A kind of paper base capacitor laser engraving preparation method with three-dimensional energy storing structure
阅读说明：本技术 一种具有三维储能结构的纸基电容器激光雕刻制备方法 (A kind of paper base capacitor laser engraving preparation method with three-dimensional energy storing structure ) 是由 姜雪宁 刘冈 罗豪 于 2019-09-05 设计创作，主要内容包括：一种具有三维储能结构的纸基电容器激光雕刻制备方法,属于储能材料与技术领域。制备步骤如下：首先制备纸质三维导电基片,然后在导电基片上进行激光雕刻,得到三维结构电极阵列,最后进行电解质双面涂敷与渗透,经过干燥,获得具有三维储能结构的纸基柔性电容器。该方法通过对电极材料纸质三维导电基片进行激光雕刻,能够简便、高效地实现不同构造纸基电容器的制备,制备工艺简单、成本低,同时由于该方法制备的电容器具有三维储能结构,器件具有很好的储能特性以及柔韧性。(A kind of paper base capacitor laser engraving preparation method with three-dimensional energy storing structure, belongs to energy storage material and technical field.Preparation step is as follows: preparing papery three-dimensional conductive substrate first, then laser engraving is carried out on conductive substrate, obtains three-dimensional structure electrod-array, finally carries out electrolyte double-coated and infiltration, by drying, the paper base flexible capacitor with three-dimensional energy storing structure is obtained.This method is by carrying out laser engraving to electrode material papery three-dimensional conductive substrate, it can simply, efficiently realize the preparation of different configuration paper base capacitor, preparation process is simple, at low cost, simultaneously because the capacitor of this method preparation has three-dimensional energy storing structure, device has good energy storage characteristic and flexibility.)
1. a kind of paper base capacitor laser engraving preparation method with three-dimensional energy storing structure, it is characterized in that: specific preparation step It is as follows:
Step 1: the preparation of papery three-dimensional conductive substrate
Electrode material slurry is prepared, using double-face vacuum suction filtration or dipping method, electrode material slurry is made to penetrate into porous flexible paper Matter base internal is attached to surface simultaneously, is then dried in 25-100 DEG C of vacuum drying oven 5-30 hours, forms papery Three-dimensional conductive substrate；
Step 2: prepared by the laser engraving of three-dimensional electrode arrays
Using the three-dimensional electrode arrays configuration of computer software design, laser pattern engraving is carried out on papery conductive substrate, During laser scanning, laser power is 1-30 watts, laser scan rate 100-10000 mm/second, and in paper substrates Upper dropwise addition deionized water or distilled water are to reduce temperature；Iterative cycles scanning is carried out, until in laser-scanning position papery matrix Electrode material be carbonized or aoxidize removing, and paper substrates are retained, to obtain three-dimensional electrode arrays configuration；
Step 3: the dual coating of electrolyte and the formation with three-dimensional energy storing structure paper base capacitor
Hydrogel electrolyte is prepared, then applies hydrogel electrolyte in the three-dimensional electrode arrays configuration tow sides prepared, Promote infiltration of the hydrogel electrolyte in paper substrates, is finally dried 5-30 hour at 25-50 DEG C in air, acquisition Paper base capacitor with three-dimensional energy storing structure.
2. a kind of paper base capacitor laser engraving preparation method with three-dimensional energy storing structure according to claim 1, Be characterized in: the three-dimensional electrode arrays configuration includes interdigital electrode configuration and other shaped electrode structures, wherein special-shaped battery Pole structure includes but is not limited to S type, L-type, A type, H-type electrode structure, and since electrode material is permeated in entire paper substrates Inside, so that electrode has three-dimensional conductive characteristic.
3. a kind of three-dimensional structure paper base capacitor laser engraving preparation method according to claim 1, it is characterized in that: described Paper base capacitor with three-dimensional energy storing structure includes the single paper base capacitor with three-dimensional energy storing structure, also includes by multiple Cascaded structure, parallel-connection structure and the serial-parallel structure that paper base capacitor with three-dimensional energy storing structure is constituted.
4. a kind of paper base capacitor laser engraving preparation method with three-dimensional energy storing structure according to claim 1, It is characterized in: the composition of the electrode material are as follows: the carbon materials powder and transition metal oxide powder that mass content is 40-95% The combination electrode material powder that body or conducting polymer materials powder are constituted；Wherein, the carbon materials powder is graphene, carbon The mixed powder of one or more of nanometer rods, carbon nanotube and activated carbon, transition metal oxide powder are vanadium oxide, oxygen Change cobalt, manganese oxide, nickel oxide or ferric oxide powder, conducting polymer materials powder is polyaniline, polypyrrole or polythiophene powder.
5. a kind of paper base capacitor laser engraving preparation method with three-dimensional energy storing structure according to claim 1, It is characterized in: the preparation steps of the electrode material slurry are as follows: disperse combination electrode material powder in solvent, be placed in ice bath Sonic oscillation 30-90 minutes, then dispersion liquid is placed in and stands 5-24 hours at room temperature, finally extracts uniform and stable supernatant As electrode material slurry；Wherein, solvent be dimethylformamide, ethyl alcohol, dimethyl sulfoxide, N-Methyl pyrrolidone, go from The mixed solvent of one or more of sub- water, isopropanol.
6. a kind of paper base capacitor laser engraving preparation method with three-dimensional energy storing structure according to claim 1, It is characterized in: the composition of the hydrogel electrolyte are as follows: deionized water includes carboxymethyl cellulose, polyvinyl alcohol or polyoxyethylene The high-molecular organic material of alkene and the inorganic matter comprising phosphoric acid, sulfuric acid, sodium sulphate, potassium hydroxide, lithium sulfate or lithium perchlorate, institute State deionized water: high-molecular organic material: the mass ratio of inorganic matter is 8-16:1-3:1；By the mixture matched above in 60- Magnetic agitation is carried out in 100 DEG C of water-baths, until solution becomes clear, obtains hydrogel electrolyte.
Technical field
The paper base capacitor laser engraving preparation method with three-dimensional energy storing structure that the present invention relates to a kind of, belongs to energy storage material Material and technical field.
Background technique
Capacitor is also referred to as electrochemical capacitor, is a kind of novel energy storage device.The power density and energy of capacitor Density is between traditional capacitor and battery, and relative to battery and fuel cell, capacitor has high power density, quickly fills The advantage of electric discharge and long circulation life；Relative to traditional capacitor, capacitor has the advantage of high-energy density.Wherein, paper base Capacitor is due to its unique high-flexibility and Miniaturized advantage, it is considered to be wearable and portable electronic device novel Energy storage device.
The micromation paper base capacitor explored effective way and research and develop new technology preparation high quality is the weight in the current field Want developing direction.Zhaoyang Liu et al. (Advanced Materials 2016,28,2217) has prepared graphite first Then the combination electrode slurry that alkene and electro-chemical activity organic polymer PH1000 are constituted assists spraying printing, In by template Interdigitation planar capacitor is prepared in paper substrates；This method is conducive to prepare the series and parallel structure of capacitor, but needs spy Different lithographic equipment carries out electrode template preparation, and complex process is at high cost；And the capacitor obtained has planar structure, storage Charge active area is small, cause the energy-storage property of capacitor it is not high (under the sweep speed of 1mV/s area specific capacitance be 5.4mF/ cm2).Zhang Haixia et al. discloses a kind of free style button capacitor based on laser graphics and manufacturing method (patent application Number 201610953666.8), preparation step specifically includes that (1) prepares PVDF Nanowire by electrostatic spinning on back electrode Dimension；(2) carbon nanotube neopelex solution is added dropwise on PVDF nanofiber and is used as flexible electrode；It (3) will be electric Pole is transferred to PVA-H3On PO4 solid electrolyte；(4) Au electrode layer is sputtered on electrolyte-flexible electrode, as capacitor collection Fluid；(5) by laser graphics mode, metal collector layer, flexible electrode layer are cut into interdigitated electrode structure, and it is following Solid-state electrolyte layer remain unchanged, obtain free style button capacitor.This method preparation capacitor have high-flexibility and It is Miniaturized, but equally there is the deficiencies of preparation step is complicated, at high cost.Wenli Zhang et al. (Adv. Energy Mater. 2018,1801840) use laser etching method by lignin conversion for graphene, it then will be without laser spoke According to lignin carry out water dissolution and remove, to obtain the interdigital electrode with three-dimensional grapheme structure, and further coating electricity Xie Zhi obtains micromation capacitor.The preparation of Different electrodes pattern can be carried out on multiple polymers substrate using this method, But lignin is influenced to the carbonisation of graphene by many factors such as laser power density and irradiation time, is not allowed The grapheme material for easily obtaining high quality, on interdigital electrode surface, vapor deposition golden film can be improved the electric conductivity and capacitor of electrode Energy storage characteristic, but process complications and cost is caused to improve；In addition, using polymethyl methacrylate in this method (PMMA), the polymer matrix films such as poly terephthalic acid class plastics (PET) are as capacitor supporter, increase device volume and Without flexibility.
Summary of the invention
In order to overcome problems of the prior art, the present invention provides a kind of paper base capacitor with three-dimensional energy storing structure Device laser engraving preparation method, this method by carrying out laser engraving to electrode material papery three-dimensional conductive substrate, can it is easy, Efficiently realize the preparation of different configuration paper base capacitor, preparation process is simple, at low cost, simultaneously because the electricity of this method preparation Container has three-dimensional energy storing structure, and the energy storage characteristic of device is optimized.
The technical solution adopted by the present invention is that: a kind of paper base capacitor laser engraving preparation side with three-dimensional energy storing structure Method, specific preparation process is as follows:
Step 1: the preparation of papery three-dimensional conductive substrate
Electrode material slurry is prepared, using double-face vacuum suction filtration or dipping method, electrode material slurry is made to penetrate into porous flexible paper Matter base internal is attached to surface simultaneously, is then dried in 25-100 DEG C of vacuum drying oven 5-30 hours, forms papery Three-dimensional conductive substrate；
Step 2: prepared by the laser engraving of three-dimensional electrode arrays configuration
Using the three-dimensional electrode arrays configuration of computer software design, laser pattern engraving is carried out on papery conductive substrate, During laser scanning, laser power is 1-30 watts, laser scan rate 100-10000 mm/second, and in paper substrates Upper dropwise addition deionized water or distilled water are to reduce temperature；Iterative cycles scanning is carried out, until in laser-scanning position papery matrix Electrode material be carbonized or aoxidize removing, and paper substrates are retained, to obtain three-dimensional electrode arrays configuration；
Step 3: the dual coating of electrolyte and the formation of three-dimensional structure capacitor
Hydrogel electrolyte is prepared, then applies hydrogel electrolyte in the three-dimensional electrode arrays configuration tow sides prepared, Promote infiltration of the hydrogel electrolyte in paper substrates, is finally dried 5-30 hour at 25-50 DEG C in air, acquisition Paper base capacitor with three-dimensional energy storing structure.
The three-dimensional electrode arrays configuration includes interdigital electrode configuration and other shaped electrode structures, wherein special-shaped battery Pole structure including but not limited to S type, L-type, A type, H-type configuration electrode structure, and due to electrode material permeate in entire papery Base internal, so that electrode has three-dimensional conductive characteristic.
The paper base capacitor with three-dimensional energy storing structure includes the single paper base capacitor with three-dimensional energy storing structure, It also include cascaded structure, parallel-connection structure and the serial-parallel knot being made of multiple paper base capacitors with three-dimensional energy storing structure Structure.
The composition of the electrode material are as follows: the carbon materials powder and transition metal oxide powder that mass content is 40-95% The combination electrode material powder that body or conducting polymer materials powder are constituted；Wherein, the carbon materials powder is graphene, carbon The mixed powder of one or more of nanometer rods, carbon nanotube and activated carbon, transition metal oxide powder are vanadium oxide, oxygen Change cobalt, manganese oxide, nickel oxide or ferric oxide powder, conducting polymer materials powder is polyaniline, polypyrrole or polythiophene powder.
The preparation steps of the electrode material slurry are as follows: disperse combination electrode material powder in solvent, be placed in ice bath Middle sonic oscillation 30-90 minutes, then dispersion liquid is placed in and stands 5-24 hours at room temperature, finally extracts uniform and stable supernatant Liquid is as electrode material slurry；Wherein, solvent is dimethylformamide, ethyl alcohol, dimethyl sulfoxide, N-Methyl pyrrolidone, goes The mixed solvent of one or more of ionized water, isopropanol.
The composition of the hydrogel electrolyte are as follows: deionized water includes carboxymethyl cellulose, polyvinyl alcohol or polyoxyethylene The high-molecular organic material of alkene and the inorganic matter comprising phosphoric acid, sulfuric acid, sodium sulphate, potassium hydroxide, lithium sulfate or lithium perchlorate, institute State deionized water: high-molecular organic material: the mass ratio of inorganic matter is 8-16:1-3:1；By the mixture matched above in 60- Magnetic agitation is carried out in 100 DEG C of water-baths, until solution becomes clear, obtains hydrogel electrolyte.
The beneficial effects of the present invention are:
1. in the preparation process of the paper base capacitor with three-dimensional energy storing structure described in, electrode material papery conductive substrate is adopted It can be realized, do not need using common commercialization laser with vacuum filtration or dipping method preparation, the engraving of electrod-array Instrument and equipment costly；In addition, prepared electrode conductivuty containing carbon materials is good, do not need additionally to prepare metal afflux Body, entire device preparation technology is simple, low in cost；
2. in the paper base capacitor with three-dimensional energy storing structure described in, electrode material, which is impregnated with, to be distributed in entire paper substrates Portion and surface, laser engraving runs through entire paper substrates, while realizing electrolyte in substrate by the coating of face electrolyte anyway It is fully penetrated, therefore the capacitor prepared has three-dimensional energy storing structure, for common two-dimentional paper base capacitor, storage Energy characteristic is optimized and is improved；
3. micromation and the special-shaped preparation of capacitor and its preparation of series and parallel structure, energy can be conveniently realized using this method Enough meet portable, wearable electronic application demand.
Detailed description of the invention
Fig. 1 is the interdigitation Graphene electrodes three-dimensional energy storing structure paper base capacitor for preparing in embodiment one in different electric currents Constant current charge-discharge curve under density, current density are respectively 0.3mA/cm2And 0.5mA/cm2。
Fig. 2 be the interdigitation Graphene electrodes three-dimensional energy storing structure paper base capacitor that is prepared in embodiment one 0.5 mA/ cm2Under current density in closed loop folding process area specific capacitance with folding times variation diagram.
Specific embodiment
With reference to the accompanying drawing, it is described further by specific embodiment.