CN109216035A - A kind of all solid state plane asymmetric miniature ultracapacitor device and preparation method thereof - Google Patents

Abstract

Translated fromChinese

本发明涉及微纳器件制造领域，具体为一种全固态平面非对称微型超级电容器及其制备方法。该全固态平面非对称微型超级电容器主要包括以下几部分：柔性基底，沉积于基底上的图案化非金属集流体和电极材料，固态电解液。本发明的有益效果是：采用高电容电极材料，既保留了超级电容器的高的功率密度的优势，又提高了超级电容器的工作电压，进而提高了能量密度。该技术具有工艺简单、加工成本低、效率高、可大规模生产的优点，可广泛的应用于微机电系统、微型机器人、植入式医疗设备等微纳器件领域，为微纳电子设备的发展奠定了基础。

The invention relates to the field of micro-nano device manufacturing, in particular to an all-solid-state planar asymmetrical micro-supercapacitor and a preparation method thereof. The all-solid-state planar asymmetric micro-supercapacitor mainly includes the following parts: a flexible substrate, a patterned non-metallic current collector and electrode material deposited on the substrate, and a solid electrolyte. The beneficial effects of the present invention are: the use of high capacitance electrode material not only retains the advantage of high power density of the supercapacitor, but also increases the working voltage of the supercapacitor, thereby increasing the energy density. This technology has the advantages of simple process, low processing cost, high efficiency, and large-scale production. It can be widely used in the fields of micro-nano devices such as micro-electromechanical systems, micro-robots, and implantable medical equipment. Foundation.

Description

A kind of all solid state plane asymmetric miniature ultracapacitor device and preparation method thereof

Technical field:

The invention belongs to micro-nano device manufacturing field, specially a kind of all solid state plane asymmetric miniature ultracapacitor device andPreparation method.

Background technique:

The fast development of miniaturized electronic devices (such as MEMS, microrobot, miniature implantable medical device)It greatly have stimulated the urgent need to miniature power source.Planar miniature supercapacitor due to power density with higher,Energy density, excellent cycle performance are increasingly becoming a kind of emerging chip energy storage device.To further increase microdeviceEnergy density, research and development plane asymmetric miniature ultracapacitor device are an effective new ways.Currently, non-about planeIn the system of symmetrical button capacitor electrode material, since its positive and negative pole material does not match preferably, electrode utilization rate is not high,Cause the coulombic efficiency of corresponding device not high, energy density is lower, and preparation method is complicated.Therefore, it matches and establishes one newlyAsymmetric electrode material system, it is asymmetric micro- to find a kind of low cost, high efficiency, easily operated, precisely controllable planeThe magnanimity technology of preparing of type supercapacitor has important strategy for plane asymmetric miniature ultracapacitor device practical applicationMeaning.

Summary of the invention:

It is asymmetric miniature super it is an object of the invention to develop a kind of high power density, all solid state plane of high-energy densityGrade capacitor provides a kind of inexpensive, high-efficient, easily operated, mask plate aided filter method that controllability is good to prepare planeAsymmetric miniature ultracapacitor device.

In order to achieve the above object, the technical solution of the present invention is as follows: a kind of all solid state plane asymmetric miniature ultracapacitorDevice mainly includes following sections: flexible substrates, the nonmetallic collector of the patterning being deposited in substrate and electrode material, GuState electrolyte.It is characterized in that the both ends of the patterned electrodes load different anode and negative electrode material respectively.This is entirely solidThe preparation method of state plane asymmetric miniature ultracapacitor device is mask plate aided filter method, it is characterised in that described is nonmetallicCollector and positive and negative electrode material are to be filtered respectively using filtering technique at the both ends of pattern mask plate.

According to above scheme, the flexible substrates that the present invention uses include various filter paper (cellulose mixture film, nylon membrane etc.),PET, polyethylene diagrams, polypropylene diaphragm, paper, textile material, preferably cellulose mixture film, nylon membrane, PET.

According to above scheme, nonmetallic collector that the present invention uses is good conductivity, smooth material, as graphene,Carbon nanotube, PH1000, with a thickness of 10nm-10 μm, preferably 100nm-2 μm of

According to above scheme, the configuration for the patterned electrodes that the present invention uses includes level-crossing finger-type, concentric ring type, puts downLine type, parallel fold lines type, concentric interdigital, having a size of 10 μm of -10cm, preferred size is 100 μm of -1cm；With a thickness of100nm-200 μm, preferred thickness is 200nm-10 μm.

According to above scheme, the present invention make in positive electrode include graphene, active carbon, carbon nanotube, Co (OH)₂、Ni(OH)₂、Co₃O₄、MnO₂, negative electrode material includes graphene, active carbon, carbon nanotube, VN, TiN, Mn₃O₄、MoO₃、Fe₂O₃.JustThe mass ratio of negative electrode material is 5:1-1:5, preferred scope 2:1-1:2.

According to above scheme, the material of high conductivity is added in the positive and negative pole material that the present invention uses, such as graphene, charcoalIt is black, additional proportion 1wt%-20wt%, preferred scope 5wt%-15wt%.

According to above scheme, electrolyte that the present invention uses is liquid electrolyte, the quasi- solid-state electrolytic solution of gel and all solid stateElectrolyte.Wherein liquid electrolyte includes acid, neutral, alkalinity aqueous electrolyte；Cation mainly has glyoxaline cation, pyrrolePyridine cation, piperidines cation, pyrroles's cation, indoles cation, quaternary ammonium cation, trialkyl sulphur cation and other, yinIon mainly has iodide ion, bromide ion, chloride ion, tetrafluoroborate, hexafluorophosphate, nitrate anion, disulfate, trifluoromethylThe example liquid electrolyte of sulfimide.The gelling agent of the quasi- solid-state electrolytic solution of gel includes PVA, PS and silica.It is all solid stateThe gelling agent of electrolyte includes PEO etc..It is preferred that water system and PVA, PEO solid-state electrolytic solution.

According to above scheme, the preparation method of all solid state plane asymmetric miniature ultracapacitor device of the invention includes followingStep: firstly, mask plate is placed on filter paper, one layer of nonmetallic current collector material is filtered respectively at the both ends of mask plate；ItsIt is secondary, anode film material is filtered in one end of mask plate, the other end filters negative film material；Later, mask plate is removed, by instituteThe device of preparation is compacted or is transferred on tablet press machine in other flexible substrates；Finally, dripping upper electrolyte, encapsulation.

According to above-mentioned steps, the mask plate that the present invention uses is made on metal or plastic-substrates respectively using lithographic techniqueKind of hollow out figure is simultaneously accurately positioned, for use in a kind of structure of filtering, configuration include level-crossing finger-type, concentric ring type,Parallel line type, parallel fold lines type, concentric interdigital.

According to above-mentioned steps, the pressure for the tablet press machine that the present invention uses is 5~50MPa, preferably 10~20MPa

According to above-mentioned steps case, encapsulating material of the invention includes flexible package and rigid package.The material of flexible package is PET；Hard Roll package material is PMMA and organic glass, is specially cut into PMMA suitably sized, and it is asymmetric miniature to be placed on planeAround supercapacitor, lid two panels organic glass piece is sealed against respectively up and down.

The present invention, which has the advantage that, proposes a kind of all solid state plane asymmetric miniature ultracapacitor device energy of raisingThe thinking of density, i.e., by screening the usage amount of matched electrode material and material, so that two electrode materials are in charge and dischargeDifferent effects is given full play in journey, and two electrode materials are all not limited solely to the electric double layer adsorbed reaction, simultaneouslyFake capacitance reaction can occur, the successful match of selected electrode material realizes plane asymmetric miniature ultracapacitor device simultaneouslyPurpose with height power density and energy density.In addition, asymmetric micro- using mask plate aided filter technology preparation planeType supercapacitor breaches traditional photo-etching processes, electrodeposition technology etc. time-consuming, technique is difficult to control, process is complicatedLimitation, processing cost greatly reduces, improves processing efficiency, quick, large batch of can prepare with specific severalThe micro super capacitor of what configuration and size.The present invention can be widely used in MEMS, microrobot, miniature plantEnter the micro-nano devices such as formula Medical Devices field.

Detailed description of the invention:

Fig. 1 mask plate aided filter method prepares plane asymmetric miniature ultracapacitor device flow chart.

Fig. 2 plane asymmetric miniature ultracapacitor device schematic diagram and electronic scanner microscope figure.

Fig. 3 present invention patterns anode and cathode configuration, and picture a-e is respectively level-crossing finger-type, concentric ring type, parallelLine style, parallel fold lines type, concentric interdigital.

Fig. 4 plane asymmetric miniature ultracapacitor device performance map.

Specific embodiment:

Embodiment 1

Electrochemical stripping graphene (EG) ultrasonic disperse in ethanol solution, is configured to the dispersion of 0.1mg/mL firstLiquid；By Co (OH)₂Mixed with EG (ratio be Co (OH)₂5wt%) ultrasound, be configured to the Co (OH) of 0.25mg/mL₂/ EG dispersionLiquid；VN and EG is mixed into (3wt% that ratio is VN) ultrasound, is configured to the VN/EG dispersion liquid of 0.25mg/mL.Then, by metalMask plate is placed on nylon filters, filters 0.5mL EG respectively as nonmetallic collector at the both ends of mask plate.In this baseCo (OH) is filtered in one end of mask plate on plinth₂/ EG material, the other end filter VN/EG material, and the mass ratio of two kinds of materials is 1:1.Mask plate is removed later, and prepared device is compacted on tablet press machine, pressure 5MPa.Finally, on the device of preparation1M KOH electrolyte in drop, rigid package carry out electro-chemical test.

Embodiment 2

First by carbon nanotube ultrasonic disperse in ethanol solution, it is configured to the dispersion liquid of 0.1mg/mL；By hole grapheneUltrasound arrangement at 0.25mg/mL dispersion liquid；By TiN ultrasound arrangement at the dispersion liquid of 0.25mg/mL.Then, by metal maskPlate is placed on cellulose mixture filter membrane, filters 1mL carbon nanotube respectively as nonmetallic collector at the both ends of mask plate.?In one end filter hole grapheme material of mask plate on the basis of this, the other end filters TiN material, and the mass ratio of two kinds of materials is 1:1.5.Mask plate is removed later, and prepared device is compacted on tablet press machine, pressure 20MPa.Finally, in the device of preparationPVA/KOH electrolyte in upper drop, rigid package carry out electro-chemical test.

Embodiment 3

First by PH1000 ultrasonic disperse in ethanol solution, it is configured to the dispersion liquid of 0.1mg/mL；By NiO and PH1000Mixing ultrasound is configured to NiO/PH1000 (15wt% that ratio is NiO) dispersion liquid of 0.25mg/mL；By Mn₃O₄With PH1000(ratio Mn₃O₄10wt%) mixing ultrasound, be configured to the Mn of 0.25mg/mL₃O₄/ PH1000 dispersion liquid.Then, by metalMask plate is placed on nylon filters, filters 2mL PH1000 respectively as nonmetallic collector at the both ends of mask plate.HereinOn the basis of mask plate one end filter NiO/PH1000 material, the other end filter Mn₃O₄/ PH1000 material, the matter of two kinds of materialsAmount is than being 1:1.5.Mask plate is removed later, and prepared device is compacted on tablet press machine, pressure 5MPa.Finally, makingUpper PS-PEO/KOH electrolyte is dripped on standby device, rigid package carries out electro-chemical test.

Embodiment 4

First by EG ultrasonic disperse in ethanol solution, it is configured to the dispersion liquid of 0.1mg/mL；Active carbon is mixed with EGUltrasound is configured to active carbon/EG (10wt% that ratio is active carbon) dispersion liquid of 0.25mg/mL；By MnO₂It is mixed with EG superSound is configured to the MnO of 0.25mg/mL₂/ EG (ratio MnO₂15wt%) dispersion liquid.Then, metal mask plate is placed onOn cellulose mixture filter membrane, 0.5mL EG is filtered respectively as nonmetallic collector at the both ends of mask plate.Exist on this basisOne end filter activity charcoal/EG material of mask plate, the other end filter MnO₂/ EG material, the mass ratio of two kinds of materials are 1:3.ItAfter remove mask plate, prepared device is transferred in PET base, pressure 15MPa.Finally, being dripped on the device of preparationUpper 1M NaSO₄Electrolyte, rigid package carry out electro-chemical test.

Embodiment 5

First by EG ultrasonic disperse in ethanol solution, it is configured to the dispersion liquid of 0.1mg/mL；By MnO₂It is mixed with EG superSound is configured to the MnO of 0.25mg/mL₂/ EG dispersion liquid；By MoO₃Ultrasound is mixed with EG, is configured to the MoO of 0.25mg/mL₃/EGDispersion liquid.Then, metal mask plate is placed on nylon filters, filters 0.5mL EG respectively as non-at the both ends of mask plateMetal collector.MnO is filtered in one end of mask plate on this basis₂/ EG material, the other end filter MoO₃/ EG material, two kindsThe mass ratio of material is 1:2.5.Mask plate is removed later, and prepared device is transferred on polyethylene diagrams under stress,Pressure is 15MPa.Finally, dripping upper PVA/NaSO on the device of preparation₄Electrolyte, flexible package carry out electro-chemical test.

Claims (10)

Translated fromChinese

1.一种全固态平面非对称微型超级电容器，其特征在于：1. an all-solid-state planar asymmetric miniature supercapacitor, characterized in that:(1)该微型超级电容器主要包括以下几部分：柔性基底，沉积于基底上的图案化非金属集流体，位于非金属集流体表面的正极材料和负极材料，以及覆盖于正极和负极所在区域上的电解液；(1) The micro-supercapacitor mainly includes the following parts: a flexible substrate, a patterned non-metallic current collector deposited on the substrate, a positive electrode material and a negative electrode material located on the surface of the non-metallic current collector, and the area covering the positive electrode and the negative electrode electrolyte;(2)在柔性基底的图案化的正极材料和负极材料所在区域部分涂覆或滴加电解液后，经封装，即制备出全固态平面非对称微型超级电容器。(2) After coating or dripping electrolyte on the area where the patterned positive electrode material and negative electrode material of the flexible substrate are located, and after encapsulation, an all-solid-state planar asymmetric micro-supercapacitor is prepared.2.根据权利要求1所述的全固态平面非对称微型超级电容器，其特征在于：所述的柔性基底包括各种滤纸(混合纤维素膜或尼龙膜等)、聚对苯二甲酸乙二酯(PET)膜、聚乙烯隔膜、聚丙烯隔膜、纸张或纺织布品；2. The all-solid planar asymmetrical micro-supercapacitor according to claim 1, wherein the flexible substrate comprises various filter papers (mixed cellulose membrane or nylon membrane, etc.), polyethylene terephthalate (PET) film, polyethylene membrane, polypropylene membrane, paper or textile;所述的非金属集流体为导电性好、平整的材料，如石墨烯，碳纳米管，聚乙烯二甲噻吩：聚苯乙烯磺酸(PH1000)中的一种或二种以上，厚度为10nm-10μm。The non-metallic current collector is a material with good conductivity and flatness, such as graphene, carbon nanotubes, polyethylene dimethyl thiophene: one or more of polystyrene sulfonic acid (PH1000), and the thickness is 10nm -10μm.3.根据权利要求1所述的全固态平面非对称微型超级电容器，其特征在于：所述的图案化电极的构型包括平面交叉指型、同心圆型、平行线型、平行折线型、同心交叉指型，微型超级电容器的尺寸为10μm-10cm，厚度为100nm-200μm。3. The all-solid-state planar asymmetrical micro-supercapacitor according to claim 1, wherein the patterned electrode has a planar interdigital shape, a concentric circular shape, a parallel line shape, a parallel broken line shape, and a concentric shape. Interdigitated, micro-supercapacitors are 10μm-10cm in size and 100nm-200μm in thickness.4.根据权利要求1或3所述的全固态平面非对称微型超级电容器，其特征在于：所述的正极材料包括石墨烯、活性炭、碳纳米管、Co(OH)₂、Ni(OH)₂、Co₃O₄、MnO₂中的一种或二种以上，负极材料包括石墨烯、活性炭、碳纳米管、VN、TiN、Mn₃O₄、MoO₃、Fe₂O₃；正极材料和负极材料的质量比为5:1-1:5。4. The all-solid-state planar asymmetric micro-supercapacitor according to claim 1 or 3, wherein the positive electrode material comprises graphene, activated carbon, carbon nanotubes, Co(OH)₂ , Ni(OH)₂ One or more of , Co₃ O₄ , MnO₂ , the negative electrode material includes graphene, activated carbon, carbon nanotubes, VN, TiN, Mn₃ O₄ , MoO₃ , Fe₂ O₃ ; positive electrode material and negative electrode The mass ratio of materials is 5:1-1:5.5.根据权利要求1或4所述的全固态平面非对称微型超级电容器，其特征在于正极材料和负极材料中分别加入高导电性的材料，如石墨烯、导电炭黑中的一种或二种，加入比例为正极或负极材料的0wt％-20wt％。5. the all-solid-state plane asymmetric miniature supercapacitor according to claim 1 or 4, is characterized in that in positive electrode material and negative electrode material, add the material of high conductivity respectively, as one or two in graphene, conductive carbon black The addition ratio is 0wt%-20wt% of the positive electrode or negative electrode material.6.根据权利要求1所述的全固态平面非对称微型超级电容器，其特征在于所述的电解液为液态电解液、凝胶准固态电解液或全固态电解液中的一种；其中液态电解液包括酸性、中性、碱性的水系电解液；阳离子主要有咪唑阳离子、吡啶阳离子、哌啶阳离子、吡咯阳离子、吲哚阳离子、季铵阳离子、三烷基硫阳离子及其他中的一种或二种以上，阴离子主要有碘离子、溴离子、氯离子、四氟硼酸盐、六氟磷酸盐、硝酸根、硫酸氢盐、三氟甲基磺酰亚胺中的一种或二种以上的离子液体电解液；凝胶准固态电解液的胶凝剂包括聚乙烯醇(PVA)、聚苯乙烯共聚物(PS)和二氧化硅中的一种或二种以上；全固态电解液的胶凝剂包括聚氧化乙烯(PEO)。6. all-solid-state planar asymmetric miniature supercapacitor according to claim 1, is characterized in that described electrolyte is a kind of in liquid electrolyte, gel quasi-solid electrolyte or all-solid electrolyte; Wherein liquid electrolyte The liquid includes acidic, neutral and alkaline aqueous electrolytes; the cations mainly include imidazolium cations, pyridinium cations, piperidine cations, pyrrole cations, indole cations, quaternary ammonium cations, trialkylsulfur cations and one or more of others. Two or more, the anions mainly include one or more of iodide ion, bromide ion, chloride ion, tetrafluoroborate, hexafluorophosphate, nitrate, hydrogen sulfate, trifluoromethanesulfonimide The ionic liquid electrolyte; the gelling agent of the gel quasi-solid electrolyte includes one or more of polyvinyl alcohol (PVA), polystyrene copolymer (PS) and silica; Gelling agents include polyethylene oxide (PEO).7.一种权利要求1-6任一所述的全固态平面非对称微型超级电容器的制备方法，其特征在于包括以下步骤：采用掩模板辅助过滤法，首先，将掩模板放置在柔性滤纸上，在掩模板的两端分别过滤一层非金属集流体材料；其次，在掩模板的一端过滤正极薄膜材料，另一端过滤负极薄膜材料；之后，取下掩模板，将所制备的器件在压片机上压实或转压到其他柔性基底上；最后，在柔性基底的图案化的正极材料和负极材料所在区域部分涂覆或滴上电解质，封装。7. a preparation method of the arbitrary described all-solid-state planar asymmetric miniature supercapacitor of claim 1-6, it is characterized in that comprising the following steps: adopt mask plate-assisted filtration method, first, mask plate is placed on flexible filter paper , filter a layer of non-metallic current collector material at both ends of the mask plate; secondly, filter the positive film material at one end of the mask plate, and filter the negative electrode film material at the other end; It is compacted or transferred onto other flexible substrates on a tablet machine; finally, electrolyte is coated or dropped on the area where the patterned positive electrode material and negative electrode material of the flexible substrate are located, and then encapsulated.8.根据权利要求7所述的全固态平面非对称微型超级电容器的制备方法，掩模板是利用刻蚀技术在金属或塑料基底上制作各种镂空图形并精确定位，以便用于过滤的一种结构，其构型包括平面交叉指型、同心圆型、平行线型、平行折线型、同心交叉指型中的一种。8. The preparation method of the all-solid-state planar asymmetrical micro-supercapacitor according to claim 7, wherein the mask plate is a kind of stencil that utilizes etching technology to make various hollow patterns on a metal or plastic substrate and position them precisely so as to be used for filtering. The structure includes one of plane interdigitated type, concentric circle type, parallel line type, parallel broken line type and concentric interdigital type.9.根据权利要求7所述的全固态平面非对称微型超级电容器的制备方法，压片机的压力为5～50MPa。9 . The preparation method of the all-solid planar asymmetric micro-supercapacitor according to claim 7 , wherein the pressure of the tablet press is 5-50 MPa. 10 .10.根据权利要求7所述的全固态平面非对称微型超级电容器的制备方法，封装包括软包装或硬包装，软包装封装材料为PET包裹；硬包装材料为聚甲基丙烯酸甲酯(PMMA)和有机玻璃，具体为将PMMA剪裁成合适的尺寸，放置在平面非对称微型超级电容器的周围，上下分别盖两片有机玻璃片将其密封。10. the preparation method of the all-solid-state planar asymmetric miniature supercapacitor according to claim 7, the encapsulation comprises a soft package or a hard package, and the soft package packaging material is PET wrapping; the hard packaging material is polymethyl methacrylate (PMMA) and organic The glass, specifically cutting PMMA into a suitable size, is placed around the flat asymmetric micro supercapacitor, and two plexiglass sheets are covered up and down to seal it.