阅读说明：本技术 一种微型储能器件在柔性薄膜基底上的批量制备方法 (Batch preparation method of micro energy storage devices on flexible film substrate ) 是由 舒珺 林蔚骁 蔡雨洋 李景昊 魏炜 徐林 于 2020-06-04 设计创作，主要内容包括：本发明提供一种微型储能器件在柔性薄膜基底上的批量制备方法,涉及微型储能器件制备技术领域。S1、将纳米纤维素粉末散于去离子水,并在一定温度的水浴条件下,用氮气吹扫排出体系内的空气；S2、向体系内加入引发剂,充分搅拌后降低温度,并加入纳米纤维素和交联剂,体系持续升温,并且在氮气氛围中充分反应。该微型储能器件在柔性薄膜基底上的批量制备方法,在使用上,实现微型储能器件在柔性薄膜基底上的批量制备,这一多技术联用的方案,相比传统技术速度更快、精度更高,并可通过不同微型电极的组装,实现多电池在同一柔性基底上的联合供能,从而实现功率密度和能量密度的协同提升。(The invention provides a batch preparation method of a micro energy storage device on a flexible film substrate, and relates to the technical field of preparation of micro energy storage devices. S1, dispersing the nano cellulose powder in deionized water, and blowing and discharging air in the system by using nitrogen under the condition of water bath at a certain temperature; and S2, adding an initiator into the system, fully stirring, reducing the temperature, adding the nano-cellulose and the cross-linking agent, continuously heating the system, and fully reacting in a nitrogen atmosphere. According to the batch preparation method of the micro energy storage device on the flexible film substrate, batch preparation of the micro energy storage device on the flexible film substrate is realized in use, compared with the traditional technology, the scheme of multi-technology combination is high in speed and high in precision, and combined energy supply of multiple batteries on the same flexible substrate can be realized through assembly of different micro electrodes, so that the cooperative improvement of power density and energy density is realized.)

1. A batch preparation method of a micro energy storage device on a flexible film substrate is characterized by comprising the following steps:

s1, dispersing the nano cellulose powder in deionized water, and blowing and discharging air in the system by using nitrogen under the condition of water bath at a certain temperature;

s2, adding an initiator into the system, fully stirring, reducing the temperature, adding the nano-cellulose and the cross-linking agent, continuously heating the system, and fully reacting in a nitrogen atmosphere;

s3, transferring the product obtained after the polymerization reaction in the S2 to a room temperature environment, and standing until the product is fully gelatinized;

s4, dropwise adding an alkali solution into the gel obtained in the S3, fully deprotonating, and washing with excessive deionized water until the pH value of the washing solution is 6-7;

s5, treating the gel treated by the S4 by using an extracting agent at room temperature, putting the precipitate in an oven, drying to constant weight, crushing, sieving, and collecting 80-100-mesh nano-cellulose hydrogel;

s6, grinding the carbonized biomass carbon and adding the nano cellulose hydrogel in the S5 into a stirring tank, and mixing and stirring to form printing slurry;

s7, filling the prepared slurry into a pneumatic pushing printing head of a BIO-X3D printer, fixing the printing head, placing a printing substrate on a printing table, and closing an outer cover;

s8, setting a program, setting a printing mode to be air pressure pushing, using 120kpa of an internal air pump, selecting a printing speed of 10mm/S, selecting a printing layer height of 0.2, selecting a density of 30%, selecting a printing size of 10 x 10, after pre-extrusion is completed, automatically leveling a printing platform and a printing head, and starting clicking after an initial printing position is manually set.

2. The method for mass production of a miniature energy storage device on a flexible film substrate as claimed in claim 1, wherein the temperature under the water bath condition is 55-65 ℃ in the operating step according to S1.

3. The method for mass production of a miniature energy storage device on a flexible film substrate according to claim 1, wherein the temperature is reduced to 35-45 ℃ in the operation step according to S2.

4. The method for batch fabrication of a micro energy storage device on a flexible film substrate according to claim 1, wherein the temperature of the system is continuously increased to 70-80 ℃ in the operation step according to S2.

5. The method of mass production of micro energy storage devices on flexible film substrates according to claim 1, further comprising the following biomass carbonization step according to the operation step in S6:

s601, sealing the biomass material in a closed container, and heating the closed container to ignite and burn the biomass material;

s602, releasing gas through a closed container, controlling the pressure in the closed container to be 1.2-1.5 Mpa, conveying supplementary air into the closed container, enabling the temperature of the whole biomass material to reach 400-500 ℃, and simultaneously controlling the pressure in the closed container to be 1.2-1.5 Mpa;

s603, releasing the gas in the closed container, and reducing the pressure of the closed container to 0.8-1.0 MPa;

s604, grinding the carbonized biomass material to prepare carbonized biomass carbon, and grinding.

6. The method of claim 1, wherein the stirring blade in the stirring tank rotates at a speed of 300r/min for a stirring time of 2h to 3h in the operation step of S6.

7. The method of mass production of a micro energy storage device on a flexible film substrate according to claim 1, wherein the printer prints for a time of 42-47S in the operation step according to S8.

8. The method of mass production of a micro energy storage device on a flexible film substrate according to claim 5, wherein in the operation step according to S603, the supplementary air is continuously supplied to the top of the closed vessel at a pressure of 0.8Mpa to 1.0Mpa to maintain the combustion for a certain period of time, and the pressure reduction by controlling the release of the gas to a lower pressure level is repeated two or more times to successively lower the pressure to completely carbonize the biomass material.

Technical Field

The invention relates to the technical field of preparation of miniature energy storage devices, in particular to a batch preparation method of miniature energy storage devices on a flexible film substrate.

Background

Under the conditions of gradual shortage of energy and continuous aggravation of environmental pollution, the development of new energy storage devices is an urgent need for breaking the bottleneck restriction of energy resources, ensuring energy safety and treating pollution. Particularly, the application of the micro energy storage device in electronic products is increasingly wider, at present, liquid electrolyte is generally adopted in commercial lithium ion batteries, and the problems of low ignition point, low flash point and liquid leakage bring great potential safety hazards. Compared with liquid electrolyte, the all-solid electrolyte reduces the risks of liquid leakage, ignition and the like in the charging and discharging processes. However, the characteristics of fragility and high hardness of the solid electrolyte hinder the application of the solid electrolyte in the field of flexible and foldable batteries, and the flexible wearable device is an emerging and promising field, which has been widely studied in the fields of smart clothing, smart bracelets, foldable mobile phones, and the like. The rigid planar structure of conventional energy devices such as lithium ion batteries and supercapacitors greatly limits their applications. Therefore, people try to research the difference between the fibrous flexible lithium ion battery and the supercapacitor and the plane, and the fibrous lithium ion battery and the supercapacitor have the characteristics of light weight, weaving and wearing, so that the fibrous lithium ion battery and the supercapacitor provide good prospects for the development of modern electronic devices. Similar to the traditional planar energy storage device, the fibrous lithium ion battery has high energy density and low power density, while the fibrous super capacitor has high power density and low energy density, but in the prior art, the flexible all-solid-state battery is mainly concentrated on the all-solid-state thin film battery, and in the electrode coating process prepared by using the 3D printing microelectrode technology, the problems of poor electrode mechanical stability and easy electrode pulverization and shedding in the battery circulation process are solved.

Disclosure of Invention

The invention aims to provide a batch preparation method of a micro energy storage device on a flexible film substrate, which can effectively solve the problems in the background technology.

In order to achieve the purpose, the invention is realized by the following technical scheme: a batch preparation method of a micro energy storage device on a flexible film substrate comprises the following steps:

and S1, dispersing the nano cellulose powder in deionized water, and blowing nitrogen to exhaust air in the system under the condition of water bath at a certain temperature.

And S2, adding an initiator into the system, fully stirring, reducing the temperature, adding the nano-cellulose and the cross-linking agent, continuously heating the system, and fully reacting in a nitrogen atmosphere.

S3, transferring the product obtained after the polymerization reaction in the S2 to a room temperature environment, and standing until the product is completely gelled.

S4, dropwise adding an alkali solution into the gel obtained in the S3, fully deprotonating, and washing with excessive deionized water until the pH value of the washing solution is 6-7.

And S5, treating the gel treated by the S4 by using an extracting agent at room temperature, putting the precipitate in an oven, drying to constant weight, crushing, sieving and collecting the 80-100-mesh nano-cellulose hydrogel.

And S6, grinding the carbonized biomass carbon and adding the nano cellulose hydrogel in the S5 into a stirring tank, and mixing and stirring to form the slurry for printing.

S7, filling the prepared slurry into the pneumatic pushing printing head of the BIO-X3D printer, fixing the printing head, placing the printing substrate on the printing table, and closing the outer cover.

S8, setting a program, setting a printing mode to be air pressure pushing, using 120kpa of an internal air pump, selecting a printing speed of 10mm/S, selecting a printing layer height of 0.2, selecting a density of 30%, selecting a printing size of 10 x 10, after pre-extrusion is completed, automatically leveling a printing platform and a printing head, and starting clicking after an initial printing position is manually set.

Further, in the operation step according to S1, the temperature under the water bath condition was 55 to 65 ℃.

Further, in the operation step according to S2, the temperature is decreased to 35 to 45 ℃.

Further, in the operation step according to S2, the temperature of the system is continuously increased to 70-80 ℃.

Further, according to the operation step in S6, the method further comprises the following biomass carbonization steps:

s601, sealing the biomass material in a closed container, and heating the closed container to ignite and burn the biomass material.

S602, releasing gas through the closed container, controlling the pressure in the closed container to be 1.2-1.5 Mpa, conveying supplementary air into the closed container, enabling the temperature of the whole biomass material to reach 400-500 ℃, and simultaneously controlling the pressure in the closed container to be 1.2-1.5 Mpa.

S603, releasing the gas in the closed container, and reducing the pressure of the closed container to 0.8-1.0 MPa.

S604, grinding the carbonized biomass material to prepare carbonized biomass carbon, and grinding.

Further, in the operation step according to S6, the rotation speed of the stirring paddle in the stirring tank is 300r/min, and the stirring time is 2h-3 h.

Further, in the operation step according to S8, the printer prints for 42 to 47S.

Further, in the operation step according to S603, the supplementary air is continuously supplied to the top of the closed vessel at a pressure of 0.8Mpa to 1.0Mpa to maintain the combustion for a certain period of time, and the pressure reduction by controlling the release of the gas to a lower pressure level is repeated two or more times to successively lower the pressure to completely carbonize the biomass material.

The invention provides a batch preparation method of a micro energy storage device on a flexible film substrate. The method has the following beneficial effects:

the batch preparation method of the micro energy storage device on the flexible film substrate comprises the steps of mixing nano cellulose powder and deionized water to prepare nano cellulose hydrogel, grinding carbonized biomass carbon and mixing the ground biomass carbon with the nano cellulose hydrogel to prepare printing slurry, filling the prepared slurry into an air pressure pushing printing head of a BIO-X3D printer, fixing the printing head, placing a printing substrate on a printing table, closing an outer cover, setting a program, setting a printing mode to be air pressure pushing, using 120kpa of an internal air pump to select a printing speed of 10mm/s, selecting a printing layer height of 0.2, selecting a density of 30%, selecting a printing size of 10X 10, automatically leveling the printing platform and the printing head after pre-extrusion is completed, starting clicking after an initial printing position is manually set, printing for a time of 42-47s, and realizing batch preparation of the micro energy storage device on the flexible film substrate in use, compared with the traditional technology, the scheme of multi-technology combination is higher in speed and higher in precision, and can realize combined energy supply of multiple batteries on the same flexible substrate through the assembly of different micro electrodes, so that the cooperative improvement of power density and energy density is realized.

Detailed Description