CN114685825B - Preparation method of fibroin eutectic gel, product and application thereof - Google Patents
Preparation method of fibroin eutectic gel, product and application thereof Download PDFInfo
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- CN114685825B CN114685825B CN202210285102.7A CN202210285102A CN114685825B CN 114685825 B CN114685825 B CN 114685825B CN 202210285102 A CN202210285102 A CN 202210285102A CN 114685825 B CN114685825 B CN 114685825B
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- 108010022355 Fibroins Proteins 0.000 title claims abstract description 91
- 230000005496 eutectics Effects 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 30
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 30
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 12
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 241000255789 Bombyx mori Species 0.000 claims abstract description 11
- 238000012983 electrochemical energy storage Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000004513 sizing Methods 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 238000007790 scraping Methods 0.000 claims abstract description 8
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000007711 solidification Methods 0.000 claims abstract description 4
- 230000008023 solidification Effects 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 27
- 150000001875 compounds Chemical group 0.000 claims description 24
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 10
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 9
- 235000019743 Choline chloride Nutrition 0.000 claims description 9
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 9
- 229960003178 choline chloride Drugs 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000000502 dialysis Methods 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- -1 phosphorus salt compound Chemical class 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 239000003292 glue Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000499 gel Substances 0.000 description 57
- 239000011701 zinc Substances 0.000 description 31
- 239000003990 capacitor Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000011244 liquid electrolyte Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 235000013877 carbamide Nutrition 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 108010013296 Sericins Proteins 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 235000008708 Morus alba Nutrition 0.000 description 1
- 240000000249 Morus alba Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000012460 protein solution Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/093—Halogenated hydrocarbons
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/14—Measuring force or stress, in general by measuring variations in capacitance or inductance of electrical elements, e.g. by measuring variations of frequency of electrical oscillators
- G01L1/142—Measuring force or stress, in general by measuring variations in capacitance or inductance of electrical elements, e.g. by measuring variations of frequency of electrical oscillators using capacitors
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L9/00—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means
- G01L9/12—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means by making use of variations in capacitance, i.e. electric circuits therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses a preparation method of fibroin eutectic gel, a product and application thereof, wherein the preparation method comprises the following steps: (1) Removing impurities from natural silkworm cocoons to obtain silk fibroin, dissolving the silk fibroin in LiBr aqueous solution to form uniform aqueous solution, and dialyzing, concentrating and drying to obtain silk protein powder; (2) Mixing the fibroin powder prepared in the step (1) with hexafluoroisopropanol to obtain slurry; (3) And (3) scraping the sizing agent on release paper or pouring the sizing agent into a mould, and then soaking the sizing agent in a eutectic solvent for solidification to form a film, thus obtaining the fibroin eutectic gel. The raw materials adopted by the preparation process disclosed by the invention are all green, environment-friendly and cheap materials, and have good environmental stability and friendliness; the prepared fibroin eutectic glue can be used as a solid electrolyte to be applied to the preparation of an electrochemical energy storage device or can be directly used as a mechanical sensor.
Description
Technical Field
The invention relates to the technical field of eutectic gel, in particular to a preparation method of fibroin eutectic gel, a fibroin eutectic gel product and application of the fibroin eutectic gel product as a solid electrolyte in preparation of electrochemical energy storage devices and mechanical sensors.
Background
With the increasing exhaustion of traditional fossil fuel energy and the serious environmental deterioration problem brought by the exhaustion, people have an urgent need for developing renewable energy. However, most renewable energy sources such as wind energy, solar energy, tidal energy and geothermal energy are greatly influenced by time, climate and the like, and have great intermittency and instability, and if the renewable energy sources are directly incorporated into a power grid for use, the renewable energy sources will have great impact on the power grid. The development of superior performance recyclable electrochemical energy storage systems is currently a key issue.
Along with the demand of people on electrochemical energy storage devices is higher and higher, people pursue the safety performance of batteries, and the demands of wearability, environmental protection, green and the like are gradually increased. At present, most telephone energy storage devices use liquid electrolytes, liquid electrolyte solvents are divided into two categories, namely organic electrolytes and inorganic electrolytes, the organic electrolytes have high conductivity, but the organic electrolytes are difficult to synthesize and expensive, and the defects of flammability, explosiveness, high toxicity and the like exist. The inorganic electrolyte is mainly water, but the aqueous electrolyte is liable to cause dendrite, hydrogen evolution from the metal electrode, self-corrosion, and other adverse effects. The eutectic solvent (DESS) is a liquid obtained by mixing Lewis acid and alkali according to a certain molar ratio, and has the advantages of low price, environment-friendly components, high room temperature stability, stability to air, biodegradability and the like.
The eutectic gel is a gel formed by taking a eutectic solvent as a dispersion medium, and is used as a novel mixed material, the ionic liquid gel not only keeps the original property of the eutectic solvent, but also solves the problem of eutectic overflow, the higher plasticity of the ionic liquid gel in shape meets the requirements of people on special materials, and the application range of the ionic liquid is expanded. Compared with liquid electrolyte, the solid electrolyte directly serves as a diaphragm and an ion conductor, liquid leakage is prevented, and the liquid electrolyte has excellent performances of flexibility, capability of inhibiting dendritic crystal growth to a certain extent and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a preparation method of fibroin eutectic gel, and the adopted raw materials are all green, environment-friendly and cheap materials, and have good environmental stability and friendliness; the prepared fibroin eutectic glue can be used as a solid electrolyte to be applied to the preparation of an electrochemical energy storage device, and compared with the existing liquid electrolyte, the fibroin eutectic glue has no leakage, can stably exist in the air, has stable vapor pressure and is not easy to lose water; compared with an aqueous electrolyte, the problems of self-corrosion, hydrogen evolution and dendritic crystal of the Zn cathode are obviously improved, and the cycling stability and the environmental adaptability of the zinc metal cathode can be improved.
The specific technical scheme is as follows:
a preparation method of a fibroin eutectic gel comprises the following steps:
(1) Removing impurities from natural silkworm cocoons to obtain silk fibroin, dissolving the silk fibroin in LiBr aqueous solution to form uniform aqueous solution, and dialyzing, concentrating and drying to obtain silk protein powder;
(2) Mixing the fibroin powder prepared in the step (1) with hexafluoroisopropanol to obtain slurry;
(3) And scraping the sizing agent on release paper or filling the sizing agent into a mould, and then soaking the sizing agent in a eutectic solvent for solidification to form a film, thus obtaining the fibroin eutectic gel.
In the step (1):
in the present invention, the natural silkworm cocoon is selected from silkworm cocoons such as mulberry silk and tussah silk.
The impurity removal is to remove Na from the natural silkworm cocoon at 0.01-0.05 mol/L 2 CO 3 Boiling in water solution for 10-60 min, and then cleaning; preferably, 0.02mol/L of Na is used 2 CO 3 Boiling in water solution for 30min.
Silk fibroin can be deconstructed by using LiBr aqueous solution to form uniform silk fibroin aqueous solution, and beta crystal form in silk fibroin is deconstructed in the LiBr aqueous solution to form disordered high-molecular aqueous solution; preferably, the concentration of the aqueous solution of LiBr is 55wt%.
The resulting homogeneous aqueous solution was dialyzed against a dialysis bag to remove LiBr, and concentrated.
Preferably, the dialysis is carried out by adopting a dialysis bag with the molecular weight of 6000 to 8000, replacing the deionized water once every 6 hours, and completely removing LiBr impurities for 6 times.
Preferably, the concentration is carried out by using a polyethylene glycol aqueous solution with a molecular weight of 2000-20000.
Preferably, the drying treatment is freeze drying, and the concentrated aqueous solution is freeze dried to obtain silk protein powder.
In the step (2):
it was found through experiments that the solvent used for dissolving the fibroin powder to form the slurry and for the successful preparation of fibroin eutectic gels in DES can only be hexafluoroisopropanol if it is replaced by other organic solvents, such as CaCl 2 The/formic acid solution, although successful in dissolving the protein powder, failed to solidify in DES and failed to successfully prepare a fibroin co-crystal gel.
Experiments show that the concentration of the slurry directly influences the mechanical property of the prepared fibroin eutectic gel and the content of the low eutectic solvent in the fibroin eutectic gel, preferably, the mass ratio of the fibroin powder to the hexafluoroisopropanol is controlled to be 1:4 to 8 percent; further preferred mass ratio is 1:6 to 8, more preferably 1:8. it will be found that, using a 1: the fibroin eutectic gel prepared under the proportion of 8 has more excellent conductivity, and the assembled electrochemical energy storage device has more excellent electrochemical performance.
In the step (3):
the eutectic solvent (DES) comprises a hydrogen bond donor compound and a hydrogen bond acceptor compound;
the hydrogen bond donor compound is selected from one or more of formamide, acetamide, urea, ethylene glycol, glycerol, N-methylacetamide, oxalic acid, maleic acid, acrylic acid, methacrylic acid, acrylamide, monoethanolamine, citric acid and sorbitol;
the hydrogen bond acceptor compound is selected from one or more of halogen-containing ammonium salt, halogen-containing quaternary ammonium salt, halogen-containing phosphorus salt compound and metal halide;
the molar ratio of the hydrogen bond donor compound to the hydrogen bond acceptor compound is 0.5-10: 1.
the preparation of the DES involves thoroughly mixing a hydrogen bond donor compound and a hydrogen bond acceptor compound to form a homogeneous, transparent liquid.
Preferably:
the hydrogen bond donor compound is selected from ethylene glycol and/or urea, and the hydrogen bond acceptor compound is selected from choline chloride and/or zinc chloride;
the molar ratio of the hydrogen bond donor compound to the hydrogen bond acceptor compound is 2-4: 1.
further preferably, the hydrogen bond donor compound is selected from ethylene glycol and urea, and the hydrogen bond acceptor compound is selected from choline chloride and zinc chloride; the mol ratio of the glycol to the urea to the choline chloride to the zinc chloride is 6:10:3:3.
in the step (3), the film thickness of the prepared fibroin eutectic gel is 50 μm-1 mm, and a specific film forming mode can be selected according to the film thickness requirement of the fibroin eutectic gel to be prepared.
When the film thickness of the fibroin eutectic gel to be prepared is smaller, such as 50-300 mu m, a film can be formed by adopting a mode of scraping a film on release paper by a scraper;
when the film thickness of the fibroin eutectic gel to be prepared is larger, such as 300 mu m-1 mm, the protein slurry can be poured into a mould for film formation.
Tests show that if the thickness is increased, DES in the prepared fibroin eutectic gel cannot be completely cured, so that the use performance is reduced, and even demoulding cannot be realized.
The invention also discloses the fibroin eutectic gel prepared by the method, the content of DES in the fibroin eutectic gel can be controlled by regulating and controlling the concentration of the protein slurry, and the content of DES can be regulated within the range of 60-95 wt%.
The invention also discloses application of the fibroin eutectic adhesive as a solid electrolyte in preparation of electrochemical energy storage devices.
The electrochemical energy storage device comprises a super capacitor and an ion battery, in particular to a Zn super capacitor and a Zn ion battery.
The invention also discloses an application of the fibroin eutectic adhesive in preparing a mechanical sensor.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of fibroin eutectic gel, which adopts green and environment-friendly materials with low price as raw materials, has good environmental stability and friendliness, adopts natural silk which can be obtained in large quantity and has reasonable price, adopts most of eutectic solvents which are nontoxic and harmless, can be degraded in natural environment, realizes industrial preparation, and has low price.
The fibroin eutectic glue prepared by the invention can be used as a solid electrolyte to be applied to the preparation of electrochemical energy storage devices, in particular to the preparation of Zn super capacitors and Zn ion batteries. Compared with the existing liquid electrolyte, the electrolyte has no leakage, can stably exist in the air, has stable vapor pressure and is difficult to dehydrate; compared with an aqueous electrolyte, the problems of self-corrosion, hydrogen evolution and dendrite of the Zn negative electrode are obviously improved, so that the cycle stability and the environmental adaptability of the zinc metal negative electrode are improved.
The fibroin eutectic glue prepared by the invention is used as a Zn-C super capacitor assembled by a solid electrolyte, the electrochemical stability window is wider and is 0-2.4V, and the working voltage (0.2-1.8V) of the conventional Zn-C super capacitor reported at present is obviously better; the assembled Zn-C super capacitor has excellent low temperature resistance and still has higher electrochemical performance at the temperature of 18 ℃ below zero; the assembled Zn-C super capacitor also has excellent cycle stability and high charge-discharge reversibility, and after 20000 charge-discharge cycles, the capacitor has a capacitance retention rate of 84.3% and coulomb efficiency close to 100%.
The fibroin eutectic adhesive prepared by the invention also has the characteristic that the conductivity changes along with the change of an external force, and can be used as a mechanical sensor.
Drawings
Fig. 1 is an SEM picture of the fibroin eutectic gel prepared in example 1;
FIG. 2 is an infrared spectrum of the fibroin co-crystal gel prepared in example 1, and shows the DES used in this example as a comparison;
fig. 3 is an XRD pattern of the fibroin eutectic gel prepared in example 1;
fig. 4 is a CV curve of different voltage ranges at room temperature, representing electrical properties of Zn ion supercapacitors assembled with the fibroin eutectic gel prepared in example 1;
fig. 5 is a GCD curve of Zn ion supercapacitor assembled with fibroin eutectic gel prepared in example 1 at room temperature for different voltage ranges;
fig. 6 is CV curves of Zn ion supercapacitors assembled with fibroin eutectic gel prepared in example 1 at different scanning rates at room temperature;
fig. 7 is a GCD curve at room temperature at different current densities for Zn ion supercapacitors assembled with fibroin eutectic gel prepared in example 1;
fig. 8 is a GCD curve at-18 ℃ at different current densities for Zn ion supercapacitors assembled with fibroin eutectic gel prepared in example 1;
FIG. 9 shows that the amount of Zn ion in the Zn ion supercapacitor assembled with the fibroin eutectic gel prepared in example 1 is 5 ag -1 A cycle performance curve at current density;
fig. 10 is a CV curve of a Zn ion battery assembled with the fibroin eutectic gel prepared in example 3;
fig. 11 is a graph of the electrical conductivity versus time resistivity of the fibroin eutectic gel prepared in example 4 as a mechanical sensor.
Detailed Description
The present invention will be described in further detail below with reference to examples and comparative examples, but the embodiments of the present invention are not limited thereto.
The starting materials used in the following examples, which are not specifically described, are commercially available products well known in the art.
Example 1
(1) Placing natural silkworm cocoon at 0.02mol/L of Na 2 CO 3 Boiling in water solution for 30min to remove sericin, and washing with deionized water for three times to remove residual Na on silk surface 2 CO 3 。
(2) Dissolving degummed silk fibroin in 55wt% LiBr aqueous solution to form uniform aqueous solution.
(3) Dialyzing the treated water solution in a dialysis bag with the molecular weight of 6000-8000, changing the deionized water once every 6h, and changing the water 6 times to fully remove LiBr impurities. The concentration of the aqueous protein solution was increased by concentration with an aqueous solution of polyethylene glycol having a molecular weight of 2000.
(4) The concentrated aqueous solution was lyophilized to obtain 2g of protein powder, and dissolved in 16g of hexafluoroisopropanol to obtain a protein slurry.
(5) Removing water from ethylene glycol, choline chloride, urea and zinc chloride in a drying oven at 60 deg.C for 6 h. The four substances were mixed as follows 6:3:10:3 in an oil bath pan at 60 ℃ for 6h to form a clear and colorless DES.
(6) And (5) scraping the protein slurry prepared in the step (4) on release paper by using a scraper of 100 micrometers, and soaking the protein slurry in the DES prepared in the step (5) for solidifying into a film to obtain fibroin eutectic gel, wherein the fibroin eutectic gel is marked as ETG. The film has a conductivity of 12.31mS -1 。
Fig. 1 is an SEM picture of the fibroin eutectic gel prepared in this example, and it can be seen from observing fig. 1 that the fibroin eutectic gel forms a wavy surface due to the use of a coagulation bath.
Fig. 2 is an infrared spectrogram of the fibroin eutectic gel prepared in this embodiment, and it can be found from observation of fig. 2 that the prepared fibroin eutectic gel already contains a large amount of DES components and forms a characteristic peak of a beta crystal form of the fibroin polymer. This characteristic peak is the main manifestation of the formation of polymer crystals.
Fig. 3 is an XRD diffraction pattern of the fibroin eutectic gel prepared in this example, and observation of the pattern also obtained characteristic peaks of the polymer crystals. The presence of such characteristic peaks contributes to the gel's improved mechanical properties.
DES in the membrane was removed by soaking the fibroin eutectic gel in alcohol and evaporating off the alcohol. In the fibroin eutectic gel prepared by the implementation, the content of DES components is 92wt%.
And (4) performance testing:
the fibroin eutectic gel prepared by the implementation is used as an electrolyte diaphragm of a Zn ion supercapacitor, a 2000-mesh polished metal zinc sheet is used as a capacitor cathode, and the active carbon, the PVDF and the conductive carbon are mixed according to the mass ratio of 8:1:1 coating the carbon cloth with the positive electrode material, preparing a positive electrode material slice, and assembling the positive electrode material slice into the Zn ion super capacitor. And placing the assembled Zn super capacitor for 12h and then carrying out electrochemical test.
Fig. 4 is a CV curve of the assembled Zn supercapacitor at different voltage ranges at room temperature. It can be seen that the CV curve is roughly rectangular, and there is a significant jump when the voltage reaches 2.0V. It is noted that the currently reported operating voltage of the Zn-C supercapacitor is usually 0.2 to 1.8V, while the electrochemical window of the Zn supercapacitor assembled in the present embodiment can reach 0 to 2.4V, which indicates that the electrochemical stability window of the assembled Zn-C battery is wider.
Fig. 5 is a GCD curve of the assembled Zn supercapacitor at the same scan rate and different voltage ranges. It can be clearly seen that the GCD curve of the Zn-C capacitance is a symmetrical triangle when the voltage window is 1.6V or less. The GCD curve deviates from the symmetrical triangle when the operating voltage is increased to 2.0V. Considering the overall performance of the supercapacitor, the optimal operating voltage of the prepared Zn-C capacitor is considered to be 1.4V.
FIG. 6 shows the different scan rates (1-50 mV s) of the assembled Zn supercapacitor at 1.4V -1 ) CV curve below. These CV curves exhibit a quasi-rectangular shape. Even at 50mV s -1 The curve is still close to a rectangle at the scanning speed of (2), which shows that the Zn-C super capacitor has rapid dynamic characteristics in electrochemical reaction.
Fig. 7 is a GCD curve of the assembled Zn supercapacitor at different current densities. According to the formula, at current densities of 0.2, 0.5, 1, 2, 5 and 10 ag -1 The specific energy density of the Zn-C capacitor is 93.3, 87.5, 77.8, 58.3, 34.0 and 5.8Wh kg -1 。
To evaluate the applicability of the fibroin eutectic gel prepared in this example in a low temperature environment, its electrochemical properties were investigated at-18 ℃. Figure 8 shows the GCD curve of the assembled Zn supercapacitor at-18 ℃ in the voltage range 0-1.4V. ETG film at 0.2A g -1 The lower part realizes 242.9F g -1 High capacitance up to room temperature70.8% of the value, energy density 66.1Wh kg -1 And the electrochemical performance at low temperature is excellent.
FIG. 9 shows the assembled Zn supercapacitor at 5 Ag -1 The current load was followed by 20000 cycles of the cycle performance curve. The results show that even at 5 Ag -1 The super capacitor assembled by the method also shows good cycle stability under high current load. After 20000 charge-discharge cycles, the capacitor has a capacity retention of 84.3% and a coulombic efficiency close to 100%. The super capacitor is shown to have excellent cycle stability and high charge-discharge reversibility.
Comparative example 1
(1) Placing natural silkworm cocoon at 0.02mol/L of Na 2 CO 3 Boiling in water solution for 30min to remove sericin, and washing with deionized water for three times to remove residual Na on silk surface 2 CO 3 。
(2) Dissolving 2g degummed silk fibroin in 15g 10wt% of CaCl 2 Protein slurry was obtained in formic acid solution.
(3) Removing water from ethylene glycol, choline chloride, urea and zinc chloride in a drying oven at 60 deg.C for 6 h. The four substances were mixed as follows 6:3:10:3 in an oil bath pan at 60 ℃ for 6h to form a clear and colorless DES.
(4) And (3) scraping the protein slurry prepared in the step (2) on release paper by using a scraper with the thickness of 100 microns, and soaking in the DES prepared in the step (3).
It was found by experiment that the protein slurry in step 2 did not form a film.
Comparative example 2
(1) As a starting material, commercially available pure silkworm silk protein was directly used, and 10g of the protein was dissolved in 55wt% LiBr aqueous solution to obtain a protein slurry.
(2) Removing water from ethylene glycol, choline chloride, urea and zinc chloride in a drying oven at 60 deg.C for 6 h. The four substances were mixed as follows 6:3:10:3 in an oil bath pan at 60 ℃ for 6h to form a clear and colorless DES.
(3) And (3) scraping the protein slurry prepared in the step (1) on release paper by using a scraper with the thickness of 100 micrometers, and soaking in the DES prepared in the step (2).
The protein slurry in the step (2) is found to be incapable of forming a film through experiments.
The comparative examples and comparative examples 1 to 2 show that silk fibroin or commercially available pure silk protein directly used as a raw material cannot be solidified into a film in DES, and thus a silk protein eutectic gel cannot be successfully prepared. According to the invention, a large number of experiments show that the natural silkworm cocoons subjected to a series of pretreatment can be solidified into a film in DES only by adopting the slurry formed by dissolving the natural silkworm cocoons in hexafluoroisopropanol as a protein raw material, so that the fibroin eutectic gel is successfully prepared.
Example 2
The preparation process was substantially the same as in example 1 except that in step (4), 2g of the protein powder added was dissolved with 8g of hexafluoroisopropanol to obtain a protein slurry.
Tests prove that the conductivity of the fibroin eutectic gel prepared by the method is 8.26mS -1 In the fibroin eutectic gel, the content of DES component is 74wt%.
Example 3
(1) Production of protein powder was exactly the same as in example 1.
(4) 2g of the protein powder was dissolved in 16g of hexafluoroisopropanol solution to prepare a protein slurry.
(5) Removing water from ethylene glycol, choline chloride, urea and zinc chloride in a drying oven at 60 deg.C for 6 h. The four substances were mixed as follows 6:3:10:3 in an oil bath at 60 ℃ for 6h to form a clear and colorless DES.
(6) And (3) scraping the slurry on release paper by using a scraper with the diameter of 100 mu m, and soaking the release paper in DES (DES) for solidifying to form a film, thereby obtaining the fibroin eutectic gel.
And (4) performance testing:
the fibroin eutectic gel prepared by the implementation is used as an electrolyte diaphragm of a Zn battery, a metal zinc sheet polished by 2000 meshes is used as a battery cathode, cobalt hexacyanoferrate, PVDF and conductive carbon are coated on carbon cloth according to a mass ratio of 8.
Fig. 10 is a CV curve of the Zn ion battery assembled in this embodiment, and it can be seen that an obvious charge-discharge curve appears in the CV curve, which proves that the fibroin eutectic gel prepared by this embodiment can work normally in the Zn ion battery as an electrolyte.
Example 4
(1) The preparation of protein slurry was exactly the same as in example 1.
(5) The ethylene glycol and choline chloride are dried in a drying oven at 60 ℃ for 6 h. The two substances were mixed as follows 2:1 molar ratio in an oil bath pan at 60 ℃ for 6h to form a clear and colorless DES.
(6) And (4) putting the prepared protein slurry into a polytetrafluoroethylene mould with a groove with the depth of 500 mu m, and soaking the protein slurry into the DES prepared in the step (5) for solidification to form a film, so as to obtain the fibroin eutectic gel.
And (3) performance testing:
the fibroin eutectic gel prepared by the implementation is directly used as a mechanical sensor, and the mechanical sensor is directly placed in a stretching machine for testing, so that the situation that the material is stretched and recovered once in 15 seconds within a period of time, the conductivity is changed when the mechanics is changed, and a mechanical signal is converted into an electrical signal in real time can be found. The change in conductivity of the sensor material during stretch recovery can be seen in fig. 11.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods.
Claims (8)
1. A preparation method of fibroin eutectic gel is characterized by comprising the following steps:
(1) Removing impurities from natural silkworm cocoons to obtain silk fibroin, dissolving the silk fibroin in LiBr aqueous solution to form uniform aqueous solution, and dialyzing, concentrating and drying to obtain silk protein powder; the concentration of the LiBr aqueous solution is 55 wt%;
the dialysis adopts a dialysis bag with the molecular weight of 6000 to 8000;
concentrating by adopting a polyethylene glycol aqueous solution with the molecular weight of 2000 to 20000;
(2) Mixing the fibroin powder prepared in the step (1) with hexafluoroisopropanol to obtain slurry;
the mass ratio of the fibroin powder to the hexafluoroisopropanol is 1:4 to 8;
(3) And scraping the sizing agent on release paper or filling the sizing agent into a mould, and then soaking the sizing agent in a eutectic solvent for solidification to form a film, thus obtaining the fibroin eutectic gel.
2. The method for preparing the fibroin eutectic gel according to claim 1, wherein in the step (2):
the mass ratio of the fibroin powder to the hexafluoroisopropanol is 1:8.
3. the method for preparing the fibroin eutectic gel according to claim 1, wherein in the step (3):
the eutectic solvent comprises a hydrogen bond donor compound and a hydrogen bond acceptor compound;
the hydrogen bond donor compound is selected from one or more of formamide, acetamide, urea, ethylene glycol, glycerol, N-methylacetamide, oxalic acid, maleic acid, acrylic acid, methacrylic acid, acrylamide, monoethanolamine, citric acid and sorbitol;
the hydrogen bond acceptor compound is selected from one or more of halogen-containing ammonium salt, halogen-containing quaternary ammonium salt, halogen-containing phosphorus salt compound and metal halide;
the molar ratio of the hydrogen bond donor compound to the hydrogen bond acceptor compound is 0.5 to 10:1.
4. the method for preparing the fibroin eutectic gel according to claim 3, characterized in that:
the hydrogen bond donor compound is selected from ethylene glycol and/or urea, and the hydrogen bond acceptor compound is selected from choline chloride and/or zinc chloride;
the molar ratio of the hydrogen bond donor compound to the hydrogen bond acceptor compound is 2 to 4:1.
5. the method for preparing the fibroin eutectic gel according to claim 1, wherein in the step (3):
the film thickness of the prepared fibroin eutectic gel is 50 mu m-1 mm.
6. A fibroin eutectic gel prepared according to the method of any one of claims 1-5.
7. Use of the fibroin eutectic gel of claim 6 as a solid electrolyte for the preparation of an electrochemical energy storage device.
8. Use of the fibroin eutectic gel according to claim 7 for the preparation of a mechanical sensor.
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