CN114621633B - Aqueous MXene-based energy storage electrode material 3D printing ink, its preparation method and application - Google Patents

Abstract

The application discloses water system MXene base energy storage electrode material 3D prints printing ink, it includes: water without oxygen, MXene, auxiliary agent and active material of energy storage electrode. The application also discloses a preparation method of the 3D printing ink, which comprises the following steps: (1) Uniformly mixing a raw material system containing MXene, an auxiliary agent and an energy storage electrode active material with an oxygen-free water solvent to obtain a mixed solution; (2) And (2) carrying out ball milling treatment on the mixed liquid obtained in the step (1) under the inert gas atmosphere condition to obtain the water system MXene-based energy storage electrode material 3D printing ink. The application also discloses application of the 3D printing ink in a printing substrate. The 3D printing ink prepared by the method has the characteristics of environmental protection and excellent conductivity.

Description

Aqueous MXene-based energy storage electrode material 3D printing ink, its preparation method and application

technical field

The invention belongs to the technical field of 3D printing of electrochemical energy storage devices, and in particular relates to a 3D printing ink for a water-based MXene-based energy storage electrode material, a preparation method and application thereof.

Background technique

3D printing technology, also known as additive manufacturing, is an emerging manufacturing technology that builds materials layer by layer to create physical objects based on digital models. Compared with traditional manufacturing techniques, 3D printing has the unique advantage of realizing rapid manufacturing of arbitrarily complex shapes, so it has been applied in many fields. 3D printing technology can be divided into different printing methods according to different materials, including: Fused Deposition Modeling (FDM), Selective Laser Sintering (SLS), Stereolithography (SLA), Layered Solid Molding (LOM) ), ink direct writing (Direct ink writing, DIW) and so on. Among them, DIW is to construct a pre-designed three-dimensional structure by directly extruding and stacking inks with shear thinning properties. This technology has been widely used in many fields due to its low cost and convenient molding. In recent years, Some progress has also been made in the field of electrochemical energy storage. In the DIW technology, the quality of the ink directly affects the performance of the printed device, so the innovation of the ink contributes to the development of this 3D printing technology application. Although many 3D printing conductive inks have been reported in the literature, there are still many problems, such as the solvent used in the ink is an organic solvent, and the conductive performance of the ink is poor. Therefore, there is an urgent need to develop a 3D printing ink that is environmentally friendly and has good electrical conductivity.

SUMMARY OF THE INVENTION

In order to solve the above problems, the inventors of the present application found that MXene materials are a kind of inorganic compounds with a two-dimensional layered structure, which are composed of transition metal carbides, nitrides or carbonitrides with a thickness of several atomic layers. The structural properties, electronic properties, and chemical properties of MXenes are increasingly used in supercapacitors, batteries, EMI shielding, and composite materials. Unlike conventional batteries, for example, the material provides more channels for the movement of ions, greatly increasing the speed of ion movement. At the same time, MXene material has good dispersibility in water and stable performance, so it can be used for the preparation of various conductive inks. Based on this, the inventors of the present application prepared a 3D printing ink for water-based MXene-based energy storage electrode materials, which has the characteristics of environmental protection and excellent electrical conductivity.

Specifically, according to one aspect of the present application, the present application provides an aqueous MXene-based energy storage electrode material 3D printing ink, the 3D printing ink comprising oxygen-free water, MXene, an auxiliary agent and an energy storage electrode active material .

Optionally, by weight, the 3D printing ink includes 40-80 parts of oxygen-free water, 10-40 parts of MXene, 1-5 parts of auxiliary agent and 10-60 parts of energy storage electrode active material.

Optionally, by weight, the 3D printing ink includes 40-80 parts of oxygen-free water, 10-40 parts of MXene, 1-5 parts of auxiliary agent and 10-40 parts of energy storage electrode active material.

Optionally, by weight, in the 3D printing ink, the fraction of oxygen-free water is any value among 40, 60, 65, 70, 75, 80, or is defined by any two values. A range of values, or any value within a range of values bounded by any two values.

Optionally, by weight, in the 3D printing ink, the number of parts of MXene is any value among 10, 20, 30, 40, or a range value defined by any two values, or a value defined by any two values Any value within the range of values.

Optionally, in the 3D printing ink, the number of copies of the auxiliary agent is any value among 1, 2.5, 3, 3.5, 4, and 5, or a range value defined by any two values, or any two values. Any value within the bounded range of values.

Optionally, in the 3D printing ink, the number of parts of the energy storage electrode active material is any value among 10, 30, 35, 40, 50, 60, or a range value defined by any two values, or Any value within the range of values bounded by any two values.

Optionally, the 3D printing ink is composed of oxygen-free water, MXene, auxiliary agent and energy storage electrode active material.

Optionally, the MXene includes at least one of Ti ₃ C ₂ , Ti ₃ CN and Mo ₂ C.

Optionally, the auxiliary agent includes methyl cellulose, hydroxyethyl cellulose, sodium alginate, sodium carboxymethyl cellulose, polyvinyl alcohol, polyethylene oxide, phenolic resin, polyacrylic acid resin, polyvinylpyrrolidone one or more of.

Optionally, the energy storage electrode active material includes at least one of a supercapacitor electrode active material, a lithium ion battery electrode active material, a sodium ion battery electrode active material, and a zinc ion battery electrode active material.

Optionally, the supercapacitor electrode active material includes one or more of carbon materials such as activated carbon, graphene, and carbon nanotubes.

Optionally, the lithium-ion battery electrode active materials include graphite, hard carbon, soft carbon, silicon carbon, lithium titanate, lithium iron phosphate, lithium cobaltate, lithium iron phosphate, lithium manganate, ternary materials, and lithium-rich manganese-based one or more of the materials.

Optionally, the sodium-ion battery electrode active material includes one or more of hard carbon, black phosphorus, sodium titanate, sulfide, sodium manganate, sodium vanadium phosphate, Prussian blue, and sodium vanadium fluoride phosphate.

Optionally, the zinc-ion battery electrode active material includes one or more of zinc powder, vanadium oxide, manganese dioxide, sodium vanadium phosphate, and zinc manganate.

According to another aspect of the present application, the present application also provides a method for preparing the above-mentioned 3D printing ink for a water-based MXene-based energy storage electrode material, the method comprising the following steps:

(1) uniformly mixing the raw material system comprising MXene, auxiliary agent, and energy storage electrode active material with an oxygen-free water solvent to obtain a mixed solution;

(2) Under the condition of an inert gas atmosphere, the mixed solution obtained in step (1) is subjected to ball milling treatment to obtain the water-based MXene-based energy storage electrode material 3D printing ink.

The specific types of MXenes, additives and energy storage electrode active materials used in the method described in this application are as described above, and will not be repeated here.

The weight parts of oxygen-containing water, MXene, auxiliary agent and energy storage electrode active material in the method described in the present application are as described above, and will not be repeated here.

Optionally, the method includes the steps of:

a) Add MXene, energy storage electrode active materials and additives into the ball mill jar;

b) Add deoxygenated water into the ball mill, and put the grinding balls, and quickly replace the air in the ball mill with inert gas;

c) Quickly perform ball milling to obtain a 3D printing ink for water-based MXene-based energy storage electrode materials.

Optionally, in the ball milling process, the ratio of ball to material is 2:1 to 10:1.

Optionally, the oxygen-free water solvent is obtained by bubbling oxygen-containing water with an inert gas before step (1).

Optionally, the ball-to-material ratio is any value among 2:1, 3:1, 4:1, 6:1, 7:1, 8:1, 9:1, 10:1, or the A range of values bounded by any two values, or any value within a range of values bounded by any two values.

Optionally, the ball-to-material ratio is the mass ratio of the grinding balls to the mixed material including MXene, auxiliary agent, energy storage electrode active material and oxygen-free water.

Optionally, the inert gas includes at least one of nitrogen and argon.

Optionally, in the ball milling treatment, the ball milling time is 10-80 min, and the ball-milling speed is 100-600 r/min.

Optionally, the method is carried out at normal temperature.

Optionally, the MXene used in the method is in the form of a solid powder or an aqueous solution of MXene. Regardless of whether MXene is used as a solid powder or an aqueous solution of MXene to prepare a 3D printing ink for an aqueous MXene-based energy storage electrode material, the weight fraction of oxygen-free water in the final 3D printing ink is as described above.

According to yet another aspect of the present application, the present application provides the application of the above-mentioned aqueous MXene-based energy storage electrode material 3D printing ink or the aqueous MXene-based energy storage electrode material 3D printing ink prepared according to the above method in a printing substrate.

Optionally, the substrate includes one or more of a PET substrate, a PI substrate, a metal substrate, a rubber substrate, and a vegetable fiber-rich substrate.

Optionally, the metal substrate includes one or more of copper foil, aluminum foil and stainless steel substrate.

Optionally, the vegetable fiber-rich substrate comprises A4 paper and/or wood board.

The water in the "MXene aqueous solution" in this application refers to water without oxygen, and the "vegetable fiber-rich substrate" refers to the substrate containing at least 50% of the total content of plant fibers.

In this application, "ternary material" refers to multi-component metal composite oxides represented by nickel-cobalt lithium manganate and nickel-cobalt aluminate, which can give full play to the advantages of the three metals, and have high battery energy density. One of the main cathode materials for power batteries. "Li-rich manganese-based material" refers to the general formula "xLi ₂ MnO ₃ ·(1~x)LiMO ₂ , where 0<x<1, and M is one of Ni, Co, and Mn".

For Ti ₃ C ₂ T _x in this application, T _x represents a termination functional group on the few-layer MXene nanosheet, the termination functional group is selected from fluorine, carboxyl or hydroxyl. "

The beneficial effects that this application can produce include:

1) The preparation method of the 3D printing ink provided in this application is simple in operation, mild in conditions, and only uses water as a solvent, so it is an environment-friendly method.

2) The preparation method of the water-based MXene-based energy storage electrode material 3D printing ink provided in the present application, the preparation process is carried out at normal temperature, so the preparation method of the present application has mild conditions.

3) The water-based MXene-based energy storage electrode material 3D printing ink prepared in this application contains MXene and energy storage electrode active materials, so the prepared 3D printing ink has excellent conductivity, and the microbattery prepared from the ink has excellent electrochemical performance.

4) The water-based MXene-based energy storage electrode material 3D printing ink prepared in this application has stable chemical properties, and can be mixed with various electrode materials to prepare a conductive ink.

5) The water-based MXene-based energy storage electrode material 3D printing ink prepared in this application has good shear rheological properties and is easy to print.

6) The additives in the 3D printing ink of the water-based MXene-based energy storage electrode material prepared in this application help to mention the adhesion between the prepared 3D printing ink and the substrate.

Description of drawings

FIG. 1 shows a TEM image of MXene nanosheets according to Example 1 of the present invention.

FIG. 2 shows a schematic diagram of a lithium-ion planar battery prepared by the aqueous MXene-based energy storage electrode material 3D printing ink according to Example 4 of the present invention.

Detailed ways

The present application will be described in detail below with reference to the examples, but the present application is not limited to these examples.

The endpoints of ranges and any values disclosed in this application are not to be limited to the precise ranges or values, which are to be understood to include approximate ranges or values. For numerical ranges, the endpoints and individual point values of each range can be combined with each other to yield one or more new numerical ranges, and these numerical ranges should be considered as specifically disclosed herein.

The present application will be described in detail below with reference to the examples, but the present application is not limited to these examples.

The endpoints of ranges and any values disclosed in this application are not to be limited to the precise ranges or values, which are to be understood to include approximate ranges or values. For numerical ranges, the endpoints and individual point values of each range can be combined with each other to yield one or more new numerical ranges, and these numerical ranges should be considered as specifically disclosed herein.

Unless otherwise specified, the raw materials in the examples of this application are all purchased through commercial channels.

The MXene of the present application is purchased through commercial channels or prepared by methods known in the art, for example, Ti ₃ C ₂ uses Selective Etching of Silicon from Ti SiC 2 (MAX) To Obtain 2D Titanium Carbide (MXene) in the method to prepare, Ti ₃ CN is prepared by the method in the document Ti ₃ CN, Nat. Commun., 2019, 10, 1795, Mo _1.33 C, by the document High-Performance Ultrathin Flexible Solid-StateSupercapacitors Based on Solution Processable Mo1.33C MXene and PEDOT:PSS method to prepare.

In the embodiments of the present application, the ball milling method is realized by ball milling equipment commonly used in the art, and the 3D printing in the embodiments of the present application is realized by a 3D printer commonly used in the art.

Unless otherwise specified, the percentages (%) in the examples of the present application are all by weight.

The JEM-2100 transmission electron microscope used for the TEM photos in the examples of this application was tested under the following test conditions: first, the sample was dispersed in absolute ethanol under the action of ultrasonic vibration, and then the dispersion was dropped on a common carbon support film or On the microgrid, the TEM test can be performed after the sample is dried.

The electrochemical performance testing equipment in the examples of this application is: electrochemical workstation (CHI760E).

Example 1

Mix 30 parts of MXene (Mo _1.33 C) (the morphology of its nanosheets is shown in Figure 1), 35 parts of graphite and 3 parts of polyvinylpyrrolidone, put it into a ball mill jar, and add 70 parts of solvent water deoxidized with nitrogen. ; Put in 600 parts of grinding balls, replace the air in the ball mill jar with nitrogen, then cover the ball mill jar, place it on the ball mill, and grind it at 200 rpm for 30 minutes. When the shear rate is 0.01s ^-1 , the viscosity of water-based MXene-based graphite electrode material 3D printing ink is about 7000Pa.s.

The obtained ink is printed by a 3D printing device, and printed on copper foil to obtain an electrode of a lithium ion battery. The counter electrode is a lithium sheet, which is assembled into a button battery, and the electrolyte is a commercial electrolyte of a lithium ion battery. The printing parameters include: the air pressure is 5-20 psi, and the printing speed is 2-10 mm/s. Under the condition of 1C (Coulomb), the areal capacity of the tested lithium-ion battery is 1.64mAh/cm ² . This shows that the prepared water-based MXene-based graphite electrode material 3D printing ink has excellent conductivity, and the lithium-ion battery assembled with the ink has excellent electrochemical performance.

Example 2

Mix 40 parts of MXene (Ti ₃ CN) with 40 parts of sodium titanate and 4 parts of hydroxyethyl cellulose and put it into a ball mill jar, add 75 parts of solvent water deoxidized with nitrogen; then put 1000 parts of grinding balls , replace the air in the ball mill jar with nitrogen, then cover the ball mill jar, place it on the ball mill, and perform ball milling at 200 rpm for 30 minutes. When the shear rate is 0.01s ^-1 , the 3D printing ink for water-based MXene-based sodium titanate electrode material with a viscosity of about 8000 Pa.s is obtained.

The obtained ink is printed by a 3D printing device, and printed on PET, PI, glass and copper foil, and the printing parameters include: the air pressure is 5-20 psi, and the printing speed is 2-10 mm/s. The aqueous MXene-based sodium titanate electrode material ink printed on the copper foil was used as the electrode of the sodium ion battery, the counter electrode was a sodium sheet, and a button battery was assembled, and the electrolyte was a commercial electrolyte of the sodium ion battery. Under the condition of 1C (Coulomb), the areal capacity of the tested sodium-ion battery is 0.83mAh/cm ² . This shows that the prepared ink has excellent electrical conductivity, and the sodium-ion battery assembled from the ink has excellent electrochemical performance.

Example 3

Mix 20 parts of MXene (Ti ₃ C ₂ ), 40 parts of sodium vanadium fluoride phosphate and 2.5 parts of sodium alginate into a ball mill, add 60 parts of solvent water deoxygenated with nitrogen; add 1000 parts of grinding Ball, replace the air in the ball mill jar with nitrogen, then cover the ball mill jar, place it on the ball mill, and perform ball milling at 200 rpm for 30 min. When the shear rate is 0.01s ^-1 , the 3D printing ink for water-based MXene-based sodium vanadium fluoride phosphate electrode material with a viscosity of about 5000 Pa.s is obtained.

The obtained ink is printed by a 3D printing device, and printed on A4, glass and aluminum foil, and the printing parameters include: the air pressure is 5-20 psi, and the printing speed is 2-10 mm/s. The water-based MXene-based fluorinated sodium vanadium phosphate electrode material ink printed on aluminum foil is used as the electrode of the sodium ion battery, the counter electrode is a sodium sheet, and a button battery is assembled, and the electrolyte is the commercial electrolyte of the sodium ion battery. Under the condition of 1C (Coulomb), the areal capacity of the tested sodium-ion battery is 0.72mAh/cm ² . This shows that the prepared ink has excellent electrical conductivity, and the sodium-ion battery assembled from the ink has excellent electrochemical performance.

Example 4

Mix 30 parts of MXene (Ti ₃ C ₂ ) with 40 parts of lithium titanate and 3 parts of sodium carboxymethyl cellulose, put it into a ball mill, add 65 parts of solvent water deoxygenated with nitrogen, and then put in 1200 parts Grind the balls, replace the air in the ball mill jar with nitrogen, then cover the ball mill jar, place it on the ball mill, and perform ball milling at 200 rpm for 30 min. When the shear rate is 0.01s ^-1 , the viscosity of the water-based MXene-based lithium titanate electrode material 3D printing ink is about 8000Pa.s.

Mix 30 parts of MXene (Ti ₃ C ₂ ), 40 parts of lithium iron phosphate and 3 parts of sodium carboxymethyl cellulose, put it into a ball mill, add 65 parts of solvent water deoxidized with nitrogen, and then put in 1200 parts Grind the balls, replace the air in the ball mill jar with nitrogen, then cover the ball mill jar, place it on the ball mill, and perform ball milling at 200 rpm for 30 min. When the shear rate is 0.01s ^-1 , the 3D printing ink of the water-based MXene-based lithium iron phosphate electrode material with a viscosity of about 8000Pa.s is obtained.

The obtained water-based MXene-based lithium titanate electrode material 3D printing ink and water-based MXene-based lithium iron phosphate electrode material 3D printing ink can be printed by a 3D printing device and printed on PET and A4 paper. The printing parameters include: the air pressure is 5 ~20psi, printing speed is 2~10mm/s. The obtained water-based MXene-based lithium titanate electrode material 3D printing ink and water-based MXene-based lithium iron phosphate electrode material 3D printing ink were respectively printed on a PET substrate to obtain the negative electrode and positive electrode of the lithium ion battery, and the number of printing layers was one layer. The commercial lithium-ion electrolyte is the electrolyte to form a lithium-ion planar battery (the schematic diagram is shown in Figure 2). Under the condition of 1C (Coulomb), the areal capacity of the tested lithium-ion planar battery is 0.76mAh/cm ² . This shows that the prepared ink has excellent electrical conductivity, and the lithium ion planar battery assembled from the ink has excellent electrochemical performance.

Example 5

Mix 40 parts of MXene (Ti ₃ C ₂ ) with 30 parts of molybdenum sulfide and 4 parts of methyl cellulose, put it into a ball mill, add 70 parts of solvent water deoxidized with nitrogen; then put 1200 parts of grinding balls, Replace the air in the ball mill jar with nitrogen, then cover the ball mill jar, place it on the ball mill, and perform ball milling at 200 rpm for 30 min. When the viscosity shear rate is 0.01s ^-1 , the water-based MXene-based molybdenum sulfide electrode material 3D printing ink with a viscosity of about 10000Pa.s is obtained.

Mix 40 parts of MXene (Ti ₃ C ₂ ), 30 parts of sodium vanadium phosphate and 4 parts of methyl cellulose into a ball mill jar, add 70 parts of solvent water deoxygenated with nitrogen; then put 1200 parts of grinding balls , replace the air in the ball mill jar with nitrogen, then cover the ball mill jar, place it on the ball mill, and perform ball milling at 200 rpm for 30 minutes. When the shear rate is 0.01s ^-1 , the 3D printing ink for water-based MXene-based sodium vanadium phosphate electrode material with a viscosity of about 10500Pa.s is obtained.

The obtained water-based MXene-based molybdenum sulfide electrode material 3D printing ink and water-based MXene-based sodium vanadium phosphate electrode material 3D printing ink can be printed by a 3D printing device and printed on PET and glass. The printing parameters include: air pressure is 5-20 psi, The printing speed is 2～10mm/s. The obtained water-based MXene-based molybdenum sulfide electrode material 3D printing ink and water-based MXene-based sodium vanadium phosphate electrode material 3D printing ink were respectively printed on a PET substrate to obtain the negative electrode and positive electrode of the sodium ion planar battery. Commercial electrolyte for sodium-ion batteries. The areal capacity of the Na-ion planar battery is 0.49 mAh/cm ² under 1C (Coulomb) conditions. This shows that the prepared ink has excellent electrical conductivity, and the sodium-ion planar battery assembled from the ink has excellent electrochemical performance.

Example 6

Mix 40 parts of MXene (Ti ₃ C ₂ ), 60 parts of zinc powder and 5 parts of methyl cellulose, put it into a ball mill, add 80 parts of solvent water deoxidized with nitrogen; put in 500 parts of grinding balls, Replace the air in the ball mill jar with nitrogen, then cover the ball mill jar, place it on the ball mill, and perform ball milling at 200 rpm for 30 min. When the viscosity shear rate is 0.01s ^-1 , the water-based MXene-based zinc powder electrode material 3D printing ink with a viscosity of about 12000Pa.s is obtained.

Mix 40 parts of MXene (Ti ₃ C ₂ ), 25 parts of manganese dioxide and 3 parts of methyl cellulose, put it into a ball mill, add 60 parts of solvent water deoxidized with nitrogen, and then put 500 parts of grinding balls , replace the air in the ball mill jar with nitrogen, then cover the ball mill jar, place it on the ball mill, and perform ball milling at 200 rpm for 30 minutes. When the shear rate is 0.01s ^-1 , the 3D printing ink of water-based MXene-based manganese dioxide electrode material with a viscosity of about 12000Pa.s is obtained.

The water-based MXene-based zinc powder electrode material 3D printing ink and the water-based MXene-based manganese dioxide electrode material 3D printing ink can be printed by a 3D printing device and printed on PI and wood. The printing parameters include: the air pressure is 5-20 psi, and the printing The speed is 2～10mm/s. The obtained water-based MXene-based zinc powder electrode material 3D printing ink and water-based MXene-based manganese dioxide electrode material 3D printing ink were respectively printed on PI substrates to obtain the negative electrode and positive electrode of the zinc-manganese planar battery. 2MZnSO ₄ 0.5 M MnSO ₄ is the electrolyte. Under the condition of 1C (Coulomb), the areal capacity of the tested zinc-manganese planar battery is 0.16mAh/cm ² . This shows that the prepared ink has excellent electrical conductivity, and the zinc-manganese planar battery assembled from the ink has excellent electrochemical performance.

Example 7

Mix 40 parts of MXene (Ti ₃ CN) with 40 parts of activated carbon and 3.5 parts of phenolic resin, put it into a ball mill, add 60 parts of solvent water deoxidized with nitrogen; put in 700 parts of grinding balls, and replace the ball mill with nitrogen. air in the jar, then cover the ball mill jar, place it on the ball mill, and mill it at 200 rpm for 30 minutes. When the shear rate is 0.01s ^-1 , the 3D printing ink of water-based MXene-based activated carbon electrode material with a viscosity of about 12000 Pa.s is obtained.

The obtained water-based MXene-based activated carbon electrode material 3D printing ink can be printed by a 3D printing device and printed on PI and PET. The printing parameters include: the air pressure is 5-20 psi, and the printing speed is 2-10 mm/s. The obtained water-based MXene-based activated carbon electrode material 3D printing ink was printed on PET to obtain two electrodes for supercapacitors, the number of printed layers was 1, the electrolyte was 20M LiCl aqueous solution, and the charge and discharge at constant current was 0.5mA/ ^cm2 The areal capacity of the tested supercapacitor under the condition is 364 mF/cm ² . This shows that the prepared ink has excellent electrical conductivity, and the supercapacitor assembled from the ink has excellent electrochemical performance.

Example 8

Mix 40 parts of MXene (Ti ₃ C ₂ ) with 40 parts of activated carbon and 3.5 parts of polyvinylpyrrolidone, put it in a ball mill, add 60 parts of solvent water deoxidized with nitrogen; Replace the air in the ball mill jar, then cover the ball mill jar, place it on the ball mill, and perform ball milling at 200 rpm for 30 minutes. When the shear rate is 0.01s ^-1 , the 3D printing ink of water-based MXene-based activated carbon electrode material with a viscosity of about 11000Pa.s is obtained.

Mix 30 parts of MXene (Ti ₃ C ₂ ), 50 parts of lithium titanate and 4 parts of polyvinylpyrrolidone into a ball mill jar, add 60 parts of solvent water deoxygenated with nitrogen; put in 1000 parts of grinding balls, Replace the air in the ball mill jar with nitrogen, then cover the ball mill jar, place it on the ball mill, and perform ball milling at 200 rpm for 30 min. When the shear rate is 0.01s ^-1 , the 3D printing ink of the water-based MXene-based lithium titanate electrode material with a viscosity of about 11000Pa.s is obtained.

The obtained water-based MXene-based activated carbon electrode material 3D printing ink and water-based MXene-based lithium titanate electrode material 3D printing ink can be printed by a 3D printing device and printed on PET. The printing parameters include: air pressure of 5-20 psi, printing speed It is 2～10mm/s. The obtained water-based MXene-based activated carbon electrode material 3D printing ink and water-based MXene-based lithium titanate electrode material 3D printing ink were printed on PET to obtain two electrodes for lithium-ion planar capacitors. The number of printed layers was 1, and the electrolyte was commercial. Lithium-ion electrolyte. Under the condition of constant current charge and discharge of 0.5mA/cm ² , the surface capacity of the lithium ion planar capacitor was tested to be 136mF/cm ² . This shows that the prepared ink has excellent electrical conductivity, and the lithium ion planar capacitor assembled from the ink has excellent electrochemical performance.

The above are only a few embodiments of the present application, and are not intended to limit the present application in any form. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Without departing from the scope of the technical solution of the present application, any changes or modifications made by using the technical content disclosed above are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims (11)

1. the application of a water-based MXene-based energy storage electrode material 3D printing ink in a printing substrate, is characterized in that, the 3D printing ink comprises oxygen-free water, MXene, auxiliary agent and energy storage electrode active material; The MXene includes at least one of Ti ₃ C ₂ , Ti ₃ CN, Mo _1.33 C and Mo ₂ C; The auxiliary agent includes one of methyl cellulose, hydroxyethyl cellulose, sodium alginate, sodium carboxymethyl cellulose, polyvinyl alcohol, polyethylene oxide, phenolic resin, polyacrylic acid resin, and polyvinylpyrrolidone or more; The energy storage electrode active material includes at least one of a supercapacitor electrode active material, a lithium ion battery electrode active material, a sodium ion battery electrode active material, and a zinc ion battery electrode active material; The supercapacitor electrode active material includes one or more of activated carbon, graphene, and carbon nanotubes; The electrode active material of the lithium ion battery includes one or one of graphite, hard carbon, soft carbon, silicon carbon, lithium titanate, lithium iron phosphate, lithium cobaltate, lithium manganate, ternary material, and lithium-rich manganese-based material. variety; The electrode active material of the sodium ion battery includes one or more of hard carbon, black phosphorus, sodium titanate, sulfide, sodium manganate, sodium vanadium phosphate, Prussian blue, and sodium vanadium fluoride phosphate; The zinc-ion battery electrode active material includes one or more of zinc powder, vanadium oxide, manganese dioxide, sodium vanadium phosphate, and zinc manganate; The 3D printing ink includes 40-80 parts of oxygen-free water, 10-40 parts of MXene, 1-5 parts of auxiliary agent and 10-60 parts of energy storage electrode active material. 2. use according to claim 1, is characterized in that, by weight, The 3D printing ink includes 40-80 parts of oxygen-free water, 10-40 parts of MXene, 1-5 parts of auxiliary agent and 10-40 parts of energy storage electrode active material. 3. The application according to claim 1, wherein the 3D printing ink is composed of oxygen-free water, MXene, auxiliary agent and energy storage electrode active material. 4. The application according to claim 1, wherein the preparation method of the water-based MXene-based energy storage electrode material 3D printing ink comprises the following steps: (1) Mix the raw material system including MXene, additives, and energy storage electrode active materials with oxygen-free water to obtain a mixed solution; (2) Under the condition of an inert gas atmosphere, the mixed solution obtained in step (1) is subjected to ball milling treatment to obtain the water-based MXene-based energy storage electrode material 3D printing ink. 5. The application according to claim 4, characterized in that, in the ball milling process, the ratio of ball to material is 2:1 to 10:1. 6 . The application according to claim 4 , wherein the oxygen-free water is obtained by bubbling the oxygen-containing water with an inert gas before step (1). 7 . 7. The application of claim 4, wherein the inert gas comprises at least one of nitrogen and argon. 8. The application according to claim 4, characterized in that, in the ball-milling treatment, the ball-milling time is 10-80min, and the ball-milling speed is 100-600r/min. 9. The application of claim 1, wherein the substrate comprises one or more of a PET substrate, a PI substrate, a metal substrate, a rubber substrate, and a vegetable fiber-rich substrate. 10. The application according to claim 9, wherein the metal substrate comprises one or more of copper foil, aluminum foil and stainless steel substrate. 11. The use according to claim 9, wherein the vegetable fiber-rich substrate comprises A4 paper and/or wood board.

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