CN117105612A - Cement-based structure electrolyte and preparation method thereof - Google Patents
Cement-based structure electrolyte and preparation method thereof Download PDFInfo
- Publication number
- CN117105612A CN117105612A CN202311382045.5A CN202311382045A CN117105612A CN 117105612 A CN117105612 A CN 117105612A CN 202311382045 A CN202311382045 A CN 202311382045A CN 117105612 A CN117105612 A CN 117105612A
- Authority
- CN
- China
- Prior art keywords
- cement
- electrolyte
- modified
- based structural
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004568 cement Substances 0.000 title claims abstract description 101
- 239000003792 electrolyte Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 52
- 239000010457 zeolite Substances 0.000 claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 31
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 31
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical class [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 26
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000012266 salt solution Substances 0.000 claims abstract description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 13
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 16
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 10
- 239000010881 fly ash Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical group CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 3
- AVWKSSYTZYDQFG-UHFFFAOYSA-M dimethyl-octadecyl-prop-2-enylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC=C AVWKSSYTZYDQFG-UHFFFAOYSA-M 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 229910021487 silica fume Inorganic materials 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 125000001979 organolithium group Chemical group 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229920002401 polyacrylamide Polymers 0.000 abstract description 8
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract description 7
- 230000006872 improvement Effects 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000009827 uniform distribution Methods 0.000 abstract description 2
- 239000010439 graphite Substances 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 9
- 238000004146 energy storage Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011083 cement mortar Substances 0.000 description 5
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000003469 silicate cement Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000009775 high-speed stirring Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 239000012237 artificial material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000002699 waste material 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
-
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/047—Zeolites
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/005—Halogen-containing compounds
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
-
- 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
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Civil Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention provides a cement-based structure electrolyte and a preparation method thereof, wherein the raw materials of the cement-based structure electrolyte comprise inorganic gel materials, polymer monomers, polyacrylic acid, an initiator and modified aluminosilicate zeolite, and the modified aluminosilicate zeolite is prepared by soaking the aluminosilicate zeolite in an organic silicon modified polyacrylate solution containing OH functional groups, taking out, performing heat treatment, and then soaking in a lithium salt solution; the polymer monomer is a mixture of acrylamide and long carbon chain alkyl acrylate hydrophobic monomer. According to the invention, through the synergistic hydrophobic effect of the modified aluminum-silicon zeolite and the multipolymer modified polyacrylamide, the dispersion of a polymer network in cement paste is promoted, the uniform distribution of the polymer network is facilitated, the improvement of the ionic conductivity of electrolyte is promoted, and meanwhile, the modified aluminum-silicon zeolite adsorbs a certain amount of lithium salt, so that the discharge window of the electrolyte with a cement-based structure is facilitated to be improved.
Description
Technical Field
The invention relates to the technical field of cement-based structure energy storage integrated materials, in particular to a cement-based structure electrolyte and a preparation method thereof.
Background
The cement-based material is used as a maximum artificial material, and is used in the fields of house construction, roads, bridges, airports and the like due to the advantages of wide raw material sources, excellent mechanical properties, wide application environment range and the like. With the rapid development of economy, there is an increasing demand for functionality of cement-based building materials, wherein imparting good electrical conductivity to cement-based materials has a very broad application prospect. The cement-based structural energy storage material for energy collection and health monitoring is a structural function integrated material which can realize electric energy storage and electric signal conduction on the basis of good mechanical properties of the cement-based material. For the conventional super capacitor, the conventional energy storage unit cannot avoid the defects that the energy storage unit is independent of the capacity energy storage system, and for some environments with more tense use space, the independent energy storage unit can cause space waste, so that the defects of overall weight improvement, cost rise and the like are brought. The cement-based electrolyte which can bear weight and realize quick ion conduction is prepared by combining the structure function and the energy storage function, and has important significance for better collecting and using energy and improving the self-sensing capability of the structure.
For cement-based materials, which are insulators themselves, the improvement of the ionic conductivity of the cement-based electrolyte can generally be achieved by constructing a suitable pore structure or adding a conductive medium. Prior studies have generally achieved this by adding polymers to the cement material, but the agglomeration of polymers in the cement system has limited the increase in ionic conductivity of the cement-based electrolyte.
Although the in-situ polymerization method of the cement-based electrolyte provided by the Chinese patent CN113436908A breaks through the upper limit of polymer doping, the triggering of the polymerization reaction of the cement-based electrolyte requires cement hydration to provide heat, and for some large-volume cement structures, the hydration heat release is uneven, so that the formed polymer network is uneven, and the improvement of ionic conductivity is greatly limited.
In summary, the existing polymer-based cement-based structural electrolytes still have many problems, such as uneven distribution of polymer networks, narrower discharge window, lower energy density, and poor practical application feasibility.
Disclosure of Invention
The invention aims to solve the technical problems that the existing cement-based structure electrolyte has uneven distribution of polymer network, narrow discharge window and the like, and provides the cement-based structure electrolyte based on the modified aluminosilicate, which has higher ionic conductivity, wider discharge window, faster charge and discharge speed and more cycle times.
In order to achieve the purpose, the invention adopts the following technical scheme:
the raw materials of the cement-based structure electrolyte comprise inorganic gel materials, wherein the inorganic gel materials comprise cement, the raw materials of the cement-based structure electrolyte further comprise polymer monomers, polyacrylic acid, an initiator and modified aluminum-silicon zeolite, and the mass ratio of the modified aluminum-silicon zeolite to the inorganic gel materials is 1:8-10;
the modified aluminum-silicon zeolite is prepared by soaking aluminum-silicon zeolite in an organic silicon modified polyacrylate solution containing OH functional groups, taking out, performing heat treatment, and then soaking in a lithium salt solution;
the polymer monomer is a mixture of acrylamide and long-carbon-chain alkyl acrylate hydrophobic monomers, and the mass ratio of the acrylamide to the long-carbon-chain alkyl acrylate hydrophobic monomers is 1:0.5-1.5;
the mixing amount of the polymer monomer is 1% -20% of the mass of the solid particles;
the mixing amount of the polyacrylic acid is 2-7% of the mass of the solid particles;
the mass of the solid particles is the sum of the masses of the modified aluminum-silicon zeolite and the inorganic cementing material.
In the invention, the polymer monomer is modified polyacrylamide for in-situ polymerization under the existence of an initiator and cement hydration heat release in the cement hydration process. The modified polyacrylamide is obtained by copolymerizing a long carbon chain alkyl acrylate hydrophobic monomer with a hydrophobic effect and acrylamide, and has a certain hydrophobic effect. The hydrophobic groups in the modified polyacrylamide in the cement slurry tend to associate into polymers, forming multiple hydrophobic domains, which eventually form a spatial network as the amount of polymers increases. Compared with the in-situ polymerization of acrylamide adopted in the prior patent, the polymer network formed in the cement paste tends to be in a uniform distribution state under the influence of the hydrophobic effect of the mixed monomer of the monomer with the hydrophobic group.
In the invention, the modified aluminosilicate is prepared by immersing the aluminosilicate in an organosilicon modified polyacrylate solution containing OH functional groups, wherein the surface of the aluminosilicate is covered with a layer of organosilicon modified polyacrylate, and the hydrophilicity of the aluminosilicate is also converted into hydrophobicity. Modified aluminosilicate zeolite with hydrophobic character is more beneficial to even distribution in inorganic cementing material.
According to the invention, through the synergistic hydrophobic effect of the modified aluminum-silicon zeolite and the modified polyacrylamide, two phases can be uniformly dispersed in the cement paste, a plurality of channels for ion transmission are created, and the promotion of the ion conductivity of the cement-based structure electrolyte is facilitated.
In some embodiments, the polyacrylic acid has a weight average molecular weight of 8000 to 150000.
According to some embodiments of the invention, the raw material of the cement-based structural electrolyte further comprises inorganic salt, wherein the inorganic salt accounts for 3-10% of the mass of the solid particles. Further, the inorganic salt is lithium chloride.
According to some embodiments of the invention, the lithium salt is an organolithium salt.
In some embodiments, the lithium salt is Li [ (CF) 3 SO 2 ) 2 N、Li[(FSO 2 ) 2 N、Li[(FSO 2 )(n-C 4 F 9 SO 2 ) N, or a combination of several.
In some embodiments, the heat treatment is performed at a temperature of 80-160 ℃ for a time of 2-24 hours.
In some embodiments, the mass ratio of the lithium salt solution to the aluminosilicate is 1-3: 1, wherein the concentration of the lithium salt solution is 15-25M.
In some embodiments, the solvent used for the OH functional group-containing silicone-modified polyacrylate solution is acetone. The organosilicon modified polyacrylate containing OH functional groups is BYK-SILCLEAN 3700.
In some embodiments, the solvent used for the lithium salt solution is acetonitrile.
In some embodiments, the concentration of the organosilicon modified polyacrylate solution containing OH functional groups is 0.05-1 g/L.
In some embodiments, the modified aluminosilicate is prepared by immersing the aluminosilicate in the solution of the organosilicon modified polyacrylate containing OH functionality, removing the aluminosilicate, washing, drying, heat treating, immersing in a lithium salt solution, stirring, and filtering.
In some embodiments, the washing is sequentially performed with ethanol and water, respectively; the stirring time is 10-14 h.
In some embodiments, the polymer monomer is incorporated in an amount of 4 to 20% by mass of the solid particles. Preferably, the mixing amount of the polymer monomer is 4-12% of the mass of the solid particles.
In some embodiments, the long carbon chain alkyl has a number of carbon atoms from C8 to C16. Preferably, the long carbon chain alkyl acrylate hydrophobic monomer is dodecyl acrylate.
In some embodiments, the raw materials of the cement-based structure electrolyte further comprise a cross-linking agent, wherein the cross-linking agent is one or a combination of more than one of N, N' -methylene bisacrylamide and octadecyl dimethyl allyl ammonium chloride, and the amount of the cross-linking agent accounts for 0.0001-0.001% of the amount of the polymer monomer.
In some embodiments, the mass of the initiator is 0.01-0.02% of the polymer monomer.
In some embodiments, the initiator is independently selected from one or a combination of several of ammonium persulfate, potassium persulfate and sodium persulfate.
In some embodiments, the inorganic gel material further comprises an admixture, wherein the admixture is one or a combination of more of fly ash, mineral powder and silica fume, and the cement accounts for 75-85% of the total weight of the inorganic gel material.
In some embodiments, the cement is 42.5 Portland cement.
In some embodiments, the raw material of the cement-based structured electrolyte further comprises water, wherein the water accounts for 30% -60% of the mass of the solid particles.
The mechanism for improving the discharge window in the invention: the high concentration lithium salt as electrolyte can reduce the proportion of free water, form a 'water in salt' structure, inhibit the decomposition of water, and thus can widen the voltage window.
The second technical scheme adopted by the invention is as follows: the preparation method of the cement-based structural electrolyte comprises the following steps:
(1) Mixing a polymer monomer, polyacrylic acid, inorganic salt, an initiator, a cross-linking agent and water to obtain a mixed solution;
(2) Mixing the modified aluminum-silicon zeolite with an inorganic gel material to obtain powder;
(3) And mixing the mixed liquid and the powder to obtain slurry, and then casting and curing the slurry.
In the step (3), the curing comprises steam curing and standard curing, wherein the steam curing temperature is 50-70 ℃ and the time is 20-28 h.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, through the synergistic hydrophobic effect of the modified aluminosilicate zeolite and the multipolymer modified polyacrylamide, the dispersion of the in-situ polymerized copolymer network in the cement paste is promoted, the polymer network which is uniformly distributed is formed, the improvement of the ionic conductivity of the electrolyte is promoted, meanwhile, the modified aluminosilicate zeolite adsorbs a certain amount of lithium salt, the movable ion content in the electrolyte with a cement-based structure is improved to a certain extent, the decomposition of the water in the electrolyte with the cement-based structure is inhibited, and the discharge window of the electrolyte with the cement-based structure is improved.
Detailed Description
As described in the background art, the existing polymer-based cement-based structural electrolyte has the problems of uneven distribution of a polymer network, narrow discharge window and the like, and the problems are well solved by using the synergistic modified aluminosilicate zeolite and the modified polyacrylamide. Firstly, the modified aluminum-silicon zeolite has better hydrophobicity and can be uniformly dispersed in cement paste; the modified polyacrylamide obtained by copolymerizing the long carbon chain alkyl acrylate hydrophobic monomer with the hydrophobic effect and the acrylamide also has a certain hydrophobic effect, compared with the common acrylamide in-situ polymerization, which is easily affected by uneven hydration heat release, the aggregation phenomenon is easy to occur, and the aggregation phenomenon is greatly reduced under the improvement of the hydrophobic effect by adopting the method for copolymerizing the composite hydrophobic monomer. In addition, the organic silicon modified polyacrylate carried on the modified aluminum-silicon zeolite can play a role of pulling polymers, so that polymer networks are more uniformly dispersed in cement paste, the formed polymer networks are more uniformly distributed in cement materials, the impedance of cement-based structural electrolytes is effectively reduced, and the ionic conductivity of an electrolyte system is greatly improved. Meanwhile, a certain amount of lithium salt can be carried on the modified aluminum-silicon zeolite in advance, the total amount of ions capable of freely moving in the cement-based electrolyte is increased, the decomposition of water is inhibited through a water-in-salt structure, and the discharge window of the cement-based structure electrolyte is obviously increased.
The following detailed description of the present invention is provided in connection with specific embodiments so that those skilled in the art may better understand and practice the present invention, but is not intended to limit the scope of the present invention.
The experimental methods in the following examples are conventional methods unless otherwise specified. The raw materials used in the following examples, unless otherwise specified, were commercially available products.
Example 1
The present example provides a cement-based structured electrolyte prepared by the following method:
(1) Immersing untreated 10 g aluminum-silicon zeolite in a modified liquid formed by blending 0.2 g/L of organosilicon modified polyacrylate containing OH functional groups (specifically BYK-SILCLEAN 3700) and acetone, taking out, washing with ethanol, and placing in a vacuum oven for heat preservation at 120 ℃ for 3h;
lithium salt Li [ (CF) 3 SO 2 ) 2 N is dissolved in acetonitrile to obtain 80g solution (the lithium salt concentration of the solution is 21M), then the treated aluminum-silicon zeolite is soaked in the lithium salt solution, the solution is magnetically stirred for 12h and then filtered, then ethanol is used for washing repeatedly, deionized water is used for washing, and the solution is placed in an oven for drying at 50 ℃ to obtain the modified aluminum-silicon zeolite.
(2) 5 g polyacrylic acid (weight average molecular weight 100000), 5 g lithium chloride, 10 g acrylamide, 10 g dodecyl acrylate, 0.0026 g ammonium persulfate and 0.000134 g of N, N' -methylenebisacrylamide were weighed and poured into 50 g water to be stirred uniformly, thus obtaining a uniform mixed solution A.
(3) Respectively weighing 90 g inorganic cementing materials (specifically 72 g of a mixture of 42.5 silicate cement and 18 g fly ash) and 10 g modified aluminum-silicon zeolite, pouring into a cement mortar stirrer, stirring at 250rpm for 90s, and ensuring that the powder is fully mixed to obtain powder B.
(4) The mixed solution was added to a stirring pot and stirred with powder B at 250rpm for 90s, after the stirring was stopped, the slurry of the blade and the pot wall was scraped into the middle of the pot, and then the high-speed stirring mode was switched, and stirred at 500rpm for 60s, to obtain mixture C.
(5) The obtained mixture C was taken out, put into a 20 mm ×20× 20 mm ×20 mm mold, then the conductive graphite sheet was cut into 20 mm ×20 mm pieces sized to be inserted into both ends of the block, and then put into a steam curing box to be cured at 60 ℃ for 24h.
(6) Taking out the die provided with the cured block, removing the part which is higher than the surface expansion of the die, removing the die to obtain the cement-based structure electrolyte provided with the graphite sheet electrode and based on the modified polymer and the modified aluminum-silicon zeolite, putting the prepared cement-based structure electrolyte into a cement standard curing chamber, curing for 28 days, and testing the compressive strength and the electrical property.
Example 2
The present example provides a cement-based structured electrolyte prepared by the following method:
(1) Immersing untreated 5 g aluminum-silicon zeolite in a modified liquid formed by blending 0.2 g/L BYK-SILCLEAN 3700 and acetone, taking out, cleaning with ethanol, and placing in a vacuum oven at 120 ℃ for 3h;
lithium salt Li [ (CF) 3 SO 2 ) 2 N is dissolved in acetonitrile to obtain 80g of solution (the lithium salt concentration of the solution is 21M), then the treated aluminum-silicon zeolite is soaked in the lithium salt solution, the solution is magnetically stirred for 12 hours and then filtered, then the solution is repeatedly washed by ethanol and then washed by deionized water, and the solution is dried in an oven at 50 ℃ to obtain the modified aluminum-silicon zeolite.
(2) 5 g polyacrylic acid, 5 g lithium chloride, 10 g acrylamide, 10 g dodecyl acrylate, 0.0026 g ammonium persulfate and 0.000134 g of N, N' -methylenebisacrylamide were weighed and poured into 40 g water to be stirred uniformly, thus obtaining a uniform mixed solution A.
(3) Respectively weighing 95 g inorganic cementing material (specifically 76 g of a mixture of 42.5 silicate cement and 19 g fly ash) and 10 g modified aluminum-silicon zeolite, pouring into a cement mortar stirrer, stirring at 250rpm for 90s, and ensuring that the powder is fully mixed to obtain powder B.
(4) The mixed solution was added to a stirring pot and stirred with powder B at 250rpm for 90s, after the stirring was stopped, the slurry of the blade and the pot wall was scraped into the middle of the pot, and then the high-speed stirring mode was switched, and stirred at 500rpm for 60s, to obtain mixture C.
(5) The obtained mixture C was taken out, put into a 20 mm ×20× 20 mm ×20 mm mold, then the conductive graphite sheet was cut into 20 mm ×20 mm pieces sized to be inserted into both ends of the block, and then put into a steam curing box to be cured at 60 ℃ for 24h.
(6) Taking out the die provided with the cured block, removing the part which is higher than the surface expansion of the die, removing the die to obtain the cement-based structure electrolyte provided with the graphite sheet electrode and based on the modified polymer and the modified aluminum-silicon zeolite, putting the prepared cement-based structure electrolyte into a cement standard curing chamber, curing for 28 days, and testing the compressive strength and the electrical property.
Example 3
The present example provides a cement-based structured electrolyte prepared by the following method:
(1) Immersing untreated 10 g aluminum-silicon zeolite in a modified liquid formed by blending 0.2 g/L BYK-SILCLEAN 3700 and acetone, taking out, cleaning with ethanol, and placing in a vacuum oven at 120 ℃ for heat preservation of 3h;
lithium salt Li [ (CF) 3 SO 2 ) 2 N is dissolved in acetonitrile to obtain 80g solution (the lithium salt concentration of the solution is 21M), then the treated aluminum-silicon zeolite is soaked in the lithium salt solution, the solution is magnetically stirred for 12h and then filtered, then ethanol is used for washing repeatedly, deionized water is used for washing, and the solution is placed in an oven for drying at 50 ℃ to obtain the modified aluminum-silicon zeolite.
(2) 5 g polyacrylic acid, 5 g lithium chloride, 5 g acrylamide, 5 g dodecyl acrylate, 0.0013 g ammonium persulfate and 0.000067 g of N, N' -methylenebisacrylamide were weighed and poured into 50 g water to be uniformly stirred, thereby preparing a uniform mixed solution A.
(3) Respectively weighing 90 g inorganic cementing materials (specifically 72 g of a mixture of 42.5 silicate cement and 18 g fly ash) and 10 g modified aluminum-silicon zeolite, pouring into a cement mortar stirrer, stirring at 250rpm for 90s, and ensuring that the powder is fully mixed to obtain powder B.
(4) The mixed solution was added to a stirring pot and stirred with powder B at 250rpm for 90s, after the stirring was stopped, the slurry of the blade and the pot wall was scraped into the middle of the pot, and then the high-speed stirring mode was switched, and stirred at 500rpm for 60s, to obtain mixture C.
(5) The obtained mixture C was taken out, put into a 20 mm ×20× 20 mm ×20 mm mold, then the conductive graphite sheet was cut into 20 mm ×20 mm pieces sized to be inserted into both ends of the block, and then put into a steam curing box to be cured at 60 ℃ for 24h.
(6) Taking out the die provided with the cured block, removing the part which is higher than the surface expansion of the die, removing the die to obtain the cement-based structure electrolyte provided with the graphite sheet electrode and based on the modified polymer and the modified aluminum-silicon zeolite, putting the prepared cement-based structure electrolyte into a cement standard curing chamber, curing for 28 days, and testing the compressive strength and the electrical property.
Example 4
The present example provides a cement-based structured electrolyte prepared by the following method:
(1) Immersing untreated 10 g aluminum-silicon zeolite in a modified liquid formed by blending 0.2 g/L BYK-SILCLEAN 3700 and acetone, taking out, cleaning with ethanol, and placing in a vacuum oven at 120 ℃ for heat preservation of 3h;
lithium salt Li [ (CF) 3 SO 2 ) 2 N is dissolved in acetonitrile to obtain 80g solution (the lithium salt concentration of the solution is 21M), then the treated aluminum-silicon zeolite is soaked in the lithium salt solution, the solution is magnetically stirred for 12h and then filtered, then ethanol is used for washing repeatedly, deionized water is used for washing, and the solution is placed in an oven for drying at 50 ℃ to obtain the modified aluminum-silicon zeolite.
(2) 5 g polyacrylic acid, 5 g lithium chloride, 2.5 g acrylamide, 2.5 g dodecyl acrylate, 0.00065 g ammonium persulfate and 0.0000335 g of N, N' -methylenebisacrylamide were weighed and poured into 50 g water to be stirred uniformly, thus obtaining a uniform mixed solution A.
(3) Respectively weighing 90 g inorganic cementing materials (specifically 72 g of a mixture of 42.5 silicate cement and 18 g fly ash) and 10 g modified aluminum-silicon zeolite, pouring into a cement mortar stirrer, stirring at 250rpm for 90s, and ensuring that the powder is fully mixed to obtain powder B.
(4) The mixed solution was added to a stirring pot and stirred with powder B at 250rpm for 90s, after the stirring was stopped, the slurry of the blade and the pot wall was scraped into the middle of the pot, and then the high-speed stirring mode was switched, and stirred at 500rpm for 60s, to obtain mixture C.
(5) The obtained mixture C was taken out, put into a 20 mm ×20× 20 mm ×20 mm mold, then the conductive graphite sheet was cut into 20 mm ×20 mm pieces sized to be inserted into both ends of the block, and then put into a steam curing box to be cured at 60 ℃ for 24h.
(6) Taking out the die provided with the cured block, removing the part which is higher than the surface expansion of the die, removing the die to obtain the cement-based structure electrolyte provided with the graphite sheet electrode and based on the modified polymer and the modified aluminum-silicon zeolite, putting the prepared cement-based structure electrolyte into a cement standard curing chamber, curing for 28 days, and testing the compressive strength and the electrical property.
Example 5
The cement-based structured electrolyte provided in this example is substantially the same as in example 1, except that: in step (1), the lithium salt dissolved in acetonitrile is changed into Li [ (FSO) 2 ) 2 N and Li [ (FSO) 2 )(n-C 4 F 9 SO 2 ) N is a mixture with the mass ratio of 1:1, and the concentration is kept unchanged.
Example 6
The cement-based structured electrolyte provided in this example is different from that in example 1 in that: in the step (2), octadecyl dimethyl allyl ammonium chloride is used to replace N, N' -methylene bisacrylamide.
Example 7
This example provides a cement-based structural electrolyte, substantially identical to example 1, except that: and (3) replacing the 18 g fly ash doped in the step (3) with 9 g mineral powder and 9 g silica fume.
Comparative example 1
The cement-based structured electrolyte provided in this comparative example is substantially the same as in example 1, except that: eliminating the polyacrylate modification procedure of the aluminum-silicon zeolite in the step (1);
in the step (3), 90 g inorganic cementing materials (specifically, a mixture of 72 g of 42.5 silicate cement and 18 g fly ash) and 10 g aluminum-silicon zeolite are respectively weighed, and poured into a cement mortar stirrer to be stirred at 250rpm for 90s, so that the powder is fully mixed, and the powder B is obtained.
Comparative example 2
The cement-based structured electrolyte provided in this comparative example is substantially the same as in example 1, except that: the step (1) is canceled, and the doping amount of the aluminum-silicon zeolite is reduced to 0;
in step (2), the solute water is changed from 50 to g to 40 to g;
in step (3), the amount of inorganic cement was increased from 90 g to 100 g (specifically 80g of a mixture of 42.5 portland cement and 20 g fly ash).
Comparative example 3
The cement-based structural electrolyte provided in this comparative example was substantially the same as in example 4, except that: and (3) eliminating the addition of the mixed polymer monomer and the corresponding initiator and cross-linking agent in the step (2).
The compressive strength test and the electrical property test were performed on the modified polymer and modified aluminosilicate zeolite-based cement-based structural electrolyte provided with the graphite sheet electrode prepared in each of the above examples, respectively. The compressive strength test of the electrolyte with the cement-based structure is carried out on a universal concrete tester, the electrical performance test is mainly carried out by using an electrochemical workstation to carry out alternating current impedance spectroscopy, and specific performance data are shown in table 1.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (16)
1. A cement-based structural electrolyte, the raw material of which comprises an inorganic gel material comprising cement, characterized in that: the raw materials of the cement-based structure electrolyte further comprise a polymer monomer, polyacrylic acid, an initiator and modified aluminum-silicon zeolite, wherein the mass ratio of the modified aluminum-silicon zeolite to the inorganic gel material is 1:8-10;
the modified aluminum-silicon zeolite is prepared by soaking aluminum-silicon zeolite in an organic silicon modified polyacrylate solution containing OH functional groups, taking out, performing heat treatment, and then soaking in a lithium salt solution;
the polymer monomer is a mixture of acrylamide and long-carbon-chain alkyl acrylate hydrophobic monomer, and the mass ratio of the acrylamide to the long-carbon-chain alkyl acrylate hydrophobic monomer is 1:0.5-1.5;
the mixing amount of the polymer monomer is 1% -20% of the mass of the solid particles;
the mixing amount of the polyacrylic acid is 2-7% of the mass of the solid particles;
the mass of the solid particles is the sum of the masses of the modified aluminum-silicon zeolite and the inorganic cementing material.
2. The cement-based structural electrolyte of claim 1, wherein: the mixing amount of the polymer monomer is 4-20% of the mass of the solid particles.
3. The cement-based structural electrolyte of claim 2, wherein: the mixing amount of the polymer monomer is 4-12% of the mass of the solid particles.
4. The cement-based structural electrolyte of claim 1, wherein: the carbon number of the long carbon chain alkyl is C8-C16.
5. The cement-based structural electrolyte of claim 4, wherein: the long carbon chain alkyl acrylate hydrophobic monomer is dodecyl acrylate.
6. The cement-based structural electrolyte of claim 1, wherein: the raw materials of the cement-based structure electrolyte further comprise a cross-linking agent, wherein the cross-linking agent is one or a combination of more of N, N' -methylene bisacrylamide and octadecyl dimethyl allyl ammonium chloride, and the dosage of the cross-linking agent accounts for 0.0001-0.001% of the dosage of the polymer monomer.
7. The cement-based structural electrolyte of claim 1, wherein: the mass of the initiator accounts for 0.01-0.02% of the using amount of the polymer monomer; and/or the initiator is independently selected from one or a combination of more of ammonium persulfate, potassium persulfate and sodium persulfate.
8. The cement-based structural electrolyte of claim 1, wherein: the raw materials of the cement-based structure electrolyte further comprise inorganic salt, and the inorganic salt accounts for 3-10% of the mass of the solid particles.
9. The cement-based structural electrolyte of claim 8, wherein: the inorganic salt is lithium chloride.
10. The cement-based structural electrolyte of claim 1, wherein: the lithium salt is an organolithium salt.
11. The cement-based structural electrolyte of claim 10, wherein: the lithium salt is Li [ (CF) 3 SO 2 ) 2 N、Li[(FSO 2 ) 2 N、Li[(FSO 2 )(n-C 4 F 9 SO 2 ) N, or a combination of several.
12. The cement-based structural electrolyte of claim 1, wherein: the temperature of the heat treatment is 80-160 ℃ and the time is 2-24 hours; and/or the number of the groups of groups,
the concentration of the lithium salt solution is controlled to be 15-25M;
the solvent used in the organic silicon modified polyacrylate solution containing OH functional groups is acetone;
the solvent used for the lithium salt solution is acetonitrile.
13. The cement-based structural electrolyte according to any one of claims 10 to 12, wherein: the modified aluminum-silicon zeolite is prepared by soaking the aluminum-silicon zeolite in the organic silicon modified polyacrylate solution containing OH functional groups, taking out, washing, drying, then carrying out heat treatment, soaking in the lithium salt solution, stirring and filtering, wherein the washing is respectively carried out by adopting ethanol and water in sequence; the stirring time is 10-14 h.
14. The cement-based structural electrolyte of claim 1, wherein: the inorganic gel material further comprises an admixture, wherein the admixture is one or a combination of more of fly ash, mineral powder and silica fume, and the cement accounts for 75-85% of the total weight of the inorganic gel material; and/or the number of the groups of groups,
the raw materials of the cement-based structure electrolyte further comprise water, wherein the water accounts for 30% -60% of the mass of the solid particles.
15. The cement-based structural electrolyte of claim 1, wherein: the raw materials of the cement-based structure electrolyte also comprise inorganic salt, water and a cross-linking agent, and the preparation method of the cement-based structure electrolyte comprises the following steps:
(1) Mixing a polymer monomer, polyacrylic acid, inorganic salt, an initiator, a cross-linking agent and water to obtain a mixed solution;
(2) Mixing the modified aluminum-silicon zeolite with an inorganic gel material to obtain powder;
(3) And mixing the mixed liquid and the powder to obtain slurry, and then casting and curing the slurry.
16. A method for preparing the cement-based structural electrolyte according to any one of claims 1 to 15, comprising the steps of:
(1) Mixing a polymer monomer, polyacrylic acid, inorganic salt, an initiator, a cross-linking agent and water to obtain a mixed solution;
(2) Mixing the modified aluminum-silicon zeolite with an inorganic gel material to obtain powder;
(3) And mixing the mixed liquid and the powder to obtain slurry, and then casting and curing the slurry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311382045.5A CN117105612B (en) | 2023-10-24 | 2023-10-24 | Cement-based structure electrolyte and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311382045.5A CN117105612B (en) | 2023-10-24 | 2023-10-24 | Cement-based structure electrolyte and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117105612A true CN117105612A (en) | 2023-11-24 |
| CN117105612B CN117105612B (en) | 2024-02-06 |
Family
ID=88798727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311382045.5A Active CN117105612B (en) | 2023-10-24 | 2023-10-24 | Cement-based structure electrolyte and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117105612B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117809988A (en) * | 2024-01-29 | 2024-04-02 | 济南大学 | Carbon-high belite cement-based supercapacitor and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090117259A (en) * | 2008-05-09 | 2009-11-12 | (주)콘스코 | Conductive cement composition and anticorrosive method using same |
| KR20220081709A (en) * | 2020-12-09 | 2022-06-16 | 재단법인대구경북과학기술원 | Solid Electrolyte Composition, Preparation Method thereof, and Battery Comprising the Same |
| CN114920510A (en) * | 2022-04-26 | 2022-08-19 | 东南大学 | Preparation method and application of cement-based-hydrogel composite electrolyte material |
| CN116177936A (en) * | 2023-02-08 | 2023-05-30 | 北京建筑材料科学研究总院有限公司 | In-situ polymerized inorganic synergistic modified cement-based composite material and preparation method thereof |
| CN116768561A (en) * | 2023-05-23 | 2023-09-19 | 河南理工大学 | Polymer-cement-metal salt solid electrolyte, preparation method thereof and structural energy storage device |
-
2023
- 2023-10-24 CN CN202311382045.5A patent/CN117105612B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090117259A (en) * | 2008-05-09 | 2009-11-12 | (주)콘스코 | Conductive cement composition and anticorrosive method using same |
| KR20220081709A (en) * | 2020-12-09 | 2022-06-16 | 재단법인대구경북과학기술원 | Solid Electrolyte Composition, Preparation Method thereof, and Battery Comprising the Same |
| CN114920510A (en) * | 2022-04-26 | 2022-08-19 | 东南大学 | Preparation method and application of cement-based-hydrogel composite electrolyte material |
| CN116177936A (en) * | 2023-02-08 | 2023-05-30 | 北京建筑材料科学研究总院有限公司 | In-situ polymerized inorganic synergistic modified cement-based composite material and preparation method thereof |
| CN116768561A (en) * | 2023-05-23 | 2023-09-19 | 河南理工大学 | Polymer-cement-metal salt solid electrolyte, preparation method thereof and structural energy storage device |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117809988A (en) * | 2024-01-29 | 2024-04-02 | 济南大学 | Carbon-high belite cement-based supercapacitor and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117105612B (en) | 2024-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN117105612B (en) | Cement-based structure electrolyte and preparation method thereof | |
| EP1268360B1 (en) | Conductive concrete composition | |
| CN107434378B (en) | Low-carbon environment-friendly waste asphalt mixture composite permeable mortar for sponge city and preparation method thereof | |
| CN104558369A (en) | Preparation method of amphoteric clay inhibitor with low relative molecular mass | |
| CN113683372B (en) | Magnetite-intelligent graphite complex phase conductive concrete | |
| CN114455874A (en) | Preparation method and application of conductive aggregate | |
| JPH02307853A (en) | Conductive cement composition and conductive hardening body obtained from composition thereof | |
| CN109133802B (en) | Cement-based material for adsorbing and curing chloride ions and preparation method thereof | |
| Shi et al. | Inorganic-organic composite solid electrolyte based on cement and Polyacrylamide prepared by a synchronous reaction method | |
| CN114853400A (en) | Carbon black-carbon fiber composite wave-absorbing foam concrete and preparation method thereof | |
| CN105646767A (en) | Super-absorbent-resin-type self-maintenance material for concrete and preparation method | |
| CN108329926A (en) | A kind of organic inorganic hybridization type soil waterproofing agent | |
| CN116462436A (en) | Conductive aggregate, intelligent cement composite material, and preparation method and application thereof | |
| CN108439903A (en) | A kind of Anti-pressure conducting concrete | |
| CN115159902B (en) | Rubber concrete based on modified rubber powder and preparation method thereof | |
| SU800169A1 (en) | Method of producing concrete articles | |
| CN114573261B (en) | Double-component modifier modified machine-made sand and preparation method thereof | |
| CN116768561A (en) | Polymer-cement-metal salt solid electrolyte, preparation method thereof and structural energy storage device | |
| CN107574731A (en) | A kind of preparation method for the special conducting concrete mortar of ice-melt that removes the snow | |
| CN112851245B (en) | Underwater concrete and preparation method thereof | |
| CN111423163A (en) | Regenerated graphite-cement mortar composite material and preparation method thereof | |
| CN106116238A (en) | A kind of dry powder and mortar plasticizing intensifier | |
| CN112479652A (en) | Novel autoclaved aerated concrete plate reinforcement preservative and preparation method thereof | |
| CN105645836A (en) | High-flowability anti-cracking concrete additive and preparation method thereof | |
| CN106278019B (en) | Water-based polypyrrole cement based conductive composite material, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |