A flexible solid-state battery and method of making using light-cured assisted stencil printing

Abstract

The application discloses a kind of preparation flexible solid-state battery and method using light curing auxiliary hole plate printing, belong to zinc ion battery field;The battery includes positive electrode layer, negative electrode layer and solid electrolyte layer;Positive electrode layer includes raw material and mass fraction ratio is positive electrode active material 25~30%, electronic conductive agent 3~6%, photosensitive polymer network matrix 65~75%;Solid electrolyte layer includes raw material and mass fraction ratio is inorganic nano active filler 28~35%, photosensitive polymer network matrix 65~72%;Negative electrode layer is zinc metal sheet;Preparation method effectively combines light curing technology and hole plate printing technology, utilizes the principle of ultraviolet light initiation polymerization to make positive electrode and electrolyte ink solidification, without performing post-processing such as degreasing, sintering, save preparation time, reduce raw material waste, reduce preparation cost, preparation process energy saving and environmental protection and can realize large-scale batch production.

Description

Technical Field

[0001] This invention belongs to the field of zinc-ion batteries, specifically relating to a method for preparing flexible solid-state batteries using photocuring-assisted stencil printing. Background Technology

[0002] With the rapid development of modern science and technology, intelligent and miniaturized wearable flexible electronic products and components are rapidly emerging in the electronics industry, and the flexible electronics market is booming worldwide. As these microelectronic devices are integrated into various intelligent systems and flexible applications, the development of matching flexible energy storage devices has become urgent. Among numerous energy storage devices, rechargeable zinc-ion batteries are considered a next-generation energy storage device that can replace lithium-ion batteries due to their advantages such as low cost, high energy density, and high safety. Traditional zinc-ion batteries still use aqueous liquid electrolytes. Although they have high ionic conductivity and good electrode wettability, they are prone to forming zinc dendrites that pierce the separator, causing short circuits. Furthermore, these batteries cannot achieve flexibility due to the risk of structural damage and electrolyte leakage. Compared to aqueous liquid zinc-ion batteries, solid-state zinc-ion batteries use non-volatile, structurally stable solid electrolytes, avoiding the risks of short circuits and electrolyte leakage, and theoretically achieving excellent flexibility and safety.

[0003] Currently, the fabrication of high-performance flexible solid-state zinc-ion batteries remains a significant challenge. In traditional fabrication processes, electrode materials are directly coated or deposited onto flexible conductive substrates (such as carbon cloth or carbon paper) to achieve the flexibility of the battery device. However, such methods often require complex processes such as hydrothermal treatment and high-temperature annealing to prepare and solidify the electrolyte and electrodes, severely limiting material selection and production scale. In contrast, stencil printing technology offers simplicity, efficiency, and scalability, showing great potential for development in the fabrication of solid-state zinc-ion batteries. For example, a method for fabricating solid-state zinc-ion batteries by directly printing electrodes onto hydrogel-reinforced cellulose paper has been reported. This battery exhibits high capacity and energy density, and demonstrates excellent mechanical properties. However, such a process still requires steps such as high-temperature drying. Furthermore, most flexible solid-state zinc-ion batteries are assembled by mechanical pressing, which inevitably leads to geometric defects in the electrolyte and electrodes, resulting in weak interfacial bonding. When subjected to external deformation, the battery struggles to maintain its inherent structure, leading to a significant decline in electrochemical performance under deformation conditions. Furthermore, interfacial defects between the solid electrolyte and the electrode lead to a significant increase in interfacial impedance, resulting in a decline in electrochemical performance. These issues are major obstacles to the commercial application of flexible solid-state zinc-ion batteries. Therefore, developing a simple battery manufacturing process, solving the problem of electrode / electrolyte interface stability, and simultaneously improving the mechanical and electrochemical performance of the battery are important research directions in the field of flexible solid-state zinc-ion batteries. Summary of the Invention

[0004] The technical problem to be solved:

[0005] To overcome the shortcomings of existing technologies, this invention provides a method for preparing flexible solid-state batteries using photocuring-assisted stencil printing. By rationally designing the electrolyte and positive electrode ink formulations and utilizing photocuring-assisted stencil printing, a solid-state zinc-ion battery is prepared in an integrated manner, eliminating the need for degreasing, sintering, or other post-processing steps. The solid electrolyte can be in-situ solidified on the positive electrode and effectively cross-linked. The interface between the two materials has no obvious geometric defects and exhibits high bonding strength, effectively solving problems related to interfacial compatibility and process compatibility between the electrode and solid electrolyte materials. The prepared battery possesses excellent mechanical properties, along with low interfacial resistance and excellent electrochemical performance.

[0006] The technical solution of the present invention is: a flexible solid-state battery prepared by photopolymerization-assisted stencil printing, comprising a positive electrode layer, a negative electrode layer and a solid electrolyte layer;

[0007] The positive electrode layer comprises the following raw materials and mass fraction ratios: 25-30% positive electrode active material, 3-6% electronic conductive agent, and 65-75% photosensitive polymer network matrix;

[0008] The solid electrolyte layer comprises the following raw materials and mass fraction ratios: 28-35% inorganic nano-active filler and 65-72% photosensitive polymer network matrix.

[0009] A further technical solution of the present invention is: the positive electrode active material includes any one of manganese dioxide or vanadium pentoxide; the electronic conductive agent includes one or more of conductive carbon black, conductive acetylene black, or carbon nanotubes.

[0010] A further technical solution of the present invention is that the inorganic nano-active filler includes any one of nano-silica or nano-alumina.

[0011] A further technical solution of the present invention is that the photosensitive polymer network matrix comprises the following components and mass fraction ratios: 10-20% photosensitive resin, 0.1-0.2% photoinitiator, and 80-90% zinc salt solution.

[0012] A further technical solution of the present invention is: the zinc salt accounts for 20-25% of the solid content of the zinc salt solution, the zinc salt includes zinc trifluoromethanesulfonate, and the solvent of the zinc salt solution includes one or more of propylene carbonate, ethylene carbonate, and triethyl phosphate.

[0013] A further technical solution of the present invention is that the photosensitive resin comprises ethoxylated trimethylolpropane triacrylate.

[0014] A further technical solution of the present invention is that the photoinitiator includes one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone.

[0015] A method for fabricating flexible solid-state batteries using photopolymerization-assisted stencil printing, comprising the following steps:

[0016] Step 1: Print positive electrode ink on the current collector using a stencil printing machine and then perform photocuring to obtain the positive electrode layer;

[0017] Step 2: Print solid electrolyte ink on the surface of the positive electrode layer using a stencil printing device, and perform in-situ photocuring to obtain a solid electrolyte layer on the surface of the positive electrode layer;

[0018] Step 3: Assemble the negative electrode layer on the solid electrolyte layer to obtain a flexible solid-state battery consisting of a positive electrode layer, an electrolyte layer, and a negative electrode layer from bottom to top.

[0019] A further technical solution of the present invention is: the current collector includes either stainless steel foil or titanium foil; the negative electrode layer is a zinc metal sheet.

[0020] A further technical solution of the present invention is: the light curing is ultraviolet light curing, and its ultraviolet light power is 1000-2000 mw / cm². 2 The photocuring time of the solid electrolyte ink is 8–15 seconds.

[0021] Beneficial effects

[0022] The beneficial effects of this invention are as follows:

[0023] (1) This invention proposes a new strategy for the integrated preparation of flexible solid-state zinc-ion batteries using photocuring-assisted stencil printing. It effectively combines photocuring technology and stencil printing technology, and uses the principle of ultraviolet light-induced polymerization to cure the positive electrode and electrolyte inks without the need for degreasing, sintering and other post-processing. This saves preparation time, reduces raw material waste, and lowers preparation costs. The preparation process is energy-saving and environmentally friendly and can achieve large-scale mass production.

[0024] (2) The solid electrolyte prepared by this invention can be solidified in situ on the positive electrode layer by ultraviolet light irradiation, thereby obtaining a tightly connected, flat and continuous chemically cross-linked positive electrode / electrolyte interface with no geometric defects. This improves the zinc ion transport between the electrode and the solid electrolyte, effectively addressing the interface problems faced by solid zinc-ion batteries. Furthermore, the positive electrode / electrolyte interface has a maximum tensile strength of up to 34.4 MPa and a maximum shear strength of 26.4 MPa, which is beneficial for obtaining high electrochemical and mechanical performance stability.

[0025] (3) The flexible solid zinc-ion battery in this invention has high precision and controllable structure. Combined with computer technology, it realizes flexible design of the aperture plate shape. Therefore, it can prepare the positive electrode, solid electrolyte and negative electrode structure of various shapes according to actual needs, which is conducive to the customized production of flexible solid batteries.

[0026] (4) The flexible solid-state zinc-ion battery of this invention possesses excellent mechanical properties and practicality. The battery can be repeatedly bent and twisted without structural damage, and neither the electrolyte nor the electrodes break. Furthermore, the battery can be bent to 180° while maintaining a high capacity retention rate. In addition, the solid-state zinc-ion battery can continuously power a red LED light even when bent, twisted, or even cut, exhibiting extremely high safety. The charge-discharge curves of the battery at three different current densities (20 mA / g, 50 mA / g, and 100 mA / g) were obtained through experiments. Figure 8 The curve represents the rate performance of the flexible solid-state zinc-ion battery. The graph shows a clear plateau, with coulombic efficiencies consistently above 95%. As current density increases, the discharge capacity gradually decreases, which is due to internal resistance and polarization at high current densities. However, it still maintains a discharge capacity of 57 mAh / g at a current density of 100 mA / g. Attached Figure Description

[0027] Figure 1 This is a flowchart of the preparation of flexible solid-state zinc-ion batteries in Examples 1-5.

[0028] Figure 2 The following is a digital photograph of the positive electrode ink prepared according to the present invention, using the sample obtained in Example 1 as an example.

[0029] Figure 3 The sample prepared in Example 1 is used as an example to show a digital photograph of the electrolyte ink prepared according to the present invention.

[0030] Figure 4 Taking the sample prepared in Example 1 as an example, a digital photograph of the positive electrode layer printed according to the present invention is shown;

[0031] Figure 5 The sample prepared in Example 1 is used as an example to show a digital photograph of the electrolyte layer printed according to the present invention.

[0032] Figure 6 Taking the sample prepared in Example 1 as an example, a scanning electron microscope image of the positive electrode / solid electrolyte layer printed according to the present invention is shown.

[0033] Figure 7 Taking the sample prepared in Example 1 as an example, a digital photograph of the battery printed according to the present invention in a bent state is shown.

[0034] Figure 8 Taking the sample prepared in Example 1 as an example, this paper shows a schematic diagram of the charge and discharge test of the flexible solid zinc-ion battery printed according to the present invention. Detailed Implementation

[0035] The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the invention, and should not be construed as limiting the invention.

[0036] This invention provides a photocurable assisted stencil printing method for preparing flexible solid-state batteries, comprising a positive electrode layer, a negative electrode layer, and a solid electrolyte layer.

[0037] The raw materials of the positive electrode layer, by mass fraction, include 25-30% positive electrode active material, 3-6% electronic conductive agent, and 65-75% photosensitive polymer network matrix.

[0038] The mass fraction of the positive electrode active material can be 25%, 26%, 27%, 28%, 29%, or 30%, etc.; the mass fraction of the electronic conductive agent can be 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, or 6%, etc.; and the mass fraction of the photosensitive polymer network matrix can be 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, or 75%, etc., but is not limited to the listed values. Other unlisted values ​​within the above ranges are also applicable.

[0039] Preferably, the positive electrode active material includes either manganese dioxide or vanadium pentoxide.

[0040] Preferably, the electronic conductive agent includes one or more of conductive carbon black, conductive acetylene black, and carbon nanotubes.

[0041] Preferably, the photosensitive polymer network matrix of the present invention comprises, by mass fraction, 10-20% photosensitive resin, 0.1-0.2% photoinitiator, and 80-90% zinc salt solution.

[0042] The mass fraction of the photosensitive resin can be 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%, etc.; the mass fraction of the photoinitiator can be 0.1%, 0.12%, 0.14%, 0.16%, 0.18%, or 0.2%, etc.; and the mass fraction of the zinc salt solution can be 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, or 90%, etc., but is not limited to the listed values. Other unlisted values ​​within the above ranges are also applicable.

[0043] Preferably, the zinc salt accounts for 20-25% of the solid content of the zinc salt solution. The solid content can be 20%, 21%, 22%, 23%, 24%, or 25%, etc., but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0044] Preferably, the zinc salt comprises zinc trifluoromethanesulfonate.

[0045] Preferably, the zinc salt solution solvent includes one or more of propylene carbonate, ethylene carbonate, and triethyl phosphate.

[0046] Preferably, the photosensitive resin comprises ethoxylated trimethylolpropane triacrylate.

[0047] Preferably, the photoinitiator comprises one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone.

[0048] The raw materials of the solid electrolyte layer, by mass fraction, include 28-35% inorganic nano-active filler and 65-72% photosensitive polymer network matrix.

[0049] The mass fraction of the inorganic nano-active filler can be 28%, 29%, 30%, 31%, 32%, 33%, 34%, or 35%, etc., and the mass fraction of the photosensitive polymer network matrix can be 65%, 66%, 67%, 68%, 69%, 70%, 71%, or 72%, etc., but is not limited to the listed values. Other unlisted values ​​within the above ranges are also applicable.

[0050] Preferably, the inorganic nano-active filler includes either nano-silica or nano-alumina.

[0051] This invention relates to a method for preparing solid-state lithium-ion batteries using photopolymerization-assisted stencil printing technology. The preparation method includes the following steps:

[0052] Positive electrode ink is printed on the current collector using a stencil printing machine and then photocured to obtain the positive electrode layer;

[0053] Solid electrolyte ink is printed on the surface of the positive electrode layer using a stencil printing device and then photocured in situ to obtain a solid electrolyte layer on the surface of the positive electrode layer.

[0054] By assembling the negative electrode layer on the solid electrolyte layer, a flexible solid-state battery with a positive electrode layer, an electrolyte layer and a negative electrode layer arranged sequentially from bottom to top can be obtained. All steps do not require post-processing procedures such as degreasing and sintering.

[0055] As a preferred embodiment of the present invention, the current collector includes either stainless steel foil or titanium foil.

[0056] Preferably, the negative electrode layer is a zinc metal sheet.

[0057] Preferably, the light curing is ultraviolet light curing, and the ultraviolet light power is 1000-2000 mw / cm². 2 .

[0058] Preferably, the photocuring time of the solid electrolyte ink is 8 to 15 seconds, wherein the time can be 8 seconds, 9 seconds, 10 seconds, 11 seconds, 12 seconds, 13 seconds, 14 seconds or 15 seconds, etc., but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0059] This invention provides an application of the printed flexible solid-state battery, which is used in the field of zinc-ion batteries.

[0060] Example 1:

[0061] This embodiment provides a method for preparing flexible solid-state batteries using photopolymerization-assisted stencil printing, including the following steps:

[0062] (1) Preparation of photosensitive polymer network matrix: The photosensitive polymer network matrix ink is obtained by mixing and stirring 15 wt% ethoxylated trimethylolpropane triacrylate photosensitive resin, 0.15 wt% 2,4,6-trimethylbenzoyl-diphenylphosphine oxide photoinitiator, and 84.85 wt% zinc salt solution until homogeneous. The zinc salt solution comprises 23 wt% zinc trifluoromethanesulfonate and 77 wt% propylene carbonate.

[0063] (2) Preparation of positive electrode ink: After mixing and stirring 28wt% vanadium pentoxide, 4wt% conductive carbon black and 68wt% photosensitive polymer network matrix evenly, the positive electrode ink can be obtained.

[0064] (3) Preparation of solid electrolyte ink: Solid electrolyte ink can be obtained by mixing 30wt% nano alumina and 70wt% photosensitive polymer network matrix evenly.

[0065] (4) Solid-state zinc-ion battery preparation: The positive electrode ink prepared in step (2) is uniformly coated onto a perforated plate, and then spread onto a stainless steel sheet at a uniform speed using a scraper. The sheet is then exposed to ultraviolet light with an ultraviolet power of 1500 mW / cm². 2By controlling the thickness to 50 μm, a vanadium pentoxide positive electrode layer can be obtained. Subsequently, the solid electrolyte ink prepared in step (3) is printed on top of the vanadium pentoxide positive electrode using the same steps, and then cured in situ on the positive electrode layer by irradiation with an ultraviolet lamp for 10 s, with the thickness controlled to 80 μm, thereby polymerizing a layer of solid electrolyte in situ on the vanadium pentoxide negative electrode. Finally, a zinc sheet polished with 1500cc sandpaper is placed on top of the solid electrolyte and gently pressed to obtain the flexible solid-state zinc-ion battery.

[0066] The intermediate and final samples prepared in Example 1 were tested in practice.

[0067] Figure 2 and Figure 3 The photos show the positive electrode ink and the electrolyte ink, respectively. As can be seen, the ink surface after uniform mixing has a bright gloss and is stable. It can be left for 15 days without any layering or agglomeration, which meets the basic requirements for printing.

[0068] Figure 6 The scanning electron microscope (SEM) images of the positive electrode / solid electrolyte of the obtained flexible solid-state zinc-ion battery show that there are no geometric defects between the positive electrode and the solid electrolyte. Furthermore, the electrolyte penetrates into the positive electrode layer, which can effectively shorten the zinc ion transport distance and improve the ion transport efficiency. These advantages are conducive to obtaining higher electrochemical performance.

[0069] Figure 7 The image shows the obtained flexible solid-state zinc-ion battery in a bent state. It can be seen that the battery maintains a good structure in the bent state, without obvious cracks or fractures, and has excellent mechanical properties.

[0070] Figure 8 The figure shows the charge-discharge curves of the battery at three different current densities: 20 mA / g, 50 mA / g, and 100 mA / g. These curves represent the rate performance of the flexible solid-state zinc-ion battery. The figure shows a clear plateau, with coulombic efficiencies all above 95%. As the current density increases, the discharge capacity gradually decreases, which is due to internal resistance and polarization at high current densities. However, it still maintains a discharge capacity of 57 mAh / g at a current density of 100 mA / g.

[0071] The above data demonstrate that the flexible solid-state zinc-ion battery prepared in this invention possesses both excellent electrochemical and mechanical properties.

[0072] Example 2:

[0073] This embodiment provides a method for preparing flexible solid-state batteries using photopolymerization-assisted stencil printing, including the following steps:

[0074] (1) Preparation of photosensitive polymer network matrix: The photosensitive polymer network matrix ink is obtained by mixing and stirring 18 wt% ethoxylated trimethylolpropane triacrylate photosensitive resin, 0.18 wt% 2-hydroxy-2-methyl-1-phenyl-1-propanone photoinitiator, and 81.82 wt% zinc salt solution until homogeneous. The zinc salt solution comprises 24 wt% zinc trifluoromethanesulfonate, 38 wt% propylene carbonate, and 38 wt% ethylene carbonate.

[0075] (2) Preparation of positive electrode ink: 29 wt% vanadium pentoxide, 5 wt% conductive acetylene black and 66 wt% photosensitive polymer network matrix are mixed and stirred evenly to obtain positive electrode ink.

[0076] (3) Preparation of solid electrolyte ink: Solid electrolyte ink can be obtained by mixing 32wt% nano alumina and 68% photosensitive polymer network matrix evenly.

[0077] (4) Solid-state zinc-ion battery preparation: The positive electrode ink prepared in step (2) is uniformly coated onto a stencil, and then spread onto a titanium foil at a uniform speed using a doctor blade. The foil is then exposed to ultraviolet light with an ultraviolet light power of 1000 mW / cm². 2 By controlling the thickness to 60 μm, a vanadium pentoxide positive electrode layer can be obtained. Subsequently, on top of the vanadium pentoxide positive electrode, the solid electrolyte ink prepared in step (3) is printed using the same steps, and then irradiated with an ultraviolet lamp for 12 s to cure it in situ on the positive electrode layer, with the thickness controlled to 60 μm, thereby polymerizing a layer of solid electrolyte in situ on the vanadium pentoxide negative electrode. Finally, a zinc sheet polished with 1500cc sandpaper is placed on top of the solid electrolyte and gently pressed to obtain the flexible solid-state zinc-ion battery.

[0078] Example 3:

[0079] This embodiment provides a method for preparing flexible solid-state batteries using photopolymerization-assisted stencil printing, including the following steps:

[0080] (1) Preparation of photosensitive polymer network matrix: The photosensitive polymer network matrix ink is obtained by mixing and stirring 20 wt% ethoxylated trimethylolpropane triacrylate photosensitive resin, 0.2 wt% 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone photoinitiator, and 79.8 wt% zinc salt solution until homogeneous. The zinc salt solution comprises 25 wt% zinc trifluoromethanesulfonate, 50 wt% propylene carbonate, and 25 wt% triethyl phosphate.

[0081] (2) Preparation of positive electrode ink: The positive electrode ink can be obtained by mixing and stirring 30wt% manganese dioxide, 4.5wt% carbon nanotubes and 65.5wt% photosensitive polymer network matrix evenly.

[0082] (3) Preparation of solid electrolyte ink: Solid electrolyte ink can be obtained by mixing 35wt% nano-silica and 65wt% photosensitive polymer network matrix evenly.

[0083] (4) Solid-state zinc-ion battery preparation: The positive electrode ink prepared in step (2) is uniformly coated onto the stencil, and then spread onto the stainless steel sheet at a uniform speed using a scraper. The sheet is then exposed to ultraviolet light with an ultraviolet power of 2000 mW / cm². 2 By controlling the thickness to 50 μm, a manganese dioxide positive electrode layer can be obtained. Subsequently, on top of the manganese dioxide positive electrode, the solid electrolyte ink prepared in step (3) is printed using the same steps, and then cured in situ on the positive electrode layer by irradiation with an ultraviolet lamp for 8 seconds, with the thickness controlled to 60 μm, thereby polymerizing a layer of solid electrolyte in situ on the manganese dioxide negative electrode. Finally, a zinc sheet polished with 1500cc sandpaper is placed on top of the solid electrolyte and gently pressed to obtain the flexible solid-state zinc-ion battery.

[0084] Example 4:

[0085] This embodiment provides a method for preparing flexible solid-state batteries using photopolymerization-assisted stencil printing, including the following steps:

[0086] (1) Preparation of photosensitive polymer network matrix: The photosensitive polymer network matrix ink is obtained by mixing and stirring 12 wt% ethoxylated trimethylolpropane triacrylate photosensitive resin, 0.12 wt% 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone photoinitiator, and 87.88 wt% zinc salt solution until homogeneous. The zinc salt solution comprises 22 wt% zinc trifluoromethanesulfonate, 39 wt% ethylene carbonate, and 39 wt% triethyl phosphate.

[0087] (2) Preparation of positive electrode ink: After mixing and stirring 26wt% manganese dioxide, 6wt% carbon nanotubes and 68wt% photosensitive polymer network matrix evenly, the positive electrode ink can be obtained.

[0088] (3) Preparation of solid electrolyte ink: Solid electrolyte ink can be obtained by mixing and stirring 29wt% nano silica and 71wt% photosensitive polymer network matrix evenly.

[0089] (4) Solid-state zinc-ion battery preparation: The positive electrode ink prepared in step (2) is uniformly coated onto a stencil, and then spread onto a stainless steel foil at a uniform speed using a doctor blade. The foil is then exposed to ultraviolet light with an ultraviolet power of 2000 mW / cm². 2By controlling the thickness to 60 μm, a manganese dioxide positive electrode layer can be obtained. Subsequently, the solid electrolyte ink prepared in step (3) is printed on top of the manganese dioxide positive electrode using the same steps, and then cured in situ on the positive electrode layer by irradiation with an ultraviolet lamp for 10 s, with the thickness controlled to 80 μm, thereby polymerizing a layer of solid electrolyte in situ on the manganese dioxide negative electrode. Finally, a zinc sheet polished with 1500cc sandpaper is placed on top of the solid electrolyte and gently pressed to obtain the flexible solid-state zinc-ion battery.

[0090] Example 5:

[0091] This embodiment provides a method for preparing flexible solid-state batteries using photopolymerization-assisted stencil printing, including the following steps:

[0092] (1) Preparation of photosensitive polymer network matrix: The photosensitive polymer network matrix ink is obtained by mixing and stirring 10 wt% ethoxylated trimethylolpropane triacrylate photosensitive resin, 0.2 wt% 2,4,6-trimethylbenzoyl-diphenylphosphine oxide photoinitiator, and 89.8 wt% zinc salt solution until homogeneous. The zinc salt solution comprises 20 wt% zinc trifluoromethanesulfonate, 50 wt% propylene carbonate, and 30 wt% triethyl phosphate.

[0093] (2) Preparation of positive electrode ink: 25wt% vanadium pentoxide, 5wt% conductive acetylene black and 70wt% photosensitive polymer network matrix are mixed and stirred evenly to obtain positive electrode ink.

[0094] (3) Preparation of solid electrolyte ink: Solid electrolyte ink can be obtained by mixing 28wt% nano-silica and 72wt% photosensitive polymer network matrix evenly.

[0095] (4) Solid-state zinc-ion battery preparation: The positive electrode ink prepared in step (2) is uniformly coated onto a stencil, and then spread onto a titanium foil at a uniform speed using a doctor blade. The foil is then exposed to ultraviolet light with an ultraviolet light power of 1500 mW / cm². 2 By controlling the thickness to 50 μm, a vanadium pentoxide positive electrode layer can be obtained. Subsequently, the solid electrolyte ink prepared in step (3) is printed on top of the vanadium pentoxide positive electrode using the same steps, and then cured in situ on the positive electrode layer by irradiation with an ultraviolet lamp for 12 s, with the thickness controlled to 50 μm, thereby polymerizing a layer of solid electrolyte in situ on the vanadium pentoxide negative electrode. Finally, a zinc sheet polished with 1500cc sandpaper is placed on top of the solid electrolyte and gently pressed to obtain the flexible solid-state zinc-ion battery.

[0096] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention without departing from the principles and spirit of the present invention.

Claims

1. A method for fabricating flexible solid-state batteries using photopolymerization-assisted stencil printing, characterized in that... The specific steps are as follows: Step 1: Print positive electrode ink on the current collector using a stencil printing device and perform photocuring to obtain the positive electrode layer; the current collector includes any one of stainless steel foil or titanium foil; Step 2: Print solid electrolyte ink on the surface of the positive electrode layer using a stencil printing device, and perform in-situ photocuring to obtain a solid electrolyte layer on the surface of the positive electrode layer; Step 3: Assemble the negative electrode layer on the solid electrolyte layer to obtain a flexible solid-state battery consisting of a positive electrode layer, a solid electrolyte layer, and a negative electrode layer from bottom to top; The flexible solid-state battery includes a positive electrode layer, a negative electrode layer, and a solid electrolyte layer; the negative electrode layer is a zinc metal sheet; the photocuring is ultraviolet light curing, with an ultraviolet light power of 1000–2000 mW / cm². 2 The photocuring time of the solid electrolyte ink is 8–15 seconds. The positive electrode layer comprises the following raw materials and mass fraction ratios: 25-30% positive electrode active material, 3-6% electronic conductive agent, and 65-75% photosensitive polymer network matrix; The solid electrolyte layer comprises the following raw materials and mass fraction ratios: 28-35% inorganic nano-active filler and 65-72% photosensitive polymer network matrix. The photosensitive polymer network matrix comprises the following components and mass fractions: 10-20% photosensitive resin, 0.1-0.2% photoinitiator, and 80-90% zinc salt solution. The zinc salt in the zinc salt solution accounts for 20-25% of the solid content of the zinc salt solution, and the zinc salt includes zinc trifluoromethanesulfonate. The solvent of the zinc salt solution includes one or more of propylene carbonate, ethylene carbonate and triethyl phosphate.

2. The method for preparing flexible solid-state batteries using photopolymerization-assisted stencil printing according to claim 1, characterized in that: The positive electrode active material includes either manganese dioxide or vanadium pentoxide; the electronic conductive agent includes either conductive carbon black or carbon nanotubes.

3. The method for preparing flexible solid-state batteries using photopolymerization-assisted stencil printing according to claim 1, characterized in that: The electronic conductive agent includes conductive acetylene black.

4. The method for preparing flexible solid-state batteries using photopolymerization-assisted stencil printing according to claim 1, characterized in that: The inorganic nano-active filler includes either nano-silica or nano-alumina.

5. The method for preparing flexible solid-state batteries using photopolymerization-assisted stencil printing according to claim 1, characterized in that: The photosensitive resin includes ethoxylated trimethylolpropane triacrylate.

6. The method for preparing flexible solid-state batteries using photopolymerization-assisted stencil printing according to claim 1, characterized in that: The photoinitiator includes one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone.

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