CN117025020A - Biomass energy storage printing ink, preparation method and application - Google Patents
Biomass energy storage printing ink, preparation method and application Download PDFInfo
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- CN117025020A CN117025020A CN202310992335.5A CN202310992335A CN117025020A CN 117025020 A CN117025020 A CN 117025020A CN 202310992335 A CN202310992335 A CN 202310992335A CN 117025020 A CN117025020 A CN 117025020A
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- alloxazine
- biomass
- energy storage
- ink
- porous graphene
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- 239000002028 Biomass Substances 0.000 title claims abstract description 78
- 238000004146 energy storage Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000007639 printing Methods 0.000 title claims description 9
- HAUGRYOERYOXHX-UHFFFAOYSA-N Alloxazine Chemical compound C1=CC=C2N=C(C(=O)NC(=O)N3)C3=NC2=C1 HAUGRYOERYOXHX-UHFFFAOYSA-N 0.000 claims abstract description 122
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 46
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 13
- 239000011780 sodium chloride Substances 0.000 claims abstract description 11
- 239000006230 acetylene black Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000003822 epoxy resin Substances 0.000 claims abstract description 9
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- HMYNUKPKYAKNHH-UHFFFAOYSA-N acetylene;hydrate Chemical compound O.C#C HMYNUKPKYAKNHH-UHFFFAOYSA-N 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000976 ink Substances 0.000 claims description 55
- 239000000126 substance Substances 0.000 claims description 9
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical group OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000003487 electrochemical reaction Methods 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 230000002441 reversible effect Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 description 9
- 230000003993 interaction Effects 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- -1 alloxazine small molecules Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- 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
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
Abstract
The invention provides a preparation method of biomass energy storage ink, the ink and application, wherein the preparation method specifically comprises the following steps: step one, under the air atmosphere, adding the alloxazine and the biomass porous graphene into a NaCl-containing solution according to a certain mass ratio; step two, adding reduced graphene oxide, acetylene black and water-based epoxy resin into the solution in the step one, and uniformly stirring to obtain a mixture; step three: heating the mixture, and performing ultrasonic treatment on the mixture at the temperature of 30-70 ℃; step four: naturally cooling to room temperature to obtain the biomass energy storage ink.
Description
Technical Field
The invention relates to the field of energy storage ink, in particular to biomass energy storage ink, a preparation method and application.
Background
The biomass material is used as the renewable material with the most potential, promotes the biomass material resource utilization with rich reserves and environmental protection, is an effective technical approach for realizing double carbon, is also an important task of energy conservation, emission reduction and environmental protection in China, and meets the current requirements of environmental protection, energy conservation and low carbon economy.
In recent years, biomass materials have become a hot spot energy storage electrode material. However, the existing biomass material has the defects of difficult regulation and control of physical and chemical structures, low specific capacity, poor activity, low cycling stability, simple buckling type assembly, no flexibility, inability of large-area designability fine preparation and the like in the preparation and application processes.
Therefore, how to improve the structure and performance of biomass materials and how to prepare biomass-based devices is a problem to be solved.
Disclosure of Invention
The invention mainly aims to provide biomass energy storage printing ink, a preparation method and application, which are used for solving the technical problems to a certain extent.
In order to achieve the above purpose, the invention adopts the following technical scheme: the preparation method of the biomass energy storage ink specifically comprises the following steps:
step one, under the air atmosphere, adding the alloxazine and the biomass porous graphene into a NaCl-containing solution according to a certain mass ratio;
step two, adding reduced graphene oxide, acetylene black and water-based epoxy resin into the solution in the step one, and uniformly stirring to obtain a mixture;
step three: heating the mixture, and performing ultrasonic treatment on the mixture at the temperature of 30-70 ℃;
step four: naturally cooling to room temperature to obtain the biomass energy storage ink.
The alloxazine is alloxazine with an alloxazine structure, and the chemical formula is as follows:
the chemical formula of the biomass porous graphene is as follows:
preferably, in the first step, the mass ratio of the alloxazine to the biomass porous graphene is 1:3-3:1.
Preferably, in step one, the concentration in the NaCl solution is between 0.1 and 0.5M.
Preferably, in the mixture of the second step, the total mass fraction of the alloxazine and the biomass porous graphene is 11.7%.
The invention also provides biomass energy storage ink which is prepared by adopting the preparation method.
Preferably, the ink comprises at least the following components: the alloxazine of the alloxazine structure, the alloxazine of the isoalloxazine structure, the reduced alloxazine and the biomass porous graphene, pi-pi stacking and hydrogen bonds exist between amino groups in the alloxazine of the alloxazine structure, the reduced alloxazine and the amino groups in the reduced alloxazine and the biomass porous graphene doped oxygen atoms, and the alloxazine of the isoalloxazine structure is obtained by reversible reaction of the alloxazine structure in electrochemical reaction.
The invention also provides application of the biomass energy storage ink in printing ink.
Compared with the prior art, the invention has the following beneficial effects:
1) The biomass energy storage ink is in a gel state at room temperature, has higher specific capacity and excellent rheological property, has better electrode or device designability compared with a biomass material of solid powder or particles, and has good printability through test, the energy storage device prepared by printing has excellent electrochemical property, the integration of printing devices can be realized, and the energy storage performance can be regulated and controlled by designing the energy storage devices with different configurations (such as regulating the line width and the line distance of the interdigital miniature super capacitor).
2) The alloxazine and the biomass porous graphene have a synergistic enhancement effect on energy storage. Compared with other inks, the method for preparing the ink is simple and easy to understand, easy to operate, free of any solvent, easy to realize in the used instrument and reaction condition, and simple in synthesis steps.
3) Compared with manganese-based ink, noble metal ink, conductive polymer ink, graphene ink, carbon nanotube ink and MXene ink, the biomass energy storage ink has excellent rheological property, higher specific capacity, energy density and excellent cycling stability, and can meet the general research requirements.
4) The ink prepared by the preparation method of the invention can be directly used without purification.
Drawings
FIG. 1 is a non-covalent interaction model between a alloxazine and a biomass porous graphene and a redox mechanism thereof provided by the invention;
FIG. 2 is an electrochemical performance of the different mass ratios of alloxazine/biomass porous graphene ink provided by the present invention;
FIG. 3 is a digital photograph of a alloxazine/biomass porous graphene ink provided by the invention in a mass ratio of 1:2;
FIG. 4 is a microscopic morphology of a alloxazine/biomass porous graphene ink provided by the invention in a mass ratio of 1:2;
FIG. 5 is a graph of the rheological properties of a 1:2 mass ratio alloxazine/biomass porous graphene ink provided by the invention;
FIG. 6 is a high-precision patterned electrode prepared by screen printing with a mass ratio of 1:2 of the alloxazine/biomass porous graphene ink provided by the invention;
fig. 7 is a specific capacity of a micro flexible supercapacitor prepared by screen printing with a mass ratio of 1:2 of the alloxazine/biomass porous graphene ink provided by the invention under different current densities.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the invention. The preferred embodiments in the following description are by way of example only and other obvious variations will occur to those skilled in the art.
Example 1
The preparation method of the biomass energy storage ink specifically comprises the following steps:
step one, under the air atmosphere, adding the alloxazine and the biomass porous graphene into NaCl solution filled with 0.1-0.5M according to the mass ratio of 1:3-3:1;
step two, adding graphene oxide, acetylene black and water-based epoxy resin into the solution in the step one, and uniformly stirring to obtain a mixture;
step three: heating the mixture, and performing ultrasonic treatment on the mixture at the temperature of 30-70 ℃;
step four: naturally cooling to room temperature (25 ℃), and obtaining the biomass energy storage ink.
The alloxazine is alloxazine with an alloxazine structure, and the chemical formula is as follows:
the chemical formula of the biomass porous graphene is as follows:
in the second step, the total mass fraction of the alloxazine and the biomass porous graphene in the mixture is 10-13%.
Example two
This example is an ink prepared using the preparation method of example one.
The ink at least comprises the following components: the method comprises the steps of preparing a porous graphene, wherein pi-pi stacking and hydrogen bonds exist between amino groups in the alloxazine structure alloxazine, the alloxazine of the alloxazine structure alloxazine and the reduced alloxazine, and the biomass porous graphene doped with oxygen atoms, so that non-covalent interaction is carried out, the biomass porous graphene can fix the alloxazine through strong pi-pi stacking and hydrogen bonds, and stable fixed redox sites and conductive channels can be provided for alloxazine molecules.
The chemical formula of alloxazine of the isoalloxazine structure is as follows:
the chemical formula of the reduced alloxazine is as follows:
the alloxazine with the isoalloxazine structure is formed by reversible reaction of the alloxazine with the alloxazine structure in electrochemical reaction, so that pseudocapacitance can be provided for the whole ink system.
Experimental example 1
Under the air atmosphere, 7.5g of alloxazine small molecules and 2.5g of biomass porous graphene are added into a reactor filled with 40ml of 0.2M NaCl solution, 18g of reduced graphene oxide, acetylene black and aqueous epoxy resin are added, and then the mixture is stirred to be uniformly mixed, heated to 30 ℃ and treated by ultrasound for 0.5 hour; and naturally cooling to room temperature (25 ℃) after the ultrasonic treatment is finished, and obtaining the biomass energy storage ink.
Experimental example two
Under an air atmosphere, 6.6g of alloxazine and 3.3g of biomass porous graphene are added into a reactor filled with 40mL of 0.2M NaCl solution, 18g of reduced graphene oxide, acetylene black and aqueous epoxy resin are added, and then the mixture is stirred to be uniformly mixed, heated to 40 ℃ and subjected to ultrasonic treatment for 1.0 hour; and naturally cooling to room temperature (25 ℃) after the ultrasonic treatment is finished, and obtaining the biomass energy storage ink.
Experimental example III
Under the air atmosphere, 5g of alloxazine small molecules and 5g of biomass porous graphene are added into a reactor filled with 40mL of 0.2M NaCl solution, 18g of reduced graphene oxide, acetylene black and aqueous epoxy resin are added, and then the mixture is stirred to be uniformly mixed, heated to 50 ℃ and subjected to ultrasonic treatment for 1.5 hours; and naturally cooling to room temperature (25 ℃) after the ultrasonic treatment is finished, and obtaining the biomass energy storage ink.
Experimental example four
Under the air atmosphere, adding 3.3g of a small fludioxohydrazine molecule and 6.6g of biomass porous graphene into a reactor filled with 40ml of 0.2M NaCl solution, then adding 18g of reduced graphene oxide, acetylene black and aqueous epoxy resin, stirring to uniformly mix, heating to 60 ℃ and carrying out ultrasonic treatment for 2.0 hours; and naturally cooling to room temperature (25 ℃) after the ultrasonic treatment is finished, and obtaining the biomass energy storage ink.
Experimental example five
Under the air atmosphere, adding 2.5g of a small fludioxohydrazine molecule and 7.5g of biomass porous graphene into a reactor filled with 40ml of 0.2M NaCl solution, then adding 18g of reduced graphene oxide, acetylene black and aqueous epoxy resin, stirring to uniformly mix, heating to 70 ℃ and carrying out ultrasonic treatment for 2.5 hours; and naturally cooling to room temperature (25 ℃) after the ultrasonic treatment is finished, and obtaining the biomass energy storage ink.
The biomass energy storage ink obtained by different mass ratios shows different electrochemical performances through analysis of the ink obtained by different experimental examples. Specifically, as shown in fig. 2, the mass ratio of the alloxazine to the biomass porous graphene is 1:3-1:2, with the increase of the additive amount of the alloxazine, the capacity of the prepared biomass energy storage ink is continuously increased; the high-strength non-covalent interaction between the alloxazine and the lignin-based porous graphene is shown; when the mass ratio of the alloxazine to the biomass porous graphene is 1:2-3:1, the capacity of the prepared biomass energy storage ink is continuously reduced along with the increase of the additive amount of the alloxazine. Thus, the biomass energy storage inks prepared in the above-described experimental examples 1 to 5 exhibited different energy storage capacities. The biomass energy storage ink prepared in the experimental example 4 has the strongest energy storage capacity, and is subjected to experimental verification, and the experimental result is as follows:
as shown in fig. 3, the biomass energy storage ink prepared in experimental example 4 had strong adhesion on a transparent and smooth glass sheet and showed little change in adhesion after standing for 1 hour.
As shown in fig. 4, the biomass energy storage ink prepared in experimental example 4 has a three-dimensional porous nano-sheet structure and has stronger interaction between the alloxazine and the biomass porous graphene.
As shown in fig. 5, the biomass energy storage ink prepared in experimental example 4 has significant shear thinning behavior and higher shear strain.
As shown in fig. 6, the biomass energy storage ink prepared in experimental example 4 can prepare a high-precision and complex patterned electrode or device through screen printing.
As shown in fig. 7, the specific capacity of the interdigital micro supercapacitor prepared by screen printing of the biomass energy storage ink prepared in experimental example 4 can be regulated and controlled by the line distance (300-600 μm) and overprinting times (1-4 times) of the device, which indicates that the prepared biomass energy storage ink can regulate and control the energy storage performance by designing devices with different configurations, so that the biomass material can be utilized in the fields of adjustable energy storage and printing electronics in a large area with high precision, and the added value of the biomass material is improved.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. The preparation method of the biomass energy storage ink is characterized by comprising the following steps of:
step one, under the air atmosphere, adding the alloxazine and the biomass porous graphene into a NaCl-containing solution according to a certain mass ratio;
step two, adding reduced graphene oxide, acetylene black and water-based epoxy resin into the solution in the step one, and uniformly stirring to obtain a mixture;
step three: heating the mixture, and performing ultrasonic treatment on the mixture at the temperature of 30-70 ℃;
step four: naturally cooling to room temperature to obtain biomass energy storage printing ink;
the alloxazine is alloxazine with an alloxazine structure, and the chemical formula is as follows:
the chemical formula of the biomass porous graphene is as follows:
2. the method of claim 1, wherein in the first step, the mass ratio of the alloxazine to the biomass porous graphene is 1:3-3:1.
3. The method according to claim 1, wherein in the first step, the concentration of NaCl in the solution is 0.1 to 0.5M.
4. The preparation method according to claim 1, wherein in the mixture of the second step, the total mass fraction of the alloxazine and the biomass porous graphene is 11.7%.
5. A biomass energy storage ink prepared by the preparation method of any one of claims 1-4.
6. A biomass energy storage ink as claimed in claim 1 wherein said ink comprises at least the following components: the alloxazine of the alloxazine structure, the alloxazine of the isoalloxazine structure, the reduced alloxazine and the biomass porous graphene, pi-pi stacking and hydrogen bonds exist between amino groups in the alloxazine of the alloxazine structure, the reduced alloxazine and the amino groups in the reduced alloxazine and the biomass porous graphene doped oxygen atoms, and the alloxazine of the isoalloxazine structure is obtained by reversible reaction of the alloxazine structure in electrochemical reaction.
7. Use of the biomass energy storage ink of claim 5 or 6 in printing inks.
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| CN202310992335.5A CN117025020A (en) | 2023-08-08 | 2023-08-08 | Biomass energy storage printing ink, preparation method and application |
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| CN202310992335.5A CN117025020A (en) | 2023-08-08 | 2023-08-08 | Biomass energy storage printing ink, preparation method and application |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017190417A1 (en) * | 2016-05-06 | 2017-11-09 | 清华大学深圳研究生院 | Method for preparing thick and dense graphene-based electrode |
| US20220363931A1 (en) * | 2019-06-25 | 2022-11-17 | Kansas State University Research Foundation | Nano-inks of carbon nanomaterials for printing and coating |
| CN115646378A (en) * | 2022-09-15 | 2023-01-31 | 哈尔滨工业大学 | Biomass colloid gel and preparation method and application thereof |
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- 2023-08-08 CN CN202310992335.5A patent/CN117025020A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017190417A1 (en) * | 2016-05-06 | 2017-11-09 | 清华大学深圳研究生院 | Method for preparing thick and dense graphene-based electrode |
| US20220363931A1 (en) * | 2019-06-25 | 2022-11-17 | Kansas State University Research Foundation | Nano-inks of carbon nanomaterials for printing and coating |
| CN115646378A (en) * | 2022-09-15 | 2023-01-31 | 哈尔滨工业大学 | Biomass colloid gel and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| TIANSHENG WANG等: "Biomass-Derived Inks with Tailored Pteridine Derivatives for Sustainable Printed Micro-Supercapacitors", 《ADV. FUNCT. MATER.》, vol. 33, pages 1 - 13 * |
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