CN117466597A - Cement-based solid electrolyte, preparation method thereof and structural supercapacitor - Google Patents
Cement-based solid electrolyte, preparation method thereof and structural supercapacitor Download PDFInfo
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- CN117466597A CN117466597A CN202311429872.5A CN202311429872A CN117466597A CN 117466597 A CN117466597 A CN 117466597A CN 202311429872 A CN202311429872 A CN 202311429872A CN 117466597 A CN117466597 A CN 117466597A
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- 239000004568 cement Substances 0.000 title claims abstract description 91
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 29
- 239000000654 additive Substances 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011268 mixed slurry Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 10
- OIWSIWZBQPTDKI-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole;hydrobromide Chemical compound [Br-].CCCC[NH+]1CN(C)C=C1 OIWSIWZBQPTDKI-UHFFFAOYSA-N 0.000 claims abstract description 5
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 claims abstract description 4
- KLFPUNSMDACYOK-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;iodide Chemical compound [I-].CCCC[NH+]1CN(C)C=C1 KLFPUNSMDACYOK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 229910021389 graphene Inorganic materials 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000007772 electrode material Substances 0.000 claims description 9
- 229920002125 Sokalan® Polymers 0.000 claims description 7
- 239000004584 polyacrylic acid Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 5
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 9
- 230000036571 hydration Effects 0.000 abstract description 4
- 238000006703 hydration reaction Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000003990 capacitor Substances 0.000 abstract description 2
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 description 19
- 239000006260 foam Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- 238000013508 migration Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- XREPTGNZZKNFQZ-UHFFFAOYSA-M 1-butyl-3-methylimidazolium iodide Chemical compound [I-].CCCCN1C=C[N+](C)=C1 XREPTGNZZKNFQZ-UHFFFAOYSA-M 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- -1 BMIMCl Chemical compound 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00844—Uses not provided for elsewhere in C04B2111/00 for electronic applications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/90—Electrical properties
- C04B2111/94—Electrically conducting materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- 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 invention discloses a cement-based solid electrolyte, a preparation method thereof and a structural supercapacitor. The preparation method of the cement-based solid electrolyte comprises the following steps: mixing cement, polymer, alkali, redox additive and water to obtain mixed slurry; placing the mixed slurry in a mould for hardening and forming, and then curing to obtain the cement-based solid electrolyte; wherein the redox additive is selected from at least one of 1-butyl-3-methylimidazole bromide, 1-butyl-3-methylimidazole chloride or 1-butyl-3-methylimidazole iodide. According to the invention, by introducing the redox additive, the cement forms pores with uniform pore diameters in the hydration process, so that the proper porosity is achieved, the number of conductive ions is increased, and the super capacitor prepared by adopting the cement-based solid electrolyte has high electronic conductivity and excellent electrochemical performance.
Description
Technical Field
The invention relates to a cement-based solid electrolyte, a preparation method thereof and a structural supercapacitor, and belongs to the technical field of electrochemical energy storage.
Background
In recent years, as the problems of energy consumption, carbon emission and the like are increasingly severe, the reduction of energy consumption and carbon emission in the building industry is urgent. According to the international energy agency data, the building is one of the world's core energy consumers, accounting for about one third of the total energy consumption, accounting for 40% of the carbon emissions. Therefore, the development of building materials (e.g., cement, concrete, brick, etc.) into large electrochemical energy storage devices is a way to achieve self-powered and green sustainable development of buildings. Through use in combination with photovoltaic panels, when illumination is sufficient, store a large amount of solar energy in structures such as building's wall and roof, can provide the electric energy for lighting system and other controllers when lack illumination. Thereby alleviating the problem of the mismatch in time and space between renewable energy and electrical power requirements.
At present, the porosity of the cement-based solid electrolyte prepared by using cement is difficult to control in the cement hydration process, and the high-concentration alkaline conductive agent also can influence the micro-void structure of the cement-based solid electrolyte, so that the porosity of the cement-based solid electrolyte is more difficult to control, and the supercapacitor adopting the cement-based solid electrolyte has the problems of low ion conductivity and poor electrochemical performance.
Disclosure of Invention
In order to solve the problems, the invention provides a cement-based solid electrolyte, a preparation method thereof and a structural supercapacitor, wherein the cement-based solid electrolyte enables cement to form pores with uniform pore diameters in the hydration process by introducing a redox additive so as to achieve proper porosity, and the number of conductive ions is increased, so that the supercapacitor prepared from the cement-based solid electrolyte has high electronic conductivity and excellent electrochemical performance.
According to a first aspect of the present invention, there is provided a method of preparing a cement-based solid electrolyte comprising the steps of:
mixing cement, polymer, alkali, redox additive and water to obtain mixed slurry;
placing the mixed slurry in a mould for hardening and forming, and then curing to obtain the cement-based solid electrolyte;
wherein the redox additive is selected from at least one of 1-butyl-3-methylimidazole bromide, 1-butyl-3-methylimidazole chloride or 1-butyl-3-methylimidazole iodide.
Optionally, the mass of the redox additive is 10% to 30% of the mass of the cement.
Optionally, the polymer is at least one of polyacrylic acid, polyacrylate or polyacrylamide, and the mass of the polymer is 1-20% of the mass of the cement.
Optionally, the alkali is at least one selected from LiOH, naOH or KOH, and the mass of the alkali is 1.4-4.2% of the mass of the cement.
Optionally, the mass of the water is 30-80% of the mass of the cement.
Optionally, the curing conditions are as follows: the temperature is 19-25 ℃, the relative humidity is more than or equal to 90 percent, and the time is 28-56 days.
According to a second aspect of the present invention, there is provided a cement-based solid electrolyte obtained according to the above-described production method, which satisfies the following conditions:
(1) The porosity is 12.5-30%;
(2) The compressive strength is 5-14 MPa;
(3) Ion conductivity of 10-80 mS cm -1 ；
(4) The internal resistance of the cement-based solid electrolyte is less than 22Ω.
According to a third aspect of the invention, a structural supercapacitor is provided, which comprises a positive electrode, a negative electrode and a solid electrolyte, wherein the positive electrode, the solid electrolyte and the negative electrode are sequentially contacted and connected in an extending direction to form a sandwich structure, and the solid electrolyte is selected from the cement-based solid electrolyte obtained by the preparation method.
Optionally, the positive electrode is selected from graphene oxide/nickel cobalt composite electrode materials, and the negative electrode is selected from graphene oxide/nickel composite electrode materials.
Optionally, the structural supercapacitor meets the following conditions:
(1) Specific capacitance > 17.50F g -1 ；
(2) At 0.1Ag -1 Under the current density, the capacitance retention rate after 1000 times of constant current charge and discharge tests is more than or equal to 80%, and the coulomb efficiency is more than or equal to 90%;
(3) The contact resistance is less than 120 omega.
According to the cement-based solid electrolyte, the redox additive is introduced to enable the cement-based solid electrolyte to form a porous network structure with the pore diameter of 20nm as a main part, the pore distribution is uniform, an ion transport channel is provided for conductive ions, and the migration rate of the conductive ions in the cement-based solid electrolyte is improved; meanwhile, ions capable of undergoing redox reaction are provided, the number of free ions is increased, the electronic conductivity is improved, and in addition, the internal resistance of the cement-based solid electrolyte is reduced by adding a redox additive. Furthermore, the structural supercapacitor prepared by adopting the cement-based solid electrolyte has high specific capacitance, excellent cycle stability and coulombic efficiency, and lower contact resistance between the electrode and the solid electrolyte.
Drawings
FIG. 1 is an SEM image of a cement-based solid electrolyte of example 1 of the present invention;
FIG. 2 is an SEM image of a cement-based solid electrolyte of example 2 of the invention;
FIG. 3 is an SEM image of a cement-based solid electrolyte of example 3 of the invention;
FIG. 4 is an SEM image of a cement-based solid electrolyte of example 4 of the invention;
FIG. 5 is an SEM image of a cement-based solid electrolyte of comparative example 1 of the present invention;
fig. 6 is the porosity of the cement-based solid electrolytes of examples 1 to 4 and comparative example 1 of the present invention;
FIG. 7 is a graph showing the cycle stability test of the structural supercapacitor prepared in example 1 of the present invention;
fig. 8 is a cycle stability test curve of the structural supercapacitor prepared in comparative example 1 of the present invention.
Detailed Description
The present invention is described in detail below with reference to examples, but the present invention is not limited to these examples.
The cement in the embodiment of the invention is Portland cement with the specification of 42.5R produced by conch cement company; the foam nickel is porous foam nickel with the thickness of 1.7mm manufactured by Tali foam metal Co., ltd; polyacrylic acid, polyacrylate, polyacrylamide, potassium hydroxide, lithium hydroxide, sodium hydroxide, 1-butyl-3-methylimidazole bromide, 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole iodide, urea, nickel nitrate hexahydrate, cobalt nitrate hexahydrate and absolute ethyl alcohol are all purchased from national chemical company of controlled-flow chemical reagent, inc., wherein the purity of 1-butyl-3-methylimidazole bromide is more than 97.0%, the purity of urea is more than 99.1%, and the concentration of absolute ethyl alcohol is 98%.
"BMIMBr" in the present invention means "1-butyl-3-methylimidazole bromide";
"BMIMCl" in the present invention represents "1-butyl-3-methylimidazole chloride";
"BMIMI" in the present invention means "1-butyl-3-methylimidazole iodide".
The ion conduction ionization and specific capacitance calculation method in the embodiment of the invention is as follows:
(1) Wherein: sigma is the ionic conductivity of the cement-based electrolyte, S.cm -1 The method comprises the steps of carrying out a first treatment on the surface of the l is the thickness of the composite electrolyte, cm; a is apparent contact area of electrolyte and electrode, cm 2 ；R b Is the bulk resistance of the composite electrolyte, Ω.
(2) Wherein: c is mass ratio capacitance, F.g -1 The method comprises the steps of carrying out a first treatment on the surface of the I is discharge current, A; m is the mass of active substances in the electrode material, g; deltaV is the voltage drop in the discharge phase, V; Δt is the discharge time, S.
According to one embodiment of the invention, the preparation method of the structural supercapacitor specifically comprises the following steps:
step 1, mixing cement, polymer, alkali, redox additive and water to obtain mixed slurry;
step 2, coating 10mg/mL graphene oxide dispersion liquid on the surface of porous foam nickel, vacuum drying at 60 ℃ for 6 hours to obtain porous foam nickel with graphene oxide loaded on the surface, and then coating the porous foam nickel with graphene oxide loaded on the surface and Co (NO) with the concentration of 2mol/L 3 ) 2 ·6H 2 O, 2mol/L Ni (NO) 3 ) 2 ·6H 2 Placing O and 0.5g of urea into a reaction kettle, reacting for 8 hours at 120 ℃, and cleaning with absolute ethyl alcohol to obtain a graphene oxide/nickel cobalt composite electrode material serving as an anode;
step 3, coating 10mg/mL graphene oxide dispersion liquid on the surface of porous foam nickel, vacuum drying at 60 ℃ for 6 hours to obtain porous foam nickel with graphene oxide loaded on the surface, placing the porous foam nickel with graphene oxide loaded on the surface, 0.5g of urea and 60mL of water into a reaction kettle, reacting for 12 hours at 180 ℃, and cleaning with absolute ethyl alcohol to obtain a graphene oxide/nickel composite electrode material serving as a negative electrode;
and 4, firstly dripping the mixed slurry prepared in the step 1 on the surfaces of the positive electrode and the negative electrode, standing for 15min at room temperature, then placing the positive electrode and the negative electrode on two sides of a die, injecting the mixed slurry into the die, hardening and forming, and then curing to obtain the structural supercapacitor.
The present invention provides Br which can undergo oxidation-reduction reaction by introducing oxidation-reduction additives such as BMIMBr, BMIMCl, BMIMI, etc. as oxidation-reduction additives - 、Cl - Or I - Can avoid OH generated by high concentration alkaline hydrolysis - The influence on the microscopic void structure of the cement-polymer matrix ensures that the cement-based solid electrolyte forms a porous network structure with the aperture of 20nm as a main part, the void distribution is uniform, an ion transport channel is provided for conductive ions, and the migration rate of the conductive ions in the cement-based solid electrolyte is improved; in addition, water is also reducedInternal resistance of the mud-based solid electrolyte. Furthermore, the structural supercapacitor prepared by adopting the cement-based solid electrolyte has high specific capacitance, excellent cycle stability and coulombic efficiency, and lower contact resistance between the electrode and the solid electrolyte.
In an embodiment, the mass of the redox additive in step S1 is 10% -30% of the mass of the cement, optionally the mass of the redox additive is any value or a range between any two values of 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30% of the mass of the cement, preferably the mass of the redox additive is 18% -25% of the mass of the cement, further preferably the mass of the redox additive is 20% -23% of the mass of the cement. By limiting the addition of the redox additive, the uniformity of the pores and the quantity of the conductive ions can be further improved, the migration rate of the conductive ions in the cement-based solid electrolyte can be improved, and the internal resistance of the cement-based solid electrolyte can be reduced. And further improves the ionic conductivity, specific capacitance and cycling stability of the structural supercapacitor prepared by adopting the cement-based solid electrolyte.
In addition, the cement-based solid electrolyte can play a plasticizing role by adding a proper amount of redox additive, so that the flexibility of the cement-based solid electrolyte is improved, and the compressive strength is properly reduced.
In an embodiment, the polymer in step S1 is at least one selected from the group consisting of polyacrylic acid, polyacrylate, and polyacrylamide, preferably, the polymer is selected from the group consisting of polyacrylic acid, and since polyacrylic acid has high solubility, it can dissolve high concentration of conductive ions as an ion conductive phase as a polymer host, and promote conductive ion migration, so that the cement-based solid electrolyte has higher ion conductivity.
In one embodiment, the mass of polymer in step S1 is 1 to 20% of the mass of the cement.
In one embodiment, the base in step S1 is selected from at least one of LiOH, naOH, or KOH.
In one embodiment, the mass of the alkali in step S1 is 2 to 3% of the mass of the cement.
In one embodiment, the mass of water in step S1 is 30-80% of the mass of the cement.
The invention can provide proper amount of conductive ions by adding proper amount of water and alkali, and further improves the ion conductivity of the cement-based solid electrolyte.
In one embodiment, the curing conditions in step S4 are: the temperature is 19-25 ℃, the relative humidity is more than or equal to 90 percent, and the time is 28-56 days.
Example 1
Step S1, 12g of polyacrylic acid and 3.36g of potassium hydroxide are dissolved in 54g of deionized water to obtain a mixed solution, 24g of BMIMBr and 120g of cement are added into the mixed solution, and the mixed solution is stirred for 2min at room temperature to obtain mixed slurry;
step S2, coating 10mg/mL graphene oxide dispersion liquid on the surface of porous foam nickel, vacuum drying at 60 ℃ for 6 hours to obtain porous foam nickel with graphene oxide loaded on the surface, and then coating the porous foam nickel with graphene oxide loaded on the surface and Co (NO) with the concentration of 2mol/L 3 ) 2 ·6H 2 O, 2mol/L Ni (NO) 3 ) 2 ·6H 2 Placing O and 0.5g of urea into a reaction kettle, and reacting for 8 hours at 120 ℃ to obtain a graphene oxide/nickel cobalt composite electrode material serving as a positive electrode;
step 3, coating 10mg/mL graphene oxide dispersion liquid on the surface of porous foam nickel, vacuum drying at 60 ℃ for 6 hours to obtain porous foam nickel with graphene oxide loaded on the surface, placing the porous foam nickel with graphene oxide loaded on the surface, 0.5g of urea and 60mL of water in a reaction kettle, and reacting for 12 hours at 180 ℃ to obtain a graphene oxide/nickel composite electrode material serving as a negative electrode;
and 4, firstly dripping the mixed slurry prepared in the step 1 on the surfaces of the positive electrode and the negative electrode, standing for 15min at room temperature, then placing the positive electrode and the negative electrode on two sides of a die, injecting the mixed slurry into the die, hardening and forming, and curing for 28 days in an environment with the relative humidity of more than 90% at 20 ℃ to obtain the structural supercapacitor.
Example 2
This example was identical to the preparation of example 1, except that BMIMBr was added in an amount of 19.2g.
Example 3
This example was identical to the preparation of example 1, except that BMIMBr was added in an amount of 30g.
Example 4
This example was identical to the preparation of example 1, except that BMIMBr was added in an amount of 36g.
Comparative example 1
This comparative example was identical to the preparation of example 1, except that BMIMBr was not added.
Test case
(1) Microstructure characterization and porosity
The microstructure and morphology of the cement-based solid electrolyte of examples 1 to 4 and comparative example 1 were analyzed by using a scanning electron microscope under an acceleration voltage of 15kv, and the test results are shown in fig. 1 to 5, and as can be seen by comparing fig. 1 and 5, respectively, the microstructure of the cement-based solid electrolyte without BMIMBr mainly comprises hydrated calcium silicate (C-S-H) gel, voids and cracks, and the microstructure with BMIMBr is loosened to distribute a larger number of small pores, thereby providing transport channels for conductive ions and water molecules, promoting migration of the conductive ions in the cement-based solid electrolyte, and accelerating transport of the conductive ions at the electrode/electrolyte interface.
The pore structure of the cement-based electrolyte slurry at 28 days was quantitatively studied using the MIP technique, as shown in fig. 6, and by comparison, the addition of BMIMBr significantly increased the porosity.
(2) Ion conductivity
The ionic conductivities of the cement-based solid electrolytes of examples 1 to 4 and comparative example 1 were calculated using Electrochemical Impedance Spectroscopy (EIS) and by formula (1), and the results are shown in table 1.
TABLE 1
From the data in table 1, it can be seen that adding BMIMBr can increase the number of free ions in the cement-based solid electrolyte, and a large number of powerful ions can enhance the mobility of carriers in the cement-based solid electrolyte, thereby increasing the ionic conductivity. It can be seen from the ionic conductivities of examples 1, 3 and 4 that an excessive amount of BMIMBr added causes a large amount of free ions to agglomerate, limiting the migration of free ions, and thus causing a decrease in ionic conductivity.
(3) Compressive Strength
The cement-based solid electrolytes of examples 1 to 4 and comparative example 1 were tested according to the chinese standard GB/T17671-2021 for compressive strength on a cement mortar strength tester (JES 300) at a loading rate of 2.4KN/s, as shown in table 2.
TABLE 2
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | |
| Compressive Strength | 11.1MPa | 11.2MPa | 11.2MPa | 11.1MPa | 14.9MPa |
From the data in Table 2, it can be seen that the addition of BMIMBr can play a certain role in plasticization, increase the non-static properties of the cement-based solid electrolyte, soften the skeleton, increase the overall flexibility of the cement-based solid electrolyte, and properly reduce the compressive strength. However, excessive BMIMBr tends to produce precipitated crystals, impeding cement hydration, forming a loose porous microstructure, resulting in a significant reduction in compressive strength.
(4) Specific capacitance
The structural supercapacitors prepared in examples 1 to 4 and comparative example 1 were respectively made at 0.05Ag -1 The specific capacitance at that time is shown in Table 3.
TABLE 3 Table 3
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | |
| Specific capacitance | 20.07F g -1 | 17.67F g -1 | 18.01F g -1 | 18.89F g -1 | 17.14F g -1 |
As can be seen from the data in table 3, the addition of BMIMBr can increase the specific capacitance of the cement solid electrolyte, but after adding too much BMIMBr, BMIMBr can produce precipitation and ion agglomeration, which hinders the progress of redox reaction.
(5) Internal resistance and contact resistance
The internal resistances of the cement-based solid electrolytes prepared in examples 1 to 4 and comparative example 1 and the contact resistances between the cement-based solid electrolytes and the electrodes were measured, respectively, as shown in table 4.
TABLE 4 Table 4
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | |
| Internal resistance of | 38.1Ω | 113.6Ω | 107.9Ω | 103Ω | 155.5 |
| Contact resistance | 5.4Ω | 21.9Ω | 20.2Ω | 18.7Ω | 25.1Ω |
From the data in table 4, it can be seen that the internal resistance of the cement-based solid electrolyte and the contact resistance between the cement-based solid electrolyte and the electrode can be significantly reduced by adding BMIMBr.
(5) Cycle stability test
Using example 1 and comparative example 1 as examples, a structured super electrode was prepared at 0.1. 0.1A g -1 At constant current density, a constant current charge-discharge test was performed 1000 times, and the specific capacitance and coulombic efficiency thereof are shown in fig. 7 and 8, respectively. According to fig. 7, after 1,000 charge-discharge cycles, the capacitance of the structural supercapacitor showed a small drop, and the capacitance retention was 83.6%. The coulomb efficiency is stable, and can reach 97.56% after 1000 times, while the capacitance retention rate is obviously reduced, and is only 72.4% after 1000 charge and discharge cycles, and the coulomb efficiency is stable and can reach 97.3% according to the graph shown in fig. 8. But sufficient to demonstrate that doping of BMIMBr gives structural capacitors with good cycling stability and coulombic efficiency.
While the invention has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the invention, and it is intended that the invention is not limited to the specific embodiments disclosed.
Claims (10)
1. A method for preparing a cement-based solid electrolyte, comprising the steps of:
mixing cement, polymer, alkali, redox additive and water to obtain mixed slurry;
placing the mixed slurry in a mould for hardening and forming, and then curing to obtain the cement-based solid electrolyte;
wherein the redox additive is selected from at least one of 1-butyl-3-methylimidazole bromide, 1-butyl-3-methylimidazole chloride or 1-butyl-3-methylimidazole iodide.
2. The method of claim 1, wherein the mass of the redox additive is 10% to 30% of the mass of the cement.
3. The method according to claim 1, wherein the polymer is at least one selected from the group consisting of polyacrylic acid, polyacrylate, and polyacrylamide, and the mass of the polymer is 1 to 20% of the mass of the cement.
4. The method according to claim 1, wherein the alkali is at least one selected from LiOH, naOH and KOH, and the mass of the alkali is 1.4 to 4.2% of the mass of the cement.
5. The method according to claim 1, wherein the mass of the water is 30 to 80% of the mass of the cement.
6. The method according to claim 1, wherein the curing conditions are: the temperature is 19-25 ℃, the relative humidity is more than or equal to 90 percent, and the time is 28-56 days.
7. A cement-based solid electrolyte obtained by the production method according to any one of claims 1 to 6, characterized in that the cement-based solid electrolyte satisfies the following condition:
(1) The porosity is 12.5-30%;
(2) The compressive strength is 5-14 MPa;
(3) Ion conductivity of 10-80 mS cm -1 ；
(4) The internal resistance of the cement-based solid electrolyte is < 22Ω.
8. A structural supercapacitor, comprising a positive electrode, a negative electrode and a solid electrolyte, wherein the positive electrode, the solid electrolyte and the negative electrode are sequentially contacted and connected in an extending direction to form a sandwich structure, and the solid electrolyte is selected from a cement-based solid electrolyte obtained by the preparation method according to any one of claims 1 to 6 or a cement-based solid electrolyte according to claim 7.
9. The structural supercapacitor of claim 8, wherein the positive electrode is selected from graphene oxide/nickel cobalt composite electrode materials and the negative electrode is selected from graphene oxide/nickel composite electrode materials.
10. The structural supercapacitor of claim 8, wherein the structural supercapacitor meets the following conditions:
(1) Specific capacitance > 17.50F g -1 ；
(2) At 0.1Ag -1 Under the current density, the capacitance retention rate after 1000 times of constant current charge and discharge tests is more than or equal to 70%, and the coulomb efficiency is more than or equal to 90%;
(3) The contact resistance is less than 120 omega.
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