CN107696471B - 3D printing method of flexible battery - Google Patents

3D printing method of flexible battery Download PDF

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CN107696471B
CN107696471B CN201710936374.8A CN201710936374A CN107696471B CN 107696471 B CN107696471 B CN 107696471B CN 201710936374 A CN201710936374 A CN 201710936374A CN 107696471 B CN107696471 B CN 107696471B
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printing
flexible battery
slurry
negative electrode
positive
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CN107696471A (en
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丁超
黄健鹏
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Dongguan South China Design and Innovation Institute
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Dongguan South China Design and Innovation Institute
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention discloses a 3D printing method of a flexible battery, which mainly comprises three-dimensional modeling, printing a matrix, a current collector, a positive electrode, a negative electrode and a baffle of the flexible battery in sequence, packaging by using a base cover, and injecting electrolyte to obtain the flexible battery. The structure of the traditional interdigital electrode is improved, so that the interdigital electrode can be suitable for a flexible battery, does not collapse or deform in the using process, and can still keep excellent electrochemical performance after being bent for many times.

Description

3D printing method of flexible battery
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to a 3D printing method of a flexible battery.
Background
The 3D printing (3D printing) technology is also called a three-dimensional printing technology, and is a technology for constructing an object by using an adhesive material such as powdered metal or plastic and the like and by printing layer by layer on the basis of a digital model file. It can directly produce parts with any shape from computer graphic data without machining or any die, thus greatly shortening the development period of products, improving productivity and reducing production cost.
With the increasing perfection of 3D printing technology, 3D printing technology has been widely applied to the fields of military, electronics, medicine, biology, new energy and the like, and particularly, the emergence of novel 3D printing integrated lithium ion batteries effectively realizes the effective integration of the cathode and anode of the lithium ion battery and the packaging system thereof, greatly improves the proportion of active substances in battery electrode materials, shortens the migration distance of the lithium ion battery in the charging and discharging process, and improves the diffusion rate and the migration rate of lithium ions.
However, the lithium ion battery prepared by the existing 3D printing technology is generally in a cathode-anode interdigital structure without a diaphragm, the structure is easy to print, but the lithium ion battery electrode material has significant volume change and large stress in the lithium storage process, and the electrode is easy to deform or even collapse in the charging and discharging process. If the interdigital structure of the cathode and the anode is applied to a flexible battery, the interdigital structure of the cathode and the anode is restored after being bent and deformed for many times, and the damage speed of the electrode is higher. Therefore, improvement of the above structure based on 3D printing technology is a key to solve this problem.
Disclosure of Invention
The invention aims to overcome the defects that the structure is easy to collapse and is not suitable for a flexible battery in the existing interdigital electrode charging and discharging process, and provides a 3D printing method of the flexible battery. The method improves the structure of the traditional interdigital electrode, so that the interdigital electrode can be used for a flexible battery, has a complete structure in the charging and discharging process, and is still complete and firm after being bent and restored for many times. In addition, the proportion of active substances of electrode materials in the flexible battery is increased, and the electrochemical performance of the flexible battery is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
A3D printing method of a flexible battery mainly comprises the following steps: (1) utilizing three-dimensional software to model, and designing the structures of the flexible battery substrate and the substrate cover, the shape and the position of the current collector, the shape and the position of the positive/negative electrode slurry and the shape and the position of the baffle; (2) printing a flexible battery substrate and a base cover according to the three-dimensional model, wherein triangular tooth-shaped surfaces which are meshed with each other are designed in the substrate and the base cover; (3) printing a conductive material on a tooth-shaped surface of a base body to form an interdigital current collector, wherein the root of the interdigital current collector is vertical to the top ridge line of the triangle, and the finger parts of the interdigital current collector are positioned at two waists of the triangle and are parallel to the top ridge line of the triangle; (4) printing the positive/negative electrode slurry on a positive/negative electrode current collector to form a positive/negative electrode of the flexible battery; (5) printing a baffle between the positive electrode and the negative electrode, wherein the distance from the top of the baffle to the triangular waist surface is more than or equal to the sum of the thicknesses of the positive electrode/negative electrode current collector and the positive electrode/negative electrode; (6) the basal body and the basal cover are packaged together, the triangle tooth-shaped areas of the basal body and the basal cover are mutually matched, and the internal gap of the basal body and the basal cover forms a storage space of electrolyte.
As an improved technical scheme of the invention, a plurality of holes are distributed in the plane of the baffle.
As an improved technical scheme of the invention, one of the positive/negative electrode active materials is printed on a positive electrode or a negative electrode current collector in a U shape, and the other material is printed on a negative electrode or a positive electrode current collector in a T shape.
As an improved technical scheme of the invention, the connecting part between the two waist surfaces of the triangle is an arc surface tangent to the two waist surfaces, and the positive/negative electrodes are positioned in the waist surfaces of the triangle and avoid the arc surface.
Further, the included angle between the waist surface and the waist surface is 30-75 degrees, and the ratio of the length of the waist surface to the radius of the cambered surface is 30: 1-10: 1.
preferably, the included angle between the waist surface and the waist surface is 40-60 degrees, and the ratio of the length of the waist surface to the radius of the cambered surface is 20: 1-15: 1.
as an improved technical scheme of the invention, the bottom side of the triangle is positioned on the bisection plane of the substrate.
As an improved technical scheme of the invention, the printing process of the substrate, the base cover and the baffle comprises the following steps: dissolving 1-8 wt% of fluoboric acid diazonium salt in 10-20 wt% of octyl acrylate, adding 0.01-1 wt% of titanium dioxide nano powder for uniform ultrasonic dispersion, then adding 10-25 wt% of hydrogen-containing silicone oil, 15-30 wt% of acrylate, 15-60 wt% of polyurethane acrylic resin, 0.1-2 wt% of diacetone alcohol and 0.1-2 wt% of octanol, and mixing together to form mixed slurry; stirring at a high speed, ultrasonically dispersing the mixed slurry, and repeating the operation for multiple times to uniformly disperse each substance in the mixed slurry to obtain the photocuring 3D printing slurry; and injecting the photocuring 3D printing slurry into a 3D printer, adjusting the wavelength of a curing light source to be 300-400 nm, printing the thickness of each layer to be 100-2000 mu m, and exposing for 2-10 s.
Further, the printing process of the substrate, the base cover and the baffle comprises the following steps: dissolving 2-6 wt% of fluoboric acid diazonium salt in 12-18 wt% of octyl acrylate, adding 0.1-0.5 wt% of titanium dioxide nano powder for uniform ultrasonic dispersion, then adding 15-22 wt% of hydrogen-containing silicone oil, 20-28 wt% of acrylate, 24-48 wt% of polyurethane acrylic resin, 0.5-1.5 wt% of diacetone alcohol and 0.5-1.5 wt% of octanol, and mixing together to form mixed slurry; stirring at a high speed, ultrasonically dispersing the mixed slurry, and repeating the operation for multiple times to uniformly disperse each substance in the mixed slurry to obtain the photocuring 3D printing slurry; and injecting the photocuring 3D printing slurry into a 3D printer, adjusting the wavelength of a curing light source to be 350-400 nm, printing the thickness of each layer to be 500-1000 mu m, and exposing for 4-8 s.
Preferably, the printing process of the substrate, the base cover and the baffle plate is as follows: dissolving 4 wt% of fluoboric acid diazonium salt in 15 wt% of octyl acrylate, adding 0.3 wt% of titanium dioxide nano powder, performing ultrasonic dispersion uniformly, and then adding 20 wt% of hydrogen-containing silicone oil, 25 wt% of acrylate, 33.7 wt% of polyurethane acrylic resin, 1 wt% of diacetone alcohol and 1 wt% of octanol, and mixing together to form mixed slurry; stirring at a high speed, ultrasonically dispersing the mixed slurry, and repeating the operation for multiple times to uniformly disperse each substance in the mixed slurry to obtain the photocuring 3D printing slurry; and injecting the photocuring 3D printing slurry into a 3D printer, adjusting the wavelength of a curing light source to 365nm, printing each layer to be 500 mu m, and exposing for 5 s.
Has the advantages that:
the invention improves the traditional interdigital electrode structure, so that the anode/cathode of the battery is positioned on the waist surface of the triangular slope, on one hand, the quantity of the anode/cathode active substances can be increased, and the electrochemical performance of the flexible battery is improved, on the other hand, when the flexible battery is subjected to bending stress, the joint of the two waist surfaces of the triangle is subjected to great extrusion acting force, but the waist surface of the triangle is not influenced by the bending stress, namely the anode/cathode active substances are not influenced by the bending deformation of the flexible battery. In addition, a baffle is printed between the positive electrode and the negative electrode, the positive electrode and the negative electrode are effectively limited in a groove formed by the baffle and support force is given to the positive electrode and the negative electrode active material, and the positive electrode and the negative electrode active material are prevented from collapsing and deforming in the charging and discharging process and are connected in series to cause short circuit of the flexible battery. The invention also provides a printing process of the substrate, the base cover and the baffle, the process is simple, the flexibility and toughness of the prepared substrate, the base cover and the baffle meet the requirements of a flexible battery, and the substrate, the base cover and the baffle are not broken or embrittled after being bent, charged and discharged for many times.
Drawings
FIG. 1 is a schematic view of the structure of a base and a base cover according to the present invention;
FIG. 2 is a diagram of an electrode structure distribution of one of the triangular surfaces;
FIG. 3 is a schematic structural view of a triangular tooth-shaped surface;
fig. 4 is a schematic structural diagram of the substrate and the substrate cover after packaging.
Detailed Description
In order that those skilled in the art will more clearly understand the present invention, the detailed description of the present invention will be given with reference to the accompanying drawings.
The 3D printing method of the flexible battery mainly comprises the following steps: (1) designing the structures of the flexible battery substrate 1 and the base cover 2, the shapes and the positions of current collectors (4, 4 '), the shapes and the positions of positive/negative electrode (7, 7') slurry and the shapes and the positions of baffles 8 by utilizing three-dimensional software modeling; (2) printing a flexible battery substrate 1 and a base cover 2 according to a three-dimensional model, wherein triangular tooth-shaped surfaces which are meshed with each other are designed inside the substrate 1 and the base cover 2, as shown in fig. 1; (3) printing a conductive material on the tooth-shaped surface of the substrate 1 to form an interdigital current collector (4, 4 '), wherein the root of the interdigital current collector (4, 4 ') is perpendicular to the top ridge of the triangle, and the finger parts of the interdigital current collector (4, 4 ') are positioned at two waists of the triangle and are parallel to the top ridge of the triangle (as an enlarged area 3 in fig. 1); (4) printing the positive/negative electrode (7, 7 ') slurry onto a positive/negative electrode current collector (4, 4') to form a positive/negative electrode (7, 7 ') of a flexible battery, preferably, one of the positive/negative electrode (7, 7') active materials is printed in a "U" shape on a positive or negative electrode current collector (4, 4 ') and the other material is printed in a "T" shape on a negative or positive electrode current collector (4, 4') as shown in fig. 2; (5) printing a baffle plate 8 between the positive/negative electrodes (7, 7 '), wherein the distance between the top of the baffle plate 8 and the triangular waist surface 5 is more than or equal to the sum of the thicknesses of the positive/negative current collectors (4, 4 ') and the positive/negative electrodes (7, 7 '), as shown in figure 3; (6) the base body and the base cover 2 are packaged together, the triangular tooth-shaped areas of the base body and the base cover are mutually matched, and the internal gaps of the base body and the base cover form a storage space of electrolyte, as shown in figure 4. Preferably, a plurality of holes are distributed in the plane of said baffle 8 to facilitate the flow of electrolyte between the positive/negative electrodes (7, 7').
In order to reduce the acting force of the bending stress on the joint of the two triangular waist surfaces 5, the joint between the two triangular waist surfaces 5 is an arc surface 6 tangent to the two waist surfaces 5, and positive/negative electrodes (7, 7') are positioned in the triangular waist surfaces 5 and avoid the arc surface 6. Further, an included angle between the waist surface 5 and the waist surface 5 is 30-75 degrees, and the ratio of the length of the waist surface 5 to the radius of the cambered surface 6 is 30: 1-10: 1. preferably, an included angle between the waist surface 5 and the waist surface 5 is 40-60 °, and a ratio of the length of the waist surface 5 to the radius of the arc surface 6 is 20: 1-15: 1.
in order to improve the overall structural strength of the flexible battery, the base of the triangle is preferably located on the bisecting plane of the substrate 1.
In addition, the invention also provides a printing process of the substrate 1, the substrate cover 2 and the baffle plate 8, which comprises the following steps: dissolving 1-8 wt% of fluoboric acid diazonium salt in 10-20 wt% of octyl acrylate, adding 0.01-1 wt% of titanium dioxide nano powder for uniform ultrasonic dispersion, then adding 10-25 wt% of hydrogen-containing silicone oil, 15-30 wt% of acrylate, 15-60 wt% of polyurethane acrylic resin, 0.1-2 wt% of diacetone alcohol and 0.1-2 wt% of octanol, and mixing together to form mixed slurry; stirring at a high speed, ultrasonically dispersing the mixed slurry, and repeating the operation for multiple times to uniformly disperse each substance in the mixed slurry to obtain the photocuring 3D printing slurry; and injecting the photocuring 3D printing paste into a 3D printer 9, adjusting the wavelength of a curing light source to be 300-400 nm, printing the thickness of each layer to be 100-2000 mu m, and exposing for 2-10 s.
The printing process of the substrate 1, the substrate cover 2 and the baffle 8 is specifically carried out as in examples 1 to 5.
Example 1
Dissolving 8 wt% of fluoboric acid diazonium salt in 20 wt% of octyl acrylate, adding 1 wt% of titanium dioxide nano powder, performing ultrasonic dispersion uniformly, then adding 25 wt% of hydrogen-containing silicone oil, 30 wt% of acrylate, 15.8 wt% of polyurethane acrylic resin, 0.1 wt% of diacetone alcohol and 0.1 wt% of octanol, and mixing together to form mixed slurry; stirring at a high speed, ultrasonically dispersing the mixed slurry, and repeating the operation for multiple times to uniformly disperse each substance in the mixed slurry to obtain the photocuring 3D printing slurry; and injecting the photocuring 3D printing paste into a 3D printer 9, adjusting the wavelength of a curing light source to be 300nm, printing the thickness of each layer to be 2000 mu m, and exposing for 10 s.
Printing effect: the printing is smooth, the nozzle is not blocked, but the manufactured substrate 1, the base cover 2 and the baffle 8 are quite soft and have general formability.
Example 2
Dissolving 6 wt% of fluoboric acid diazonium salt in 18 wt% of octyl acrylate, adding 0.5 wt% of titanium dioxide nano powder, performing ultrasonic dispersion uniformly, and then adding 22 wt% of hydrogen-containing silicone oil, 28 wt% of acrylate, 24.5 wt% of polyurethane acrylic resin, 0.5 wt% of diacetone alcohol and 0.5 wt% of octanol, and mixing together to form mixed slurry; stirring at a high speed, ultrasonically dispersing the mixed slurry, and repeating the operation for multiple times to uniformly disperse each substance in the mixed slurry to obtain the photocuring 3D printing slurry; and injecting the photocuring 3D printing paste into a 3D printer 9, adjusting the wavelength of a curing light source to 365nm, printing each layer to be 1000 microns in thickness, and exposing for 8 s.
Printing effect: the printing is smooth, the nozzle is not blocked, and the manufactured base body 1, the base cover 2 and the baffle 8 are relatively soft and bendable, and have good formability.
Example 3
Dissolving 4 wt% of fluoboric acid diazonium salt in 15 wt% of octyl acrylate, adding 0.3 wt% of titanium dioxide nano powder, performing ultrasonic dispersion uniformly, and then adding 20 wt% of hydrogen-containing silicone oil, 25 wt% of acrylate, 33.7 wt% of polyurethane acrylic resin, 1 wt% of diacetone alcohol and 1 wt% of octanol, and mixing together to form mixed slurry; stirring at a high speed, ultrasonically dispersing the mixed slurry, and repeating the operation for multiple times to uniformly disperse each substance in the mixed slurry to obtain the photocuring 3D printing slurry; and injecting the photocuring 3D printing paste into a 3D printer 9, adjusting the wavelength of a curing light source to 365nm, printing each layer to be 500 mu m, and exposing for 5 s.
Printing effect: the printing is smooth, the nozzle is not blocked, and the manufactured substrate 1, the substrate cover 2 and the baffle 8 are moderate in flexibility, bendable and good in formability.
Example 4
Dissolving 2 wt% of fluoboric acid diazonium salt in 12 wt% of octyl acrylate, adding 0.1 wt% of titanium dioxide nano powder for uniform ultrasonic dispersion, then adding 15 wt% of hydrogen-containing silicone oil, 20 wt% of acrylate, 47.9 wt% of polyurethane acrylic resin, 1.5 wt% of diacetone alcohol and 1.5 wt% of octanol, and mixing together to form mixed slurry; stirring at a high speed, ultrasonically dispersing the mixed slurry, and repeating the operation for multiple times to uniformly disperse each substance in the mixed slurry to obtain the photocuring 3D printing slurry; and injecting the photocuring 3D printing paste into a 3D printer 9, adjusting the wavelength of a curing light source to 365nm, printing each layer to be 500 mu m, and exposing for 4 s.
Printing effect: the printing is smooth, the nozzle is not blocked, and the manufactured substrate 1, the substrate cover 2 and the baffle 8 are moderate in flexibility, bendable and good in formability.
Example 5
Dissolving 1 wt% of fluoboric acid diazonium salt in 10 wt% of octyl acrylate, adding 0.01 wt% of titanium dioxide nano powder for uniform ultrasonic dispersion, and then adding 10 wt% of hydrogen-containing silicone oil, 15 wt% of acrylate, 59.99 wt% of polyurethane acrylic resin, 2 wt% of diacetone alcohol and 2 wt% of octanol for mixing together to form mixed slurry; stirring at a high speed, ultrasonically dispersing the mixed slurry, and repeating the operation for multiple times to uniformly disperse each substance in the mixed slurry to obtain the photocuring 3D printing slurry; and injecting the photocuring 3D printing paste into a 3D printer 9, adjusting the wavelength of a curing light source to 365nm, printing each layer to be 100 mu m, and exposing for 2 s.
Printing effect: the printing is smooth, the nozzle is slightly blocked, and the manufactured substrate 1, the base cover 2 and the baffle 8 are general in flexibility, bendable and good in formability.
It is apparent that the above examples are only examples for clearly illustrating the present invention, and are not to be construed as limiting the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modifications made on the basis of the examples of the present invention, which are common knowledge, are within the scope of the present invention.

Claims (10)

1. A3D printing method of a flexible battery comprises the following steps: (1) utilizing three-dimensional software to model, and designing the structures of the flexible battery substrate and the substrate cover, the shape and the position of the current collector, the shape and the position of the positive/negative electrode slurry and the shape and the position of the baffle; (2) printing a flexible battery substrate and a base cover according to the three-dimensional model, wherein triangular tooth-shaped surfaces which are meshed with each other are designed in the substrate and the base cover; (3) printing a conductive material on a tooth-shaped surface of a base body to form an interdigital current collector, wherein the root of the interdigital current collector is vertical to the top ridge line of the triangle, and the finger parts of the interdigital current collector are positioned at two waists of the triangle and are parallel to the top ridge line of the triangle; (4) printing the positive/negative electrode slurry on a positive/negative electrode current collector to form a positive/negative electrode of the flexible battery; (5) printing a baffle between the positive electrode and the negative electrode, wherein the distance from the top of the baffle to the triangular waist surface is more than or equal to the sum of the thicknesses of the positive electrode/negative electrode current collector and the positive electrode/negative electrode; (6) the basal body and the basal cover are packaged together, the triangle tooth-shaped areas of the basal body and the basal cover are mutually matched, and the internal gap of the basal body and the basal cover forms a storage space of electrolyte.
2. The 3D printing method of the flexible battery according to claim 1, wherein: and a plurality of holes are distributed on the plane of the baffle.
3. The 3D printing method of the flexible battery according to claim 1, wherein: one of the positive/negative electrode active materials is printed on a positive electrode or a negative electrode current collector in a U shape, and the other material is printed on a negative electrode or a positive electrode current collector in a T shape.
4. The 3D printing method of the flexible battery according to claim 1, wherein: the connecting part between the two waist surfaces of the triangle is an arc surface tangent to the two waist surfaces, and the positive/negative electrodes are positioned in the waist surfaces of the triangle and avoid the arc surface.
5. The 3D printing method of the flexible battery according to claim 4, wherein: the included angle between the waist surface and the waist surface is 30-75 degrees, the ratio of the length of the waist surface to the radius of the cambered surface is 30: 1-10: 1.
6. the 3D printing method of the flexible battery according to claim 5, wherein: the included angle between the waist surface and the waist surface is 40-60 degrees, and the ratio of the length of the waist surface to the radius of the cambered surface is 20: 1-15: 1.
7. the 3D printing method of the flexible battery according to claim 1, wherein: the bottom edge of the triangle is positioned on the middle split surface of the base body.
8. The 3D printing method of the flexible battery according to claim 1, wherein the printing process of the substrate, the base cover and the baffle is as follows: dissolving 1-8 wt% of fluoboric acid diazonium salt in 10-20 wt% of octyl acrylate, adding 0.01-1 wt% of titanium dioxide nano powder for uniform ultrasonic dispersion, then adding 10-25 wt% of hydrogen-containing silicone oil, 15-30 wt% of acrylate, 15-60 wt% of polyurethane acrylic resin, 0.1-2 wt% of diacetone alcohol and 0.1-2 wt% of octanol, and mixing together to form mixed slurry; stirring at a high speed, ultrasonically dispersing the mixed slurry, and repeating the operation for multiple times to uniformly disperse each substance in the mixed slurry to obtain the photocuring 3D printing slurry; and injecting the photocuring 3D printing slurry into a 3D printer, adjusting the wavelength of a curing light source to be 300-400 nm, printing the thickness of each layer to be 100-2000 mu m, and exposing for 2-10 s.
9. The 3D printing method of the flexible battery according to claim 8, wherein the printing process of the substrate, the base cover and the baffle is as follows: dissolving 2-6 wt% of fluoboric acid diazonium salt in 12-18 wt% of octyl acrylate, adding 0.1-0.5 wt% of titanium dioxide nano powder for uniform ultrasonic dispersion, then adding 15-22 wt% of hydrogen-containing silicone oil, 20-28 wt% of acrylate, 24-48 wt% of polyurethane acrylic resin, 0.5-1.5 wt% of diacetone alcohol and 0.5-1.5 wt% of octanol, and mixing together to form mixed slurry; stirring at a high speed, ultrasonically dispersing the mixed slurry, and repeating the operation for multiple times to uniformly disperse each substance in the mixed slurry to obtain the photocuring 3D printing slurry; and injecting the photocuring 3D printing slurry into a 3D printer, adjusting the wavelength of a curing light source to be 350-400 nm, printing the thickness of each layer to be 500-1000 mu m, and exposing for 4-8 s.
10. The 3D printing method of the flexible battery according to claim 9, wherein the printing process of the substrate, the base cover and the baffle is as follows: dissolving 4 wt% of fluoboric acid diazonium salt in 15 wt% of octyl acrylate, adding 0.3 wt% of titanium dioxide nano powder, performing ultrasonic dispersion uniformly, and then adding 20 wt% of hydrogen-containing silicone oil, 25 wt% of acrylate, 33.7 wt% of polyurethane acrylic resin, 1 wt% of diacetone alcohol and 1 wt% of octanol, and mixing together to form mixed slurry; stirring at a high speed, ultrasonically dispersing the mixed slurry, and repeating the operation for multiple times to uniformly disperse each substance in the mixed slurry to obtain the photocuring 3D printing slurry; and injecting the photocuring 3D printing slurry into a 3D printer, adjusting the wavelength of a curing light source to 365nm, printing each layer to be 500 mu m, and exposing for 5 s.
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