CN114621633A - Water-based MXene-based energy storage electrode material 3D printing ink, and preparation method and application thereof - Google Patents

Water-based MXene-based energy storage electrode material 3D printing ink, and preparation method and application thereof Download PDF

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CN114621633A
CN114621633A CN202011458267.7A CN202011458267A CN114621633A CN 114621633 A CN114621633 A CN 114621633A CN 202011458267 A CN202011458267 A CN 202011458267A CN 114621633 A CN114621633 A CN 114621633A
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mxene
energy storage
printing ink
water
storage electrode
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CN114621633B (en
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吴忠帅
郑双好
刘瑜
马佳鑫
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • 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
    • Y02E60/13—Energy storage using capacitors

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-based 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

Water-based MXene-based energy storage electrode material 3D printing ink, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of 3D printing of electrochemical energy storage devices, and particularly relates to water-based MXene-based energy storage electrode material 3D printing ink, a preparation method and application thereof.
Background
The 3D printing technology, also known as additive manufacturing, is a new manufacturing technology that builds up materials layer by layer to manufacture solid objects based on digital models. 3D printing has a unique advantage of enabling rapid manufacturing of arbitrary complex shapes, compared to conventional manufacturing techniques, and thus is applied to various fields. The 3D printing technology can be classified into different printing methods according to different materials, which include: fused Deposition Modeling (FDM), Selective Laser Sintering (SLS), Stereolithography (SLA), Layered Object Modeling (LOM), Direct Ink Writing (DIW), and the like. The DIW is a pre-designed three-dimensional structure constructed by directly extruding and stacking ink with shear thinning performance layer by layer, and the technology has been widely applied in a plurality of fields due to the characteristics of low cost, convenient forming and the like, and has made a certain progress in the field of electrochemical energy storage in recent years. In the DIW technology, the quality of the ink directly affects the performance of the printing device, so the innovation of the ink is helpful for the development of the 3D printing technology. Although many conductive inks for 3D printing have been reported in the literature, there are still many problems, such as the use of organic solvents as solvents, poor conductivity of the inks, etc. Therefore, there is a need in the art to develop an environmentally friendly and highly conductive 3D printing ink.
Disclosure of Invention
In order to solve the above problems, the present inventors found that MXene material is a class of inorganic compounds having a two-dimensional layered structure, which is composed of transition metal carbide, nitride or carbonitride with a thickness of several atomic layers, and has been increasingly widely used in supercapacitors, batteries, electromagnetic interference shields, composite materials, and the like due to its unique structural properties, electronic characteristics and chemical properties. For example, unlike conventional batteries, the material provides more channels for the movement of ions, greatly increasing the speed of the movement of ions. Meanwhile, the MXene material has good dispersibility in water and stable performance, so that the MXene material can be used for preparing various conductive inks. Based on the method, the water-based MXene-based energy storage electrode material 3D printing ink is prepared, and has the characteristics of environmental protection and excellent conductivity.
Specifically, according to one aspect of the application, the application provides a water-based MXene-based energy storage electrode material 3D printing ink, and the 3D printing ink comprises water without oxygen, MXene, an auxiliary agent and an energy storage electrode active material.
Optionally, the 3D printing ink comprises, by weight, 40-80 parts of oxygen-free water, 10-40 parts of MXene, 1-5 parts of an auxiliary agent and 10-60 parts of an energy storage electrode active material.
Optionally, the 3D printing ink comprises, by weight, 40-80 parts of oxygen-free water, 10-40 parts of MXene, 1-5 parts of an auxiliary agent and 10-40 parts of an energy storage electrode active material.
Optionally, the fraction of oxygen-free water in the 3D printing ink is any of 40, 60, 65, 70, 75, 80, or a range of values defined by any two values, or any value within a range of values defined by any two values, by weight.
Optionally, the number of parts of MXene in the 3D printing ink is any of 10, 20, 30, 40, or a range of values defined by any two of the values, or any value within a range of values defined by any two of the values, by weight.
Optionally, in the 3D printing ink, the number of the auxiliary agent is any of 1, 2.5, 3, 3.5, 4, and 5, or a range of values defined by any two of the above values, or any value within a range of values defined by any two of the above values.
Optionally, in the 3D printing ink, the fraction of the energy storage electrode active material is any of 10, 30, 35, 40, 50, 60, or is a value in a range defined by any two values, or is any value within a range defined by any two values.
Optionally, the 3D printing ink consists of oxygen-free water, MXene, an adjuvant and an energy storage electrode active material.
Optionally, the MXene comprises Ti3C2、Ti3CN and Mo2C.
Optionally, the auxiliary agent comprises one or more of methylcellulose, hydroxyethyl cellulose, sodium alginate, sodium carboxymethyl cellulose, polyvinyl alcohol, polyethylene oxide, phenolic resin, polyacrylic resin, and polyvinylpyrrolidone.
Optionally, the energy storage electrode active material comprises 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 comprises one or more of carbon materials such as activated carbon, graphene, carbon nanotubes and the like.
Optionally, the lithium ion battery electrode active material comprises one or more of graphite, hard carbon, soft carbon, silicon carbon, lithium titanate, lithium iron phosphate, lithium cobaltate, lithium iron phosphate, lithium manganate, a ternary material, and a lithium-rich manganese-based material.
Optionally, the sodium ion battery electrode active material comprises one or more of hard carbon, black phosphorus, sodium titanate, sulfide, sodium manganate, sodium vanadium phosphate, prussian blue, and sodium vanadium phosphate fluoride.
Optionally, the zinc-ion battery electrode active material comprises one or more of zinc powder, vanadium oxide, manganese dioxide, sodium vanadium phosphate, zinc manganate.
According to another aspect of the application, the application also provides a preparation method of the water-based MXene-based energy storage electrode material 3D printing ink, and the method 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-based MXene-based energy storage electrode material 3D printing ink.
The specific types of MXene, additives and active materials of the energy storage electrode used in the method of the present application are as described above and will not be described herein again.
The parts by weight of the oxygen-containing water, the MXene, the auxiliary agent and the energy storage electrode active material in the method are as described above, and are not described in detail herein.
Optionally, the method comprises the steps of:
a) adding MXene, an energy storage electrode active material and an auxiliary agent into a ball milling tank;
b) adding deoxygenated water into a ball milling tank, adding grinding balls, and quickly replacing air in the ball milling tank with inert gas;
c) and (3) performing ball milling treatment quickly to obtain the water-based MXene-based energy storage electrode material 3D printing ink.
Optionally, in the ball milling treatment, the ball-to-material ratio is 2: 1-10: 1.
Alternatively, the oxygen-free aqueous solvent is obtained by bubbling oxygen-containing water with an inert gas before step (1).
Optionally, the ball-to-feed ratio is any value of 2:1, 3:1, 4:1, 6:1, 7:1, 8:1, 9:1, 10:1, or is a range value defined by any two values, or is any value within a range value defined by any two values.
Optionally, the ball material ratio is the mass ratio of the grinding ball to the mixed material comprising MXene, the auxiliary agent, the energy storage electrode active material and oxygen-free water.
Optionally, the inert gas comprises 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 rotation speed is 100-600 r/min.
Alternatively, the method is carried out at ambient temperature.
Alternatively, the method uses MXene in the form of a solid powder or in the form of an aqueous solution of MXene. Whether MXene is a solid powder or an aqueous solution of MXene is used to prepare the water based MXene based energy storage electrode material 3D printing ink, the parts by weight of oxygen free water in the final 3D printing ink are as described above.
According to a further aspect of the application, the application provides the application of the water-based MXene-based energy storage electrode material 3D printing ink or the water-based MXene-based energy storage electrode material 3D printing ink prepared according to the method in a printing substrate.
Optionally, the substrate comprises one or more of a PET substrate, a PI substrate, a metal substrate, a rubber substrate, and a plant fiber rich substrate.
Optionally, the metal substrate comprises one or more of a copper foil, an aluminum foil, and a stainless steel substrate.
Optionally, the plant fiber rich substrate comprises a4 paper and/or wood board.
The water in the "aqueous MXene solution" in this application refers to water free of oxygen and the "substrate rich in plant fibres" refers to a substrate in which the content of plant fibres is at least 50% of the total content.
In the application, the ternary material refers to a multi-metal composite oxide represented by lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate, can fully exert the advantages of three metals, has high battery energy density, and is one of the main positive electrode materials of the power battery. "lithium-rich manganese-based material" refers to a material having the general formula "xLi2MnO3·(1～x)LiMO2Wherein 0 is<x<1, M is one of Ni, Co and Mn.
For Ti in the present application3C2Tx，TxRepresents a terminating functional group on the few-layer MXene nano-sheets, wherein the terminating 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 is simple to operate, mild in condition and environment-friendly because only water is used as a solvent.
2) The preparation method of the water-based MXene-based energy storage electrode material 3D printing ink provided by the application is carried out at normal temperature in the preparation process, so that the preparation method is mild in condition.
3) The water-based MXene-based energy storage electrode material 3D printing ink prepared by the method contains MXene and an energy storage electrode active material, so that the prepared 3D printing ink has excellent conductivity, and a micro battery prepared from the ink has excellent electrochemical performance.
4) The water-based MXene-based energy storage electrode material 3D printing ink prepared by the method is stable in chemical property, and can be mixed with various electrode materials to prepare conductive ink.
5) The water-based MXene-based energy storage electrode material 3D printing ink prepared by the method has good shear rheological property and is easy to print.
6) The auxiliary agent in the water-based MXene-based energy storage electrode material 3D printing ink prepared by the method helps to improve the adhesion between the prepared 3D printing ink and a substrate.
Drawings
Fig. 1 shows TEM images of MXene nanoplatelets according to example 1 of the present invention.
Fig. 2 shows a schematic diagram of a lithium ion planar battery prepared from a water-based MXene-based energy storage electrode material 3D printing ink according to example 4 of the present invention.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to include proximity to such ranges or values. For numerical ranges, the endpoints of each of the ranges and the individual points between each may be combined with each other to give 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 with reference to examples, but the present application is not limited to these examples.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to include proximity to such ranges or values. For numerical ranges, the endpoints of each of the ranges and the individual points between each may be combined with each other to give one or more new numerical ranges, and these numerical ranges should be considered as specifically disclosed herein.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
MXene of the present application is commercially available or prepared by methods known in the art, for example, Ti3C2Prepared using the method of Selective Etching of Silicon from Ti3SiC2(MAX) To octain 2D Titanium Carbide (MXene)3CN passing document Ti3CN, nat. commun., 2019,10,1795, Mo1.33C, prepared by the method in the literature High-Performance Ultrathin Flexible Solid-State Supercapacitors Based on Solution Processable Mo1.33C MXene and PEDOT PSS.
The ball milling method in the embodiment of the application is realized by ball milling equipment commonly used in the field, and the 3D printing in the embodiment of the application is realized by a 3D printer commonly used in the field.
Unless otherwise specified, percentages (%) in the examples of the present application are by weight.
The JEM-2100 transmission electron microscope used for TEM photographs in the examples of the present application was tested under the following test conditions: firstly, a sample is dispersed in absolute ethyl alcohol under the action of ultrasonic oscillation, then the dispersed liquid is dripped on a common carbon supporting film or a micro-grid, and a TEM test can be carried out after the sample is dried.
The electrochemical performance test equipment in the application example is as follows: electrochemical workstation (CHI 760E).
Example 1
Mixing 30 parts of MXene (Mo)1.33C) (the shape of the nano-sheet is shown in figure 1), 35 parts of graphite and 3 parts of polyvinylpyrrolidone are mixed and then put into a ball milling tank, 70 parts of nitrogen is added to remove the graphiteWater, a solvent for oxygen; then 600 parts of grinding balls are put in, the air in the ball milling tank is replaced by nitrogen, then the ball milling tank is covered and placed on a ball mill, and ball milling is carried out for 30min at 200 r/min. A shear rate of 0.01s was obtained-1And the viscosity of the water-based MXene-based graphite electrode material is about 7000 Pa.s.
And printing the obtained printing ink by a 3D printing device, printing the printing ink on a copper foil to obtain an electrode of the lithium ion battery, assembling the electrode into a button battery by taking a lithium sheet as a counter electrode, and using the electrolyte as commercial electrolyte of the lithium ion battery. The printing parameters are as follows: the air pressure is 5-20 psi, and the printing speed is 2-10 mm/s. Under the condition of 1C (coulomb), the surface capacity of the lithium ion battery is tested to be 1.64mAh/cm2. Therefore, the prepared water-based MXene-based graphite electrode material 3D printing ink has excellent conductivity, and a lithium ion battery assembled by the ink has excellent electrochemical performance.
Example 2
Mixing 40 parts of MXene (Ti)3CN), 40 parts of sodium titanate and 4 parts of hydroxyethyl cellulose are mixed and then put into a ball milling pot, and 75 parts of solvent water deoxidized by nitrogen is added; and then 1000 parts of grinding balls are put in, the air in the ball milling tank is replaced by nitrogen, then the ball milling tank is covered and placed on a ball mill, and ball milling is carried out for 30min at 200 r/min. A shear rate of 0.01s was obtained-1The viscosity of the water-based MXene-based sodium titanate electrode material is about 8000 Pa.s.
Printing the obtained printing ink by a 3D printing device, printing the printing ink on PET, PI, glass and copper foil, wherein the printing parameters comprise: the air pressure is 5-20 psi, and the printing speed is 2-10 mm/s. A button cell is assembled by using the aqueous MXene-based sodium titanate electrode material ink printed on the copper foil as an electrode of a sodium ion battery and a sodium sheet as a counter electrode, wherein the electrolyte is a commercial electrolyte of the sodium ion battery. Under the condition of 1C (coulomb), the surface capacity of the sodium-ion battery is tested to be 0.83mAh/cm2. Therefore, the prepared ink has excellent conductivity, and a sodium ion battery assembled by the ink has excellent electrochemical performance.
Example 3
Mixing 20 parts of MXene (Ti)3C2) Mixing with 40 parts of sodium vanadium phosphate fluoride and 2.5 parts of sodium alginate, putting into a ball milling tank, and adding 60 parts of solvent water deoxidized by nitrogen; and then 1000 parts of grinding balls are put in, the air in the ball milling tank is replaced by nitrogen, then the ball milling tank is covered and placed on a ball mill, and ball milling is carried out for 30min at 200 r/min. A shear rate of 0.01s was obtained-1The viscosity of the water-based MXene-based sodium vanadium phosphate fluoride electrode material is about 5000 Pa.s.
Printing the obtained ink by a 3D printing device to A4, glass and aluminum foil, wherein the printing parameters comprise: the air pressure is 5-20 psi, and the printing speed is 2-10 mm/s. A button cell is assembled by using aqueous MXene-based vanadium sodium phosphate fluoride electrode material ink printed on an aluminum foil as an electrode of a sodium ion cell and a sodium sheet as a counter electrode, wherein the electrolyte is a commercial electrolyte of the sodium ion cell. Under the condition of 1C (coulomb), the surface capacity of the sodium-ion battery is tested and tested to be 0.72mAh/cm2. Therefore, the prepared ink has excellent conductivity, and a sodium ion battery assembled by the ink has excellent electrochemical performance.
Example 4
Mixing 30 parts of MXene (Ti)3C2) Mixing the lithium titanate, 40 parts of lithium titanate and 3 parts of sodium carboxymethylcellulose, putting the mixture into a ball milling tank, and adding 65 parts of solvent water for removing oxygen by using nitrogen; and then 1200 parts of grinding balls are put in, the air in the ball milling tank is replaced by nitrogen, then the ball milling tank is covered and placed on a ball mill, and ball milling is carried out for 30min at 200 revolutions per minute. A shear rate of 0.01s was obtained-1The viscosity of the water-based MXene-based lithium titanate electrode material 3D printing ink is about 8000 Pa.s.
30 parts of MXene (Ti)3C2) Mixing the mixture with 40 parts of lithium iron phosphate and 3 parts of sodium carboxymethylcellulose, putting the mixture into a ball milling tank, and adding 65 parts of solvent water for removing oxygen by using nitrogen; and then 1200 parts of grinding balls are put in, the air in the ball milling tank is replaced by nitrogen, then the ball milling tank is covered and placed on a ball mill, and ball milling is carried out for 30min at 200 revolutions per minute. A shear rate of 0.01s was obtained-1And the viscosity of the water-based MXene-based lithium iron phosphate electrode material is about 8000Pa.s, so that the ink can be printed in a 3D manner.
The obtained water system MXene groupLithium titanate electrode material 3D prints printing ink and water system MXene base lithium iron phosphate electrode material 3D and prints printing ink and prints through 3D printing device, prints to PET and A4 paper on, and the printing parameter is for including: the air pressure is 5-20 psi, and the printing speed is 2-10 mm/s. The obtained water-based MXene-based lithium titanate electrode material 3D printing ink and the water-based MXene-based lithium iron phosphate electrode material 3D printing ink are respectively printed on a PET substrate to obtain a negative electrode and a positive electrode of a lithium ion battery, the number of printing layers is 1, and commercial lithium ion electrolyte is used as electrolyte to form the lithium ion planar battery (the schematic diagram is shown in FIG. 2). Under the condition of 1C (coulomb), the surface capacity of the lithium ion planar battery is tested to be 0.76mAh/cm2. Therefore, the prepared ink has excellent conductivity, and the lithium ion planar battery assembled by the ink has excellent electrochemical performance.
Example 5
Mixing 40 parts of MXene (Ti)3C2) Mixing with 30 parts of molybdenum sulfide and 4 parts of methyl cellulose, putting into a ball milling tank, and adding 70 parts of solvent water deoxidized by nitrogen; and then 1200 parts of grinding balls are put in, the air in the ball milling tank is replaced by nitrogen, then the ball milling tank is covered and placed on a ball mill, and ball milling is carried out for 30min at 200 revolutions per minute. A viscosity shear rate of 0.01s was obtained-1And the viscosity of the water-based MXene-based molybdenum sulfide electrode material is about 10000 Pa.s.
Mixing 40 parts of MXene (Ti)3C2) Mixing with 30 parts of sodium vanadium phosphate and 4 parts of methyl cellulose, putting into a ball milling tank, and adding 70 parts of solvent water deoxidized by nitrogen; and then 1200 parts of grinding balls are put in, the air in the ball milling tank is replaced by nitrogen, then the ball milling tank is covered and placed on a ball mill, and ball milling is carried out for 30min at 200 revolutions per minute. A shear rate of 0.01s was obtained-1The viscosity of the water-based MXene-based sodium vanadium phosphate electrode material is about 10500 Pa.s.
The obtained water system MXene-based molybdenum sulfide electrode material 3D printing ink and the water system MXene-based vanadium sodium phosphate electrode material 3D printing ink can be printed on PET and glass through a 3D printing device, and the printing parameters comprise: the air pressure is 5-20 psi, and the printing speed is 2-10 mm/s. Vulcanizing the obtained water system MXene groupThe molybdenum electrode material 3D printing ink and the water system MXene-based vanadium sodium phosphate electrode material 3D printing ink are respectively printed on a PET substrate to obtain the cathode and the anode of the sodium ion planar battery, the number of printing layers is 1, and the electrolyte is commercial electrolyte of the sodium ion battery. Under the condition of 1C (coulomb), the surface capacity of the sodium ion planar battery is 0.49mAh/cm2. Therefore, the prepared ink has excellent conductivity, and the sodium ion planar battery assembled by the ink has excellent electrochemical performance.
Example 6
Mixing 40 parts of MXene (Ti)3C2) Mixing with 60 parts of zinc powder and 5 parts of methyl cellulose, putting into a ball milling tank, and adding 80 parts of solvent water deoxidized by nitrogen; and then 500 parts of grinding balls are put in, the air in the ball milling tank is replaced by nitrogen, then the ball milling tank is covered and placed on a ball mill, and ball milling is carried out for 30min at 200 r/min. A viscosity shear rate of 0.01s was obtained-1And the viscosity of the water-based MXene-based zinc powder electrode material is about 12000 Pa.s.
Mixing 40 parts of MXene (Ti)3C2) Mixing with 25 parts of manganese dioxide and 3 parts of methyl cellulose, putting into a ball milling tank, and adding 60 parts of solvent water deoxidized by nitrogen; and then 500 parts of grinding balls are put in the ball mill, the air in the ball mill tank is replaced by nitrogen, then the ball mill tank is covered and placed on the ball mill, and ball milling is carried out for 30min at 200 r/min. A shear rate of 0.01s was obtained-1And the viscosity is about 12000Pa.s, and the water-based MXene-based manganese dioxide electrode material is 3D printing ink.
Can print water system MXene base zinc powder electrode material 3D printing ink and water system MXene base manganese dioxide electrode material 3D printing ink through 3D printing device, print to PI, plank on, print the parameter and be including: the air pressure is 5-20 psi, and the printing speed is 2-10 mm/s. Respectively printing the obtained water-based MXene-based zinc powder electrode material 3D printing ink and the water-based MXene-based manganese dioxide electrode material 3D printing ink on a PI substrate to obtain a negative electrode and a positive electrode of the zinc-manganese planar battery, wherein the number of printing layers is 1, and 2MZnSO is adopted40.5 M MnSO4Is an electrolyte. Under the condition of 1C (coulomb), the surface capacity of the zinc-manganese planar battery is tested to be 0.16mAh/cm2. Thus saidObviously, the prepared ink has excellent conductivity, and the zinc-manganese planar battery assembled by the ink has excellent electrochemical performance.
Example 7
Mixing 40 parts of MXene (Ti)3CN), 40 parts of activated carbon and 3.5 parts of phenolic resin are mixed and then put into a ball milling pot, and 60 parts of solvent water deoxidized by nitrogen is added; and then 700 parts of grinding balls are put in, the air in the ball milling tank is replaced by nitrogen, then the ball milling tank is covered and placed on a ball mill, and ball milling is carried out for 30min at 200 r/min. A shear rate of 0.01s was obtained-1And the viscosity of the 3D printing ink is about 12000 Pa.s.
The obtained water system MXene-based active carbon electrode material 3D printing ink can be printed by a 3D printing device and is printed on PI and PET, and the printing parameters comprise: the air pressure is 5-20 psi, and the printing speed is 2-10 mm/s. Printing the obtained water system MXene-based activated carbon electrode material 3D printing ink on PET to obtain two electrodes of a supercapacitor, wherein the number of printing layers is 1, an electrolyte is a 20M LiCl aqueous solution, and constant-current charging and discharging are carried out at 0.5mA/cm2The surface capacity of the super capacitor tested under the condition is 364mF/cm2. Therefore, the prepared ink has excellent conductivity, and the supercapacitor assembled by the ink has excellent electrochemical performance.
Example 8
Mixing 40 parts of MXene (Ti)3C2) Mixing with 40 parts of active carbon and 3.5 parts of polyvinylpyrrolidone, putting into a ball milling pot, and adding 60 parts of solvent water deoxidized by nitrogen; and then 1000 parts of grinding balls are put in, the air in the ball milling tank is replaced by nitrogen, then the ball milling tank is covered and placed on a ball mill, and ball milling is carried out for 30min at 200 r/min. A shear rate of 0.01s was obtained-1And then, 3D printing ink of the water-based MXene-based activated carbon electrode material with the viscosity of about 11000Pa.s is prepared.
Mixing 30 parts of MXene (Ti)3C2) Mixing the lithium titanate, 50 parts of lithium titanate and 4 parts of polyvinylpyrrolidone, putting the mixture into a ball milling tank, and adding 60 parts of solvent water deoxidized by nitrogen; then 1000 parts of grinding balls are put in, the air in the ball milling tank is replaced by nitrogen, then the ball milling tank is covered,placing on a ball mill, and ball milling for 30min at 200 r/min. A shear rate of 0.01s was obtained-1And the viscosity of the water-based MXene-based lithium titanate electrode material is about 11000 Pa.s.
The obtained water system MXene-based activated carbon electrode material 3D printing ink and the water system MXene-based lithium titanate electrode material 3D printing ink can be printed on PET through a 3D printing device, and the printing parameters include: the air pressure is 5-20 psi, and the printing speed is 2-10 mm/s. And printing the obtained water-based MXene-based activated carbon electrode material 3D printing ink and the water-based MXene-based lithium titanate electrode material 3D printing ink on PET to obtain two electrodes of the lithium ion planar capacitor, wherein the number of printing layers is 1, and the electrolyte is commercial lithium ion electrolyte. The constant current charging and discharging is 0.5mA/cm2The surface capacity of the lithium ion planar capacitor tested under the condition is 136mF/cm2. Therefore, the prepared ink has excellent conductivity, and the lithium ion planar capacitor assembled by the ink has excellent electrochemical performance.
Although the present invention has been described with reference to a few preferred embodiments, it should be understood that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. The water-based MXene-based energy storage electrode material 3D printing ink is characterized by comprising oxygen-free water, MXene, an auxiliary agent and an energy storage electrode active material.
2. The water-based MXene-based energy storage electrode material 3D printing ink as claimed in claim 1, wherein the 3D printing ink comprises 40-80 parts by weight of water without oxygen, 10-40 parts by weight of MXene, 1-5 parts by weight of auxiliary agent and 10-60 parts by weight of energy storage electrode active material;
preferably, the 3D printing ink comprises 40-80 parts of oxygen-free water, 10-40 parts of MXene, 1-5 parts of auxiliaries and 10-40 parts of energy storage electrode active materials;
preferably, the 3D printing ink consists of oxygen-free water, MXene, an adjuvant and an energy storage electrode active material.
3. The aqueous MXene-based energy storage electrode material 3D printing ink of claim 1, wherein the MXene comprises Ti3C2、Ti3CN、Mo1.33C and Mo2C.
4. The aqueous MXene-based energy storage electrode material 3D printing ink as claimed in claim 1, wherein the auxiliary agent comprises one or more of methylcellulose, hydroxyethylcellulose, sodium alginate, sodium carboxymethylcellulose, polyvinyl alcohol, polyethylene oxide, phenolic resin, polyacrylic resin, polyvinyl pyrrolidone.
5. The aqueous MXene-based energy storage electrode material 3D printing ink as claimed in claim 1, wherein the energy storage electrode active material comprises at least one of supercapacitor electrode active material, lithium ion battery electrode active material, sodium ion battery electrode active material, zinc ion battery electrode active material;
preferably, the supercapacitor electrode active material comprises one or more of activated carbon, graphene and carbon nanotubes;
preferably, the lithium ion battery electrode active material comprises one or more of graphite, hard carbon, soft carbon, silicon carbon, lithium titanate, lithium iron phosphate, lithium cobaltate, lithium iron phosphate, lithium manganate, ternary material and lithium-rich manganese-based material;
preferably, the sodium ion battery electrode active material comprises one or more of hard carbon, black phosphorus, sodium titanate, sulfide, sodium manganate, sodium vanadium phosphate, prussian blue, and sodium vanadium phosphate fluoride;
preferably, the zinc-ion battery electrode active material comprises one or more of zinc powder, vanadium oxide, manganese dioxide, sodium vanadium phosphate, zinc manganate.
6. A method for preparing a water-based MXene-based energy storage electrode material 3D printing ink according to any one of claims 1 to 5, characterized in that the method comprises the following steps:
(1) uniformly mixing a raw material system containing MXene, an auxiliary agent and an energy storage electrode active material with oxygen-free water 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-based MXene-based energy storage electrode material 3D printing ink.
7. The preparation method according to claim 6, wherein in the ball milling treatment, a ball-to-material ratio is 2:1 to 10: 1.
8. The production method according to claim 6, wherein the oxygen-free water solvent is obtained by bubbling oxygen-containing solvent water using an inert gas before step (1);
preferably, the inert gas comprises at least one of nitrogen and argon;
preferably, in the ball milling treatment, the ball milling time is 10-80 min, and the ball milling rotating speed is 100-600 r/min.
9. Use of a water-based MXene-based energy storage electrode material 3D printing ink according to any one of claims 1 to 5 and/or a water-based MXene-based energy storage electrode material 3D printing ink prepared according to the method of any one of claims 6 to 8 in a printing substrate.
10. The use according to claim 9, wherein the substrate comprises one or more of a PET substrate, a PI substrate, a metal substrate, a rubber substrate, and a plant fiber rich substrate;
preferably, the metal substrate comprises one or more of a copper foil, an aluminum foil, and a stainless steel substrate;
preferably, the plant fiber-rich substrate comprises a4 paper and/or wood board.
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