Preparation method of a fibrous flexible battery based on liquid metal

Abstract

The present invention relates to a preparation method of a fibrous flexible battery based on liquid metal, belonging to the technical field of electrochemical energy storage. The method uses 3D printing ink direct writing technology to print an organic polymer hollow solid electrolyte, selects liquid metal as the positive and negative electrodes of the battery, and prepares a fibrous flexible battery after encapsulation. The cyclic stability performance test is carried out on the battery prepared by the method. The theoretical capacity of the battery is 62.7 Ah, and the capacity does not significantly decay after 50 cycles. The coulombic efficiency and energy efficiency are maintained at about 99% and 62% respectively.

Description

Technical Field

[0001] The present invention relates to a preparation method of a fibrous flexible battery based on liquid metal, belonging to the technical field of electrochemical energy storage. Background Art

[0002] With the gradual progress of the scientific and technological strength of chemical power sources, Daniell cells, lead-acid batteries, silver oxide batteries, nickel-cadmium batteries, zinc-manganese batteries, etc. have been continuously invented. These batteries can meet the electricity demand of humans, but if they are not properly disposed of after being discarded, they will also cause irreversible environmental problems and even affect human health. Instead of remedying pollution after it occurs, it is better to eliminate the generation of pollution from the source. Against this background, rechargeable metal batteries have come into people's view. Nowadays, lithium-ion, sodium-ion, and zinc-ion batteries have become battery systems that researchers focus on more. However, due to limitations in raw material costs, capacity density, energy density, structure manufacturing, etc., more emerging energy storage technologies need to be developed for future power grid storage. Especially in terms of structure manufacturing, in order to meet today's diverse and non-standard user scenarios, the requirements for battery structures are becoming more and more variable, no longer limited to a patterned fixed structure, but rather more pursuing the flexibility of battery structures. For example, in high-performance complex electronic devices such as smart bracelets, electronic skins, implantable electronic devices, pacemakers, or flexible wearable devices, traditional rigid-shell batteries cannot meet the requirements of their variable structures, and thus more and more researchers have begun to focus on the development of flexible batteries. Nowadays, the preparation process of flexible batteries is mainly divided into two major directions. One is to make battery components such as electrode materials and packaging materials flexible, and the other is to make the battery structure flexible.

[0003] As an amorphous metal, liquid metal exists in a liquid state within a specific temperature range, and liquid metal batteries do not have explosiveness, flammability, or temperature sensitivity, and there are no safety problems with these batteries caused by overcharging, short circuit, or temperature. From its own physical and chemical properties, it well meets the requirements for the design and manufacture of high-performance, high-safety, and flexible batteries. However, currently, when liquid metal is used for battery electrodes, it is usually encapsulated in a rigid shell, with relatively weak shape plasticity and difficulty in meeting the requirements of the structured battery for special scenarios. Organic polymer electrolytes have a certain degree of flexibility and also have a certain degree of shape plasticity, and as a new technology, 3D inkjet direct writing printing technology can be used to customize the structural design and manufacture of organic polymer electrolytes through program control. Fibrous flexible batteries can achieve different shapes through weaving, winding, stacking, etc. Therefore, using liquid metal as an electrode material to match the 3D inkjet direct-written organic polymer electrolyte to manufacture fibrous flexible batteries combines the flexible preparation processes of battery components and battery structures, which is a new development direction for future electrochemical energy storage devices.

[0004] In the prior art, Patent CN114551111A discloses an inkjet direct writing 3D printed conductive polymer-based micro-supercapacitor and its preparation method. However, its battery structure does not have plasticity and cannot meet the flexible requirements of multiple scenarios. Patent CN112803063A uses a laminated structure to set the positive electrode, negative electrode and separator, and prepares a flexible battery by zigzag folding. However, the plasticity of its structure is also limited by the size of the laminated sheet, making it difficult to meet the higher flexible structure requirements. Summary of the Invention

[0005] To overcome the defects existing in the prior art, one of the objectives of the present invention is to provide a preparation method of a fibrous flexible battery based on liquid metal.

[0006] To achieve the objective of the present invention, the following technical solutions are provided.

[0007] A preparation method of a fibrous flexible battery based on liquid metal, the steps of the method are as follows:

[0008] (1) Design a 3D model of a solid electrolyte through modeling software and convert it into a layered path file, and import it into a 3D printer;

[0009] The model of the 3D printer is FisnarF4200n;

[0010] (2) Mix an organic polymer matrix material and an inorganic filler and dissolve them in a solvent to prepare a 3D printing inkjet direct writing ink, and inject it into a syringe of the 3D printer;

[0011] The organic polymer matrix material is one of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), and polyacrylonitrile (PAN);

[0012] The inorganic filler is one of Al2O3, SiO2, TiO2, BaTiO3, Li3N, LAGP(Li 1.5 Al 0.5 Ge 1.5 (PO4)3), LATP(Li 1.3 Al 0.3 Ti 1.7 (PO4)3), LLTO(Li 0.34 La 0.567 TiO3), LLZO(Li 6.3 La3Zr 1.65 W 0.35 O 12 );

[0013] The solvent is water, ethylene glycol or a water-ethylene glycol mixed solvent;

[0014] (3) Using the inkjet direct writing 3D printing technology, extrude the ink obtained in step (2) through the syringe of the 3D printer, and under the drive of the program-controlled motion platform, print it into a solid electrolyte according to the model layer path file preset in step (1);

[0015] (4) Encapsulate the obtained solid electrolyte in a silicone resin shell material;

[0016] (5) Inject the positive and negative liquid metals into the hollow solid electrolyte and the area between the electrolyte and the silicone resin shell material respectively;

[0017] The positive liquid metal is: Sb, Pb, Ti, Bi, and alloys containing the above two elements;

[0018] The negative liquid metal is: Li, Na, K, Na-K alloy, and Ga-based alloy, where the Ga-based alloy is Ca-Bi, Ca-Sb, Ca-Mg, Ca-Ge, Ga-In;

[0019] (6) After encapsulation, a fibrous flexible battery is obtained.

[0020] Advantages

[0021] 1. The present invention provides a preparation method of a fibrous flexible battery based on liquid metal. The method selects the 3D printing inkjet direct writing technology, which can manufacture complex 3D multi-scale architectures, with low cost and simple controllability. When applied to printing an organic polymer solid electrolyte, it can well meet the shape requirements of fibrous and hollow shapes, and due to the printing process being program-controlled, different batches have a certain shape consistency.

[0022] 2. The present invention provides a preparation method of a fibrous flexible battery based on liquid metal. The method uses liquid metal as the positive and negative electrodes of the battery. The liquid metal is in a liquid state, can flow, and has high electrical and thermal conductivity, and can well meet the changing shape requirements of the flexible battery while maintaining a certain energy density. And the liquid metal battery does not have explosiveness, flammability, or temperature sensitivity, and there are no safety problems such as overcharging, short circuit, or temperature for these batteries. Description of the Drawings

[0023] Figure 1 It is a schematic diagram of the shape of a fibrous flexible battery based on liquid metal. Where A is the negative electrode, B is the electrolyte, and C is the positive electrode.

[0024] Figure 2 It is a curve graph of the 50-week cycle stability test of the battery prepared in Example 1. Specific Embodiments

[0025] The present invention will be described in detail below in conjunction with the accompanying drawings and specific embodiments, but it is not intended to limit the patent of the present invention.

[0026] For the reagents and other instruments whose manufacturers are not indicated, they are all conventional reagent products that can be obtained through commercial purchase.

[0027] The following tests were carried out on a fibrous flexible battery based on liquid metal prepared in the following examples:

[0028] (1) Charge and discharge test: The instrument is a Neware button battery charge and discharge tester, model CT-4008T-5V10Ma-164, purchased from Shenzhen Neware Electronic Co., Ltd.

[0029] Test method:

[0030] (1) Cycle stability test, the current density is 200 mA cm -3 , and the voltage range is 0.01 V to 1.40 V.

[0031] Example 1

[0032] A preparation method of a fibrous flexible battery based on liquid metal, the method steps are as follows:

[0033] (1) Design a 3D model of a solid electrolyte through modeling software and convert it into a layered path file, and import it into a 3D printer;

[0034] (2) Mix the organic polymer matrix material PEO and the inorganic filler Al2O3 at mass fractions of 70 wt% and 30 wt% respectively and dissolve them in water to prepare a direct ink writing ink for 3D printing. The surface tension of the ink is 15 mN / m and the viscosity is 1 mPa·s, and inject it into the syringe of the 3D printer;

[0035] (3) Use the direct ink writing 3D printing technology to extrude the ink obtained in step (2) through the syringe of the 3D printer. Set the nozzle size of the 3D printer to 0.3 mm, the ink extrusion flow rate to 40 nL / S, and the moving speed of the program-controlled motion platform to 500 mm / min. Driven by the program-controlled motion platform, print it into a solid electrolyte according to the model layered path file preset in step (1);

[0036] (4) Encapsulate the obtained solid electrolyte in a silicone resin shell material, and the diameter ratio of the solid electrolyte to the silicone resin shell material is 0.3;

[0037] (5) Inject Sb as the positive electrode and Ca-In as the negative electrode into the hollow solid electrolyte and the area between the electrolyte and the silicone resin shell material respectively;

[0038] (6) After encapsulation, a fibrous flexible battery is obtained with a diameter of 5 mm.

[0039] Perform a cyclic stability performance test on a fibrous flexible battery based on liquid metal prepared in Example 1. The theoretical capacity of the battery is 62.7 Ah. After 50 cycles, the capacity shows no obvious attenuation, and the coulombic efficiency and energy efficiency are maintained at approximately 99% and 62% respectively.

[0040] Example 2

[0041] A preparation method of a fibrous flexible battery based on liquid metal, the method steps are as follows:

[0042] (1) Design a 3D model of a solid electrolyte through modeling software and convert it into a layered path file, and import it into a 3D printer;

[0043] (2) Mix the organic polymer matrix material PVDF and the inorganic filler SiO2 at mass fractions of 80 wt% and 20 wt% respectively, dissolve them in water to prepare a direct ink writing ink for 3D printing. The surface tension of the ink is 25 mN / m and the viscosity is 10 mPa·s, and inject it into the syringe of the 3D printer;

[0044] (3) Use the direct ink writing 3D printing technology to extrude the ink obtained in step (2) through the syringe of the 3D printer. Set the nozzle size of the 3D printer to 0.4 mm, the ink extrusion flow rate to 18 nL / S, and the moving speed of the program-controlled motion platform to 450 mm / min. Driven by the program-controlled motion platform, print it into a solid electrolyte according to the model layered path file preset in step (1);

[0045] (4) Encapsulate the obtained solid electrolyte in a silicone resin shell material, and the diameter ratio of the solid electrolyte to the silicone resin shell material is 0.5;

[0046] (5) Inject Pb as the positive electrode and Li as the negative electrode into the hollow solid electrolyte and the area between the electrolyte and the silicone resin shell material respectively;

[0047] (6) After encapsulation, a fibrous flexible battery is obtained with a diameter of 4 mm.

[0048] Perform a cyclic stability performance test on a fibrous flexible battery based on liquid metal prepared in Example 2. The theoretical capacity of the battery is 80.5 Ah. After 50 cycles, the capacity shows no obvious attenuation, and the coulombic efficiency and energy efficiency are maintained at approximately 98.1% and 64.3% respectively.

[0049] Example 3

[0050] A preparation method of a fibrous flexible battery based on liquid metal, the method steps are as follows:

[0051] (1) Design a 3D model of the solid electrolyte through modeling software, convert it into a layered path file, and import it into a 3D printer;

[0052] (2) Mix the organic polymer matrix material PMMA and the inorganic filler TiO2 at mass fractions of 90 wt% and 10 wt% respectively, dissolve them in ethylene glycol, prepare a direct ink writing ink for 3D printing, with the surface tension of the ink being 40 mN / m and the viscosity being 18 mPa·s, and inject it into the syringe of the 3D printer;

[0053] (3) Use the direct ink writing 3D printing technology to extrude the ink obtained in step (2) through the syringe of the 3D printer. Set the nozzle size of the 3D printer to 0.8 mm, the ink extrusion flow rate to 50 nL / S, and the moving speed of the programmed control motion platform to 600 mm / min. Driven by the programmed control motion platform, print it into a solid electrolyte according to the pre-set model layered path file in step (1);

[0054] (4) Package the obtained solid electrolyte in a silicone resin shell material, and the diameter ratio of the solid electrolyte to the silicone resin shell material is 0.6;

[0055] (5) Inject Ti as the positive electrode and Na as the negative electrode into the hollow interior of the solid electrolyte and the area between the electrolyte and the silicone resin shell material respectively;

[0056] (6) After packaging, a fibrous flexible battery with a diameter of 2 mm is obtained.

[0057] Perform a cyclic stability performance test on a fibrous flexible battery based on liquid metal prepared in Example 3. The theoretical capacity of the battery is 80.7 Ah, and the capacity does not show obvious attenuation after 50 cycles. The coulombic efficiency and energy efficiency are maintained at approximately 97.5% and 58.8% respectively.

[0058] Example 4

[0059] A preparation method of a fibrous flexible battery based on liquid metal, and the steps of the method are as follows:

[0060] (1) Design a 3D model of the solid electrolyte through modeling software, convert it into a layered path file, and import it into a 3D printer;

[0061] (2) Mix the organic polymer matrix material PAN and the inorganic filler BaTiO3 at mass fractions of 95 wt% and 5 wt% respectively, dissolve them in a mixed solvent of water and ethylene glycol, prepare a direct ink writing ink for 3D printing, with the surface tension of the ink being 60 mN / m and the viscosity being 25 mPa·s, and inject it into the syringe of the 3D printer;

[0062] (3) Using the inkjet direct writing 3D printing technology, extrude the ink obtained in step (2) through the syringe of the 3D printer. Set the nozzle size of the 3D printer to 0.75 mm, the ink extrusion flow rate to 60 nL / S, and the moving speed of the program-controlled moving platform to 700 mm / min. Driven by the program-controlled moving platform, print it into a solid electrolyte according to the model layer path file preset in step (1);

[0063] (4) Encapsulate the obtained solid electrolyte in a silicone resin housing material, and the diameter ratio of the solid electrolyte to the silicone resin housing material is 0.8;

[0064] (5) Inject Bi as the positive electrode and K as the negative electrode into the hollow solid electrolyte and the area between the electrolyte and the silicone resin housing material respectively;

[0065] (6) After encapsulation, a fibrous flexible battery with a diameter of 3 mm is obtained.

[0066] Perform a cyclic stability performance test on a fibrous flexible battery based on liquid metal prepared in Example 4. The theoretical capacity of the battery is 43.2 Ah. After 50 cycles, the capacity does not show obvious attenuation, and the Coulomb efficiency and energy efficiency are maintained at approximately 96.9% and 65.7% respectively.

[0067] Example 5

[0068] A preparation method of a fibrous flexible battery based on liquid metal, the method steps are as follows:

[0069] (1) Design a 3D model of the solid electrolyte through modeling software and convert it into a layer path file, and import it into the 3D printer;

[0070] (2) Mix the organic polymer matrix material PEO and the inorganic filler Li3N with mass fractions of 75 wt% and 25 wt% respectively, dissolve them in ethylene glycol, prepare an inkjet direct writing ink for 3D printing, the surface tension of the ink is 50 mN / m, the viscosity is 21 mPa·s, and inject it into the syringe of the 3D printer;

[0071] (3) Using the inkjet direct writing 3D printing technology, extrude the ink obtained in step (2) through the syringe of the 3D printer. Set the nozzle size of the 3D printer to 0.6 mm, the ink extrusion flow rate to 50 nL / S, and the moving speed of the program-controlled moving platform to 650 mm / min. Driven by the program-controlled moving platform, print it into a solid electrolyte according to the model layer path file preset in step (1);

[0072] (4) Encapsulate the obtained solid electrolyte in a silicone resin housing material, and the diameter ratio of the solid electrolyte to the silicone resin housing material is 0.45;

[0073] (5) Inject the Sb-Pb alloy as the positive electrode and the Na-K alloy as the negative electrode into the interior of the hollow solid electrolyte and the region between the electrolyte and the silicone resin casing material, respectively.

[0074] (6) After encapsulation, a fibrous flexible battery with a diameter of 3.5 mm is obtained.

[0075] Perform a cyclic stability performance test on a fibrous flexible battery based on liquid metal prepared in Example 5. The theoretical capacity of the battery is 112.5 Ah. After 50 cycles, the capacity does not show significant attenuation, and the coulombic efficiency and energy efficiency are maintained at approximately 98.5% and 67.7%, respectively.

[0076] Example 6

[0077] A preparation method of a fibrous flexible battery based on liquid metal, the method steps are as follows:

[0078] (1) Design a 3D model of the solid electrolyte through modeling software and convert it into a layered path file, and import it into a 3D printer.

[0079] (2) Mix the organic polymer matrix material PEO and the inorganic filler LAGP at mass fractions of 85 wt% and 15 wt% respectively, dissolve them in water, prepare a direct ink writing ink for 3D printing, the surface tension of the ink is 15 mN / m, the viscosity is 17 mPa·s, and inject it into the syringe of the 3D printer.

[0080] (3) Use the direct ink writing 3D printing technology to extrude the ink obtained in step (2) through the syringe of the 3D printer. Set the nozzle size of the 3D printer to 0.35 mm, the ink extrusion flow rate to 80 nL / S, and the moving speed of the program-controlled motion platform to 530 mm / min. Driven by the program-controlled motion platform, print it into a solid electrolyte according to the pre-set model layered path file in step (1).

[0081] (4) Encapsulate the obtained solid electrolyte in a silicone resin casing material, and the diameter ratio of the solid electrolyte to the silicone resin casing material is 0.35.

[0082] (5) Inject the Sb-Ti alloy as the positive electrode and the Ca-Bi alloy as the negative electrode into the interior of the hollow solid electrolyte and the region between the electrolyte and the silicone resin casing material, respectively.

[0083] (6) After encapsulation, a fibrous flexible battery with a diameter of 4 mm is obtained.

[0084] The cyclic stability performance of a fiber-shaped flexible battery based on liquid metal prepared in Example 6 was tested. The theoretical capacity of the battery is 54.6 Ah, and the capacity did not significantly decay after 50 cycles. The Coulomb efficiency and energy efficiency were maintained at approximately 97.6% and 61.2% respectively.

[0085] Example 7

[0086] A method for preparing a fiber-shaped flexible battery based on liquid metal, the steps of the method are as follows:

[0087] (1) Design a 3D model of the solid electrolyte through modeling software and convert it into a layered path file, and import it into a 3D printer;

[0088] (2) Mix the organic polymer matrix material PAN and the inorganic filler LATP at mass fractions of 70 wt% and 30 wt% respectively, dissolve them in water to prepare a direct ink writing ink for 3D printing. The surface tension of the ink is 15 mN / m and the viscosity is 2 mPa·s, and inject it into the syringe of the 3D printer;

[0089] (3) Use the direct ink writing 3D printing technology to extrude the ink obtained in step (2) through the syringe of the 3D printer. Set the nozzle size of the 3D printer to 0.45 mm, the ink extrusion flow rate to 40 nL / S, and the moving speed of the programmed control motion platform to 400 mm / min. Driven by the programmed control motion platform, print it into a solid electrolyte according to the model layered path file preset in step (1);

[0090] (4) Encapsulate the obtained solid electrolyte in a silicone resin shell material, and the diameter ratio of the solid electrolyte to the silicone resin shell material is 0.5;

[0091] (5) Inject the Sb-Bi alloy as the positive electrode and the Ca-Sb alloy as the negative electrode into the hollow solid electrolyte and the area between the electrolyte and the silicone resin shell material respectively;

[0092] (6) After encapsulation, a fiber-shaped flexible battery with a diameter of 5 mm is obtained.

[0093] The cyclic stability performance of a fiber-shaped flexible battery based on liquid metal prepared in Example 7 was tested. The theoretical capacity of the battery is 58.3 Ah, and the capacity did not significantly decay after 50 cycles. The Coulomb efficiency and energy efficiency were maintained at approximately 99.1% and 61.1% respectively.

[0094] Example 8

[0095] A method for preparing a fiber-shaped flexible battery based on liquid metal, the steps of the method are as follows:

[0096] (1) Design a 3D model of the solid electrolyte through modeling software, convert it into a layered path file, and import it into a 3D printer;

[0097] (2) Mix the organic polymer matrix material PVDF and the inorganic filler LLTO at mass fractions of 80 wt% and 20 wt% respectively, dissolve them in water to prepare a direct ink writing ink for 3D printing. The surface tension of the ink is 60 mN / m and the viscosity is 25 mPa·s, and inject it into the syringe of the 3D printer;

[0098] (3) Use the direct ink writing 3D printing technology to extrude the ink obtained in step (2) through the syringe of the 3D printer. Set the nozzle size of the 3D printer to 0.4 mm, the ink extrusion flow rate to 30 nL / S, and the moving speed of the program-controlled motion platform to 300 mm / min. Driven by the program-controlled motion platform, print it into a solid electrolyte according to the pre-set model layered path file in step (1);

[0099] (4) Encapsulate the obtained solid electrolyte in a silicone resin shell material, and the diameter ratio of the solid electrolyte to the silicone resin shell material is 0.6;

[0100] (5) Inject the Pb-Ti alloy as the positive electrode and the Ca-Sb alloy as the negative electrode into the hollow solid electrolyte and the area between the electrolyte and the silicone resin shell material respectively;

[0101] (6) After encapsulation, a fibrous flexible battery is obtained with a diameter of 2 mm.

[0102] Perform a cyclic stability performance test on a fibrous flexible battery based on liquid metal prepared in Example 8. The theoretical capacity of the battery is 57.3 Ah, and the capacity shows no obvious attenuation after 50 cycles. The Coulomb efficiency and energy efficiency are maintained at approximately 97.9% and 54.3% respectively.

[0103] Example 9

[0104] A preparation method of a fibrous flexible battery based on liquid metal, the method steps are as follows:

[0105] (1) Design a 3D model of the solid electrolyte through modeling software, convert it into a layered path file, and import it into a 3D printer;

[0106] (2) Mix the organic polymer matrix material PEO and the inorganic filler LLZO at mass fractions of 85 wt% and 15 wt% respectively, dissolve them in water to prepare a direct ink writing ink for 3D printing. The surface tension of the ink is 48 mN / m and the viscosity is 20 mPa·s, and inject it into the syringe of the 3D printer;

[0107] (3) Using the inkjet direct writing 3D printing technology, extrude the ink obtained in step (2) through the syringe of the 3D printer. Set the nozzle size of the 3D printer to 0.55 mm, the ink extrusion flow rate to 45 nL / S, and the moving speed of the program-controlled moving platform to 350 mm / min. Driven by the program-controlled moving platform, print it into a solid electrolyte according to the model layer path file preset in step (1);

[0108] (4) Encapsulate the obtained solid electrolyte in a silicone resin housing material, and the diameter ratio of the solid electrolyte to the silicone resin housing material is 0.8;

[0109] (5) Inject Pb-Ti as the positive electrode and Ca-Ge alloy as the negative electrode into the hollow solid electrolyte and the area between the electrolyte and the silicone resin housing material respectively;

[0110] (6) After encapsulation, a fibrous flexible battery is obtained, with a diameter of 5 mm.

[0111] Perform a cyclic stability performance test on a fibrous flexible battery based on liquid metal prepared in Example 9. The theoretical capacity of the battery is 59.9 Ah, and the capacity does not show obvious attenuation after 50 cycles. The Coulomb efficiency and energy efficiency are maintained at approximately 96.5% and 62.3% respectively.

[0112] Example 10

[0113] A preparation method of a fibrous flexible battery based on liquid metal, the method steps are as follows:

[0114] (1) Design a 3D model of the solid electrolyte through modeling software and convert it into a layer path file, and import it into the 3D printer;

[0115] (2) Mix the organic polymer matrix material PAN and the inorganic filler LLZO with mass fractions of 85 wt% and 15 wt% respectively, dissolve them in water, prepare an inkjet direct writing ink for 3D printing, the surface tension of the ink is 50 mN / m, the viscosity is 25 mPa·s, and inject it into the syringe of the 3D printer;

[0116] (3) Using the inkjet direct writing 3D printing technology, extrude the ink obtained in step (2) through the syringe of the 3D printer. Set the nozzle size of the 3D printer to 0.5 mm, the ink extrusion flow rate to 50 nL / S, and the moving speed of the program-controlled moving platform to 400 mm / min. Driven by the program-controlled moving platform, print it into a solid electrolyte according to the model layer path file preset in step (1);

[0117] (4) Encapsulate the obtained solid electrolyte in a silicone resin housing material, and the diameter ratio of the solid electrolyte to the silicone resin housing material is 0.7;

[0118] (5) Inject Ti-Bi as the positive electrode and Li as the negative electrode into the interior of the hollow solid electrolyte and the region between the electrolyte and the silicone resin outer shell material, respectively;

[0119] (6) After encapsulation, a fibrous flexible battery is obtained with a diameter of 4.5 mm.

[0120] Perform a cyclic stability performance test on a fibrous flexible battery based on liquid metal prepared in Example 10. The theoretical capacity of the battery is 34.5 Ah. After 50 cycles, the capacity does not show obvious attenuation, and the coulombic efficiency and energy efficiency are maintained at approximately 98.4% and 61.1%, respectively.

Claims

1. A preparation method of a fibrous flexible battery based on liquid metal, characterized in that: The method steps are as follows: (1) Design a 3D model of the solid electrolyte through modeling software, convert it into a layered path file, and import it into a 3D printer; The model of the 3D printer is Fisnar F4200n; (2) Mix the organic polymer matrix material and the inorganic filler and dissolve them in a solvent to prepare a direct ink writing ink for 3D printing, and inject it into the syringe of the 3D printer; The organic polymer matrix material is one of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), and polyacrylonitrile (PAN); The inorganic filler is one of Al2O3, SiO2, TiO2, BaTiO3, Li3N, LAGP(Li 1.5 Al 0.5 Ge 1.5 (PO4)3), LATP(Li 1.3 Al 0.3 Ti 1.7 (PO4)3), LLTO(Li 0.34 La 0.567 TiO3), LLZO(Li 6.3 La3Zr 1.65 W 0.35 O 12 ); The solvent is water, ethylene glycol, or a water-ethylene glycol mixed solvent; (3) Use the direct ink writing 3D printing technology to extrude the ink obtained in step (2) through the syringe of the 3D printer, and under the drive of a program-controlled motion platform, print it into a solid electrolyte according to the pre-set model layered path file in step (1); (4) Package the obtained solid electrolyte in a silicone resin housing material; (5) Inject the positive and negative liquid metals into the hollow solid electrolyte and the area between the electrolyte and the silicone resin housing material respectively; The positive liquid metal is: Sb, Pb, Ti, Bi, and alloys containing the above two elements; The negative liquid metal is: Li, Na, K, Na-K alloy, and Ga-based alloy, where the Ga-based alloy is Ca-Bi, Ca-Sb, Ca-Mg, Ca-Ge, Ga-In; (6) After packaging, a fibrous flexible battery is obtained.

2. The preparation method of a fibrous flexible battery based on liquid metal according to claim 1, wherein: The mass ratio of the organic polymer to the inorganic filler is (70-95):(30-5).

3. The preparation method of a fibrous flexible battery based on liquid metal according to claim 1, characterized in that: The surface tension of the ink is 15 mN / m to 60 mN / m, and the viscosity is 1 mPa·s to 25 mPa·s.

4. The preparation method of a fibrous flexible battery based on liquid metal according to claim 1, characterized in that: The nozzle size of the 3D printer is 0.3 mm - 0.8 mm, the ink extrusion flow rate is 18 nL / S to 80 nL / s, and the moving speed of the program-controlled motion platform is 300 mm / min to 700 mm / min.

5. The preparation method of a fibrous flexible battery based on liquid metal according to claim 1, characterized in that: The shape of the hollow solid electrolyte is a hollow cylindrical shape.

6. The preparation method of a fibrous flexible battery based on liquid metal according to claim 1, characterized in that: The shape of the silicone resin housing material is a hollow cylindrical shape.

7. The preparation method of a fibrous flexible battery based on liquid metal according to claim 1, characterized in that: The diameter ratio of the hollow solid electrolyte to the silicone resin housing material is 0.3 to 0.

8.

8. The preparation method of a fibrous flexible battery based on liquid metal according to claim 1, characterized in that: The diameter of the fibrous flexible battery is 2 mm to 5 mm.

9. The preparation method of a fibrous flexible battery based on liquid metal according to claim 1, characterized in that: The model of the 3D printer is Fisnar F4200n; the mass ratio of the organic polymer to the inorganic filler is (70-95):(30-5); the surface tension of the ink is 15 - 60 mN / m, and the viscosity is 1 - 25 mPa·s; the shape of the hollow solid electrolyte is a hollow cylindrical shape; the nozzle size of the 3D printer is 0.3 mm - 0.8 mm, the ink extrusion flow rate is 18 nL / S to 80 nL / s, and the moving speed of the program-controlled motion platform is 300 mm / min to 700 mm / min; the shape of the silicone resin housing material is a hollow cylindrical shape; the diameter ratio of the hollow solid electrolyte to the silicone resin housing material is 0.3 to 0.8; the diameter of the fibrous flexible battery is 2 mm to 5 mm.

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