S1、制备固态聚合物电解质层（50）：首先将高分子链的共聚物溶解在有机溶剂中，然后将锂基化合物盐加入上述溶液中，配置质量比为10 wt.%~50 wt.%溶液，无机纳米颗粒可继续掺杂至溶液中，在惰性气体的氛围中搅拌充足时间, 最后采用溶液铸膜法工艺得到固态聚合物电解质层（50）；S1, preparing a solid polymer electrolyte layer (50): first dissolving the copolymer of the polymer chain in an organic solvent, and then adding a lithium-based compound salt to the above solution, and the mass ratio is 10 wt.% to 50 wt.%. The solution, the inorganic nanoparticles can continue to be doped into the solution, stirred for a sufficient time in an inert gas atmosphere, and finally a solid polymer electrolyte layer (50) is obtained by a solution casting process;
    S2、制备复合电极片（30）：将1维、2维的无机碳材料和固态离子导电聚合物混合后加入有机溶剂中，并在一定温度下充分搅拌均匀后，电极浆料制备完成，将电极浆料用涂布方法均匀涂在由导电石墨纸组成的柔性导电基底层（20）上，高温充分烘干后得到覆盖有复合电极片（30）的柔性导电基底层（20）；S2, preparing composite electrode sheet (30): mixing 1D, 2D inorganic carbon material and solid ion conductive polymer into organic solvent, and fully stirring at a certain temperature, the electrode slurry preparation is completed, The electrode slurry is uniformly coated on the flexible conductive substrate layer (20) composed of conductive graphite paper by a coating method, and is sufficiently dried at a high temperature to obtain a flexible conductive substrate layer (20) covered with the composite electrode sheet (30);
    S3、组装：选取两片步骤S2制备完成覆盖有复合电极片（30）的柔性导电基底层（20），在复合电极片（30）的表面上沉积离子导电共聚聚合物浆料，在真空环境中烘烤一定的时间形成粘合剂层（40），从而获得柔性导电基底层（20）-复合电极片（30）-粘合剂层（40）的多层结构，将步骤S1制备的固态聚合物电解质层（50）夹在两个相同的柔性导电基底层（20）-复合电极片（30）-粘合剂层（40）之间，并在80-200 ℃的温度下进行压制得到顺次为柔性导电基底层（20）-复合电极片（30）-粘合剂层（40）-固态聚合物电解质层（50）-粘合剂层（40）-复合电极片（30）-柔性导电基底层（20）的多层结构，并使用包装层（10）封装，至此，一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器制备完成。S3, assembly: two steps S2 are selected to complete the flexible conductive substrate layer (20) covered with the composite electrode sheet (30), and the ion conductive copolymer polymer slurry is deposited on the surface of the composite electrode sheet (30) in a vacuum environment. The baking is performed for a certain period of time to form the adhesive layer (40), thereby obtaining a multilayer structure of the flexible conductive base layer (20)-composite electrode sheet (30)-adhesive layer (40), and the solid state prepared in the step S1 The polymer electrolyte layer (50) is sandwiched between two identical flexible conductive substrate layers (20) - composite electrode sheets (30) - adhesive layer (40) and pressed at a temperature of 80-200 ° C. In turn, the flexible conductive substrate layer (20) - composite electrode sheet (30) - adhesive layer (40) - solid polymer electrolyte layer (50) - adhesive layer (40) - composite electrode sheet (30) - The multilayer structure of the flexible conductive substrate layer (20) is packaged using the packaging layer (10). Thus, an all-solid lithium ion electric double layer supercapacitor without liquid additive and without a separator is prepared.
  9. 如权利要求9所述的一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器的制备方法，其特征在于，包括以下方法：所述步骤S1具体包括以下步骤：The method for preparing an all-solid-state lithium-ion electric double layer supercapacitor without a liquid additive and having a separator according to claim 9, comprising the following method: the step S1 specifically comprises the following steps:
    首先将聚偏二氟乙烯的共聚物溶解在二甲基甲酰胺中，然后加入硼酸盐基锂盐，配置不同质量比聚偏二氟乙烯的共聚物/硼酸盐基锂盐的溶液，在温度为60-90℃的氩气环境中混合以形成均匀溶液，将混合溶液滴落至平整的表面皿中，在真空干燥箱80°-100°C中放置超过48h后，得到聚偏二氟乙烯的共聚物/硼酸盐基锂盐的固态聚合物电解质层（50），厚度约10-100 μm。First, a copolymer of polyvinylidene fluoride is dissolved in dimethylformamide, and then a borate-based lithium salt is added, and a solution of a copolymer of different weight ratio of polyvinylidene fluoride/borate-based lithium salt is disposed. Mixing in an argon atmosphere at a temperature of 60-90 ° C to form a homogeneous solution, dropping the mixed solution into a flat surface dish, and placing it in a vacuum drying oven at 80 ° - 100 ° C for more than 48 h to obtain a polydisperse A solid polymer electrolyte layer (50) of a copolymer of vinyl fluoride/borate-based lithium salt having a thickness of about 10 to 100 μm.
  10. 如权利要求9所述的一种无液态添加剂、无隔膜的全固态锂离子双电层超级电容器的制备方法，其特征在于，包括以下方法：所述步骤S2具体包括以下步骤：将活性炭、氧化石墨烯、多壁碳纳米管和固态聚合物电解质混合的浆料，其中活性炭重量比为20~30wt.%，氧化石墨烯重量比为15〜25wt.％，多壁碳纳米管重量比35〜35wt.％，固态聚合物电解质重量比10〜20wt.％，混匀后以300转的速度球磨3h，得到电极浆料，然后涂布在由石墨纸组成的柔性导电基底层（20）表面，之后放置在真空干燥箱中，在100°C温度下干燥超过24h，即可得到复合电极片（30）。The method for preparing a solid-state lithium ion electric double layer supercapacitor without a liquid additive and having no separator, according to claim 9, comprising the following method: the step S2 specifically comprises the steps of: activating activated carbon, oxidizing A slurry of graphene, multi-walled carbon nanotubes and a solid polymer electrolyte, wherein the weight ratio of activated carbon is 20 to 30 wt.%, the weight ratio of graphene oxide is 15 to 25 wt.%, and the weight ratio of multi-walled carbon nanotubes is 35~ 35wt.%, solid polymer electrolyte weight ratio of 10~20wt.%, after mixing, ball milling at 300 rpm for 3h, to obtain electrode slurry, and then coated on the surface of flexible conductive substrate layer (20) composed of graphite paper, Thereafter, it was placed in a vacuum drying oven and dried at a temperature of 100 ° C for more than 24 hours to obtain a composite electrode sheet (30).
PCT/CN2018/116354 2018-02-13 2018-11-20 Liquid-additive-free, separator-free all-solid-state lithium-ion dual-electric-layer supercapacitor and preparation method therefor WO2019157845A1 (en)

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Publication number Priority date Publication date Assignee Title
JP2012018932A (en) * 2011-09-12 2012-01-26 Nissan Motor Co Ltd Solid electrolyte cell
CN103035416A (en) * 2011-10-04 2013-04-10 逢甲大学 Super capacitor and manufacturing method thereof
CN106450394A (en) * 2016-11-24 2017-02-22 东莞理工学院 PVDF-PEO solid composite polymer electrolyte and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012018932A (en) * 2011-09-12 2012-01-26 Nissan Motor Co Ltd Solid electrolyte cell
CN103035416A (en) * 2011-10-04 2013-04-10 逢甲大学 Super capacitor and manufacturing method thereof
CN106450394A (en) * 2016-11-24 2017-02-22 东莞理工学院 PVDF-PEO solid composite polymer electrolyte and preparation method thereof

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