CN-115051035-B - Method for preparing flexible solid-state battery by using photo-curing assisted stencil printing

CN115051035BCN 115051035 BCN115051035 BCN 115051035BCN-115051035-B

Abstract

The invention relates to a method for preparing a flexible solid-state battery by using photo-curing assisted porous printing, belonging to the field of zinc ion batteries; the battery comprises an anode layer, a cathode layer and a solid electrolyte layer, wherein the anode layer comprises 25-30% of anode active material, 3-6% of electronic conductive agent and 65-75% of photopolymer network matrix, the solid electrolyte layer comprises 28-35% of inorganic nanometer active filler and 65-72% of photopolymer network matrix, the cathode layer is zinc metal sheet, the preparation method effectively combines a photocuring technology and a stencil printing technology, and utilizes the ultraviolet light initiated polymerization principle to solidify anode and electrolyte ink without post-treatment such as degreasing, sintering and the like, so that the preparation time is saved, the raw material waste is reduced, the preparation cost is reduced, the preparation process is energy-saving and environment-friendly, and large-scale mass production can be realized.

Inventors

LIU XIANGYE
BU FAN
LI CHUN
Wang Qiangzheng
GUAN CAO

Assignees

西北工业大学

Dates

Publication Date: 20260512
Application Date: 20220607

Claims (6)

1. A preparation method for preparing a flexible solid-state battery by using photo-curing assisted stencil printing is characterized by comprising the following specific steps: Printing positive electrode ink on a current collector by using a stencil printing device, and performing photo-curing to obtain a positive electrode layer, wherein the current collector comprises any one of stainless steel foil and titanium foil; Step 2, printing solid electrolyte ink on the surface of the positive electrode layer by adopting a stencil printing device, and performing in-situ photo-curing to obtain a solid electrolyte layer on the surface of the positive electrode layer; Step 3, assembling a negative electrode layer on the solid electrolyte layer to obtain a flexible solid-state battery which sequentially comprises a positive electrode layer, a solid electrolyte layer and a negative electrode layer from bottom to top; The flexible solid-state battery comprises an anode layer, a cathode layer and a solid-state electrolyte layer, wherein the cathode layer is a zinc metal sheet, the photo-curing is ultraviolet curing, the ultraviolet power of the ultraviolet curing is 1000-2000 mw/cm 2 , and the photo-curing time of the solid-state electrolyte ink is 8-15 s; the positive electrode layer comprises 25-30% of positive electrode active material, 3-6% of electron conductive agent and 65-75% of photopolymer network matrix by mass percent; The solid electrolyte layer comprises 28-35% of inorganic nanometer active filler and 65-72% of photopolymer network matrix by mass percent; the photosensitive polymer network matrix comprises, by mass, 10-20% of photosensitive resin, 0.1-0.2% of photoinitiator and 80-90% of zinc salt solution; the solid content of zinc salt in the zinc salt solution is 20-25%, the zinc salt comprises zinc trifluoromethane sulfonate, and the zinc salt solution solvent comprises one or more of propylene carbonate, ethylene carbonate and triethyl phosphate.
2. The method for producing a flexible solid-state battery using photo-curing assisted stencil printing according to claim 1, wherein the positive electrode active material comprises any one of manganese dioxide and vanadium pentoxide, and the electron conductive agent comprises one or both of conductive carbon black and carbon nanotubes.
3. The method for manufacturing a flexible solid-state battery using photo-curing assisted stencil printing according to claim 1, wherein the electron conductive agent comprises conductive acetylene black.
4. The method for manufacturing a flexible solid-state battery using photo-curing assisted stencil printing according to claim 1, wherein the inorganic nano-active filler comprises any one of nano-silica or nano-alumina.
5. The method for manufacturing a flexible solid-state battery using photo-curing assisted stencil printing according to claim 1, wherein the photosensitive resin comprises ethoxylated trimethylol propane triacrylate.
6. The method for producing a flexible solid-state battery using photo-curing assisted stencil printing according to claim 1, wherein the photoinitiator comprises one or more of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone and 2-methyl-1- (4-methylthiophenyl) -2-morpholin-1-propanone.

Description

Method for preparing flexible solid-state battery by using photo-curing assisted stencil printing Technical Field The invention belongs to the field of zinc ion batteries, and particularly relates to a method for preparing a flexible solid-state battery by utilizing photo-curing assisted stencil printing. Background With the rapid development of modern science and technology, some intelligent and miniaturized wearable flexible electronic products and components are rapidly rising in the electronic industry, and flexible electronic markets around the world are also rapidly developing. As these microelectronic devices are integrated in various smart systems and flexible applications, development of a compatible flexible energy storage device has been urgent. Among the numerous energy storage devices, the secondary zinc ion battery is considered to be a new generation energy storage device capable of replacing the lithium ion battery due to the advantages of low cost, high energy density, high safety and the like. The traditional zinc ion batteries still adopt aqueous liquid electrolyte, and although the ionic conductivity is high and the electrode wettability is good, zinc dendrites are easy to generate to pierce through a diaphragm to cause short circuit of the batteries, and meanwhile, the batteries cannot realize flexibility due to structural damage and the risk of electrolyte leakage. Compared with a water-based liquid zinc ion battery, the solid zinc ion battery adopts a solid electrolyte which is free of volatilization and stable in structure, avoids the risks of battery short circuit and electrolyte leakage, and can realize excellent flexibility and safety theoretically. Currently, the preparation of high performance flexible solid state zinc ion batteries remains an important challenge. In the conventional manufacturing process, electrode materials are directly coated or deposited on a flexible conductive substrate (e.g., carbon cloth, carbon paper) to achieve the flexibility of the battery device. However, such methods often require complex processes such as hydrothermal, high temperature annealing, etc. to prepare and cure the electrolyte and electrodes, severely limiting the choice of materials and the scale of production. Compared with the method, the porous printing technology has the characteristics of simplicity, high efficiency and large-scale production, and has great development potential in the preparation direction of the solid zinc ion battery. For example, a method of preparing a solid zinc ion battery by directly printing electrodes on hydrogel-reinforced cellulose paper has been reported. The battery has high capacity and energy density, and exhibits excellent mechanical properties. But such a process still requires high temperature drying and the like. In addition, most flexible solid zinc ion batteries are assembled by mechanical pressing, which inevitably causes geometric defects of electrolyte and electrodes, and the interface binding force generated by the flexible solid zinc ion batteries is weak, so that the batteries are difficult to maintain the inherent structure when being deformed from outside, and the electrochemical performance is seriously reduced under the deformation condition. In addition, interface defects between the solid electrolyte and the electrode can lead to a significant increase in interface resistance and a consequent decrease in electrochemical performance, which are major obstacles to commercial application of flexible solid zinc-ion batteries. Therefore, the development of a simple battery manufacturing process solves the problem of stability of an electrode/electrolyte interface, improves the mechanical performance and the electrochemical performance of the battery, and is an important research direction in the field of flexible solid zinc ion batteries. Disclosure of Invention The technical problems to be solved are as follows: In order to avoid the defects of the prior art, the invention provides the flexible solid-state battery and the method for preparing the flexible solid-state battery by utilizing the photo-curing auxiliary porous printing, wherein the solid-state zinc ion battery is integrally prepared by reasonably designing the formulas of electrolyte and positive electrode ink and utilizing the photo-curing auxiliary porous printing method, and the post-treatment procedures such as degreasing, sintering and the like are not needed in all steps. The solid electrolyte can be cured on the positive electrode in situ and effectively crosslinked, the interface of the solid electrolyte and the positive electrode has no obvious geometric defect and has higher binding force, the problems of interfacial compatibility and process compatibility between the electrode and the solid electrolyte material are effectively solved, and the prepared battery has excellent mechanical properties, and simultaneously has lower interfacial resistance and excellent elec