CN116768561A - Polymer-cement-metal salt solid electrolyte, preparation method thereof and structural energy storage device - Google Patents
Polymer-cement-metal salt solid electrolyte, preparation method thereof and structural energy storage device Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 146
- 239000002184 metal Substances 0.000 title claims abstract description 146
- 150000003839 salts Chemical class 0.000 title claims abstract description 142
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 88
- 238000004146 energy storage Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 108
- 239000004568 cement Substances 0.000 claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000178 monomer Substances 0.000 claims abstract description 44
- 239000007800 oxidant agent Substances 0.000 claims abstract description 41
- 239000003792 electrolyte Substances 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 235000002639 sodium chloride Nutrition 0.000 claims description 155
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 50
- 230000001590 oxidative effect Effects 0.000 claims description 31
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 26
- 235000011152 sodium sulphate Nutrition 0.000 claims description 26
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 25
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 25
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 24
- 239000011398 Portland cement Substances 0.000 claims description 23
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 14
- -1 alkali metal salt Chemical class 0.000 claims description 13
- 229960001763 zinc sulfate Drugs 0.000 claims description 13
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 11
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 7
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 7
- 235000011151 potassium sulphates Nutrition 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 235000005074 zinc chloride Nutrition 0.000 claims description 7
- 239000011592 zinc chloride Substances 0.000 claims description 7
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 6
- 108010010803 Gelatin Proteins 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 229920000159 gelatin Polymers 0.000 claims description 6
- 239000008273 gelatin Substances 0.000 claims description 6
- 235000019322 gelatine Nutrition 0.000 claims description 6
- 235000011852 gelatine desserts Nutrition 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- 229940047670 sodium acrylate Drugs 0.000 claims description 6
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 6
- 229920001285 xanthan gum Polymers 0.000 claims description 6
- 239000000230 xanthan gum Substances 0.000 claims description 6
- 229940082509 xanthan gum Drugs 0.000 claims description 6
- 235000010493 xanthan gum Nutrition 0.000 claims description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 4
- 125000002734 organomagnesium group Chemical group 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 4
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 12
- 239000003469 silicate cement Substances 0.000 description 10
- 230000007423 decrease Effects 0.000 description 8
- 230000003993 interaction Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- 230000009286 beneficial effect Effects 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
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- 230000000979 retarding effect Effects 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Conductive Materials (AREA)
Abstract
The application belongs to the technical field of solid electrolytes, and particularly relates to a polymer-cement-metal salt solid electrolyte, a preparation method thereof and a structural energy storage device. The polymer-cement-metal salt solid electrolyte comprises the following raw materials: cement, aqueous polymer, metal salt and water; the aqueous polymer may be replaced with a polymer monomer and an oxidizing agent. The polymer-cement-metal salt electrolyte of the application has a wide voltage window), high ionic conductivity, high compressive strength, porous structure, large specific surface area (10 ‑3 ～10m 2 g ‑1 ) And the components are tightly combined with each other. Meanwhile, the preparation method of the polymer-cement-metal salt electrolyte has low requirements on production equipment and personnel, short production period and low production cost, and the whole process does not generate three wastes and does not influence the environment.
Description
Technical Field
The application belongs to the technical field of solid electrolytes, and particularly relates to a polymer-cement-metal salt solid electrolyte, a preparation method thereof and a structural energy storage device.
Background
The efficient and safe energy storage technology can solve the problem of unbalanced electric power and electricity quantity between renewable energy power generation and electric loads such as wind/light, so that renewable energy sources are fully utilized, and further the realization of energy conservation and emission reduction demarcation targets is promoted. The structural energy storage device is a novel spatial distributed energy storage device, has energy storage and structural functions, and can be embedded into various structural bodies to realize energy conversion and storage. Cement is a cementing material of concrete, the cement yield and consumption in China are newly created in recent years, a large amount of formed buildings can provide huge volume for embedded electrode materials, and after the cement is hardened, the cement can be used as solid electrolyte to realize internal charge migration, so that the energy storage device based on the cement structure is expected to be constructed. However, cement-based energy storage devices have a lower energy density than energy storage devices such as lithium ion batteries. The research on how to improve the performance of cement-based energy storage devices is mainly focused on the ion conductivity/compressive strength of cement-based electrolytes, which is a key to promote the wide application of the cement-based energy storage devices in the energy storage field.
At present, the prepared cement-based solid state electrolysis mainly comprises the following steps: (1) The polymer-magnesium phosphate cement compound has the defects of over-fast setting, large brittleness, poor shock resistance and the like; (2) Silicate cement, a curing agent and a carbon nanomaterial are mixed to improve the conductivity of the electrolyte, but the carbon nanomaterial with high specific surface area often has high surface energy, is difficult to uniformly disperse in the cement, and leads to low conductivity of the electrolyte;
(3) The additives such as salt, plasticizer, silica powder and the like are added into the cement, but the current output and the service life are still obviously different from those of the traditional energy storage device, the inorganic solid electrolyte is in point-to-point contact with the electrode material, the poor contact performance leads to the formation and expansion of cracks under the stress change, and the polarization problem of the electrolyte/electrode interface is also caused; (4) The polymer-cement-alkali electrolyte, while improving the interfacial contact problem, has a narrower voltage window, resulting in a lower device energy density.
Accordingly, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The application aims to provide a polymer-cement-metal salt solid electrolyte, a preparation method thereof and a structural energy storage device.
In order to achieve the above object, the present application provides the following technical solutions: a polymer-cement-metal salt solid electrolyte, the polymer-cement-metal salt solid electrolyte comprising: cement, aqueous polymer, metal salt and water; the aqueous polymer may be replaced with a polymer monomer and an oxidizing agent; the mass ratio of the cement to the water-based polymer to the metal salt to the water is (20-70): (0.2-35): (0.2-10): (10-50); or the mass ratio of the cement to the polymer monomer to the oxidant to the metal salt to the water is (20-70), 0.2-35, 0.5-10, 0.2-10 and 10-50.
Preferably, the cement is portland cement; the portland cement is at least one of 42.5, 42.5R, 52.5R, 62.5 and 62.5R grade portland cement.
Preferably, the aqueous polymer is at least one of polyacrylamide, polyvinyl alcohol, polyacrylic acid, sodium polyacrylate, polyethylene oxide, gelatin, and xanthan gum; the polymer monomer is at least one of acrylamide, acrylic acid, sodium acrylate and ethylene oxide; the mass purity of the aqueous polymer is more than or equal to 95 percent.
Preferably, the aqueous polymer is polyvinyl alcohol; the polymer monomer is acrylamide or acrylic acid.
Preferably, the oxidant is at least one of ammonium persulfate, potassium persulfate and ferric trichloride hexahydrate; the mass purity of the oxidant is more than or equal to 95 percent.
Preferably, the metal salt is at least one of lithium sulfate, lithium chloride, lithium triflate, sodium sulfate, sodium chloride, sodium triflate, potassium chloride, potassium sulfate, zinc chloride, aluminum sulfate, aluminum chloride, aluminum nitrate, organomagnesium chloroaluminate, and magnesium borate; the mass purity of the metal salt is more than or equal to 95 percent.
Preferably, the metal salt is an alkali metal salt.
Preferably, the alkali metal salt is at least one of triflate, sulfate and hydrochloride.
More preferably, the metal salt is at least one of lithium triflate, sodium triflate, lithium chloride, sodium chloride, zinc chloride, sodium sulfate, potassium sulfate, and zinc sulfate.
Preferably, the polymer-cement-metal salt solid electrolyte has a voltage window of 1 to 4.5V and an ion conductivity of 5 to 75mS cm -1 Compressive strength of 10-52MPa and pore volume of 10 -4 ～10 -1 cm 3 g -1 A specific surface area of 10 -3 ～10m 2 g -1 。
The application also provides a preparation method of the polymer-cement-metal salt solid electrolyte, which adopts the following technical scheme: a method of preparing a polymer-cement-metal salt solid electrolyte as described above comprising the steps of: uniformly mixing the cement, the water-based polymer, the metal salt and the water; or alternatively, the first and second heat exchangers may be,
uniformly mixing the polymer monomer, the metal salt and water to obtain a mixed solution; adding cement into the mixed solution and uniformly mixing to obtain slurry; and adding an oxidant into the slurry, and uniformly mixing.
The application also provides a structural energy storage device, which adopts the following technical scheme: a structural energy storage device employing a polymer-cement-metal salt solid state electrolyte as described above.
The beneficial effects are that:
the polymer-cement-metal salt electrics of the applicationThe electrolyte has a wide voltage window (1-4.5V), high ion conductivity (5-5 mS cm) -1 ) High compressive strength (10-52 MPa), porous structure (pore volume 10) -4 ～10 -1 cm 3 g -1 ) Large specific surface area (10) -3 ～10m 2 g -1 ) And the components are tightly combined with each other. Meanwhile, the preparation method of the polymer-cement-metal salt electrolyte has low requirements on production equipment and personnel, short production period and low production cost, and the whole process does not generate three wastes and does not influence the environment.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. Wherein:
FIG. 1 is a flow chart of a method for preparing a polymer-cement-metal salt solid electrolyte according to an embodiment of the present application;
fig. 2 is a flow chart of a method for preparing a polymer-cement-metal salt solid electrolyte according to another embodiment of the present application.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the application, fall within the scope of protection of the application.
The present application will be described in detail with reference to examples. It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other.
Aiming at the problem of low ionic conductivity and/or compressive strength of the existing cement-based electrolyte, the application provides a polymer-cement-metal salt solid electrolyte, which comprises the following raw materials: portland cement, an aqueous polymer, a metal salt, and water; wherein the aqueous polymer is replaceable with the polymer monomer and the oxidizing agent; the mass ratio of cement, aqueous polymer, metal salt and water is (20-70): (0.2-35): (0.2-10): (10-50) (for example, the mass ratio of cement, aqueous polymer, metal salt and water is 20:0.2:0.2:10, 20:0.2:1:20, 40:25:5:30, 40:25:5:20 or 70:35:10:50); the mass ratio of cement, polymer monomer, oxidant, metal salt and water is (20-70): 0.2-35): 0.5-10): 0.2-10): 10-50 (e.g., the mass ratio of cement, polymer monomer, oxidant, metal salt and water is 20:0.2:0.5:0.2:10, 20:1:3:2:15, 40:15:12:5:30, 40:20:8:5:25 or 70:35:10:10:50). When the polymer monomer is adopted, the polymer monomer can be polymerized on the cement surface in situ, and interact with the metal salt in a hydrogen bond, coordination complexing mode and the like, so that the metal salt has stronger migration capability in the solid electrolyte, and the conductivity of the solid electrolyte is increased; when the polymer is adopted, cement and the polymer interact in an intercalation mode, so that the contact performance of the electrode/electrolyte can be improved, and the construction of the cement-based solid-state energy storage device is facilitated. Too high cement, polymer monomer, too low metal salt content can result in poor electrolyte ionic conductivity; too high polymer monomer, metal salt and too low cement result in low compressive strength; too low a metal salt content results in a narrower voltage window.
In a preferred embodiment of the application, the mass ratio of cement, aqueous polymer, metal salt and water is 40 (0.2-12.8): (0.2-3.75): 16 (e.g., 40:0.2:0.2:16, 40:2:1:16, 40:5:2:16 or 40:12.8:3.75:16); the mass ratio of cement, polymer monomer, oxidant, metal salt and water is 40 (0.2-12.8): (0.75-3): (0.2-3.75): 16 (e.g., 40:0.2:0.75:0.2:16, 40:2:2:1:16, 40:5:1.5:3:16, 40:8:2.75:3:16 or 40:12:3:3.75:16).
In a preferred embodiment of the application, the cement is Portland cement. More preferably, the portland cement is at least one of 42.5, 42.5R, 52.5R, 62.5 and 62.5R grade portland cement. As the cement strength increases, the electrode/electrolyte contact performance decreases, but the compressive strength increases. The silicate cement has higher compressive strength and flexural strength, is beneficial to the structural function of the structural energy storage device, and meets the requirements of the structural energy storage field.
In a preferred embodiment of the present application, the aqueous polymer is at least one of polyacrylamide, polyvinyl alcohol, polyacrylic acid, sodium polyacrylate, polyethylene oxide, gelatin, and xanthan gum; the polymer monomer is at least one of acrylamide, acrylic acid, sodium acrylate and ethylene oxide; the mass purity of the aqueous polymer is more than or equal to 95 percent. The purity of the aqueous polymer monomer determines the purity and physicochemical properties of the aqueous polymer after polymerization, and thus greatly affects the ionic conductivity and compressive strength of the polymer-cement-metal salt solid electrolyte, thus limiting the purity of the aqueous polymer monomer.
In a preferred embodiment of the application, the aqueous polymer is polyvinyl alcohol; the polymer monomer is acrylamide or acrylic acid.
In a preferred embodiment of the application, the oxidant is at least one of ammonium persulfate, potassium persulfate and ferric trichloride hexahydrate; the mass purity of the oxidant is more than or equal to 95 percent. The oxidant can polymerize the polymer monomer, and the oxidant with lower purity is easy to introduce impurities which cannot be removed into the polymer-cement-metal salt electrolyte, so that various properties of the polymer-cement-metal salt solid electrolyte are affected, and the purity of the oxidant is limited.
In a preferred embodiment of the present application, the metal salt is at least one of lithium sulfate, lithium chloride, lithium triflate, sodium sulfate, sodium chloride, sodium triflate, potassium chloride, potassium sulfate, zinc chloride, aluminum sulfate, aluminum chloride, aluminum nitrate, organomagnesium chloroaluminate, and magnesium borate; the mass purity of the metal salt is more than or equal to 95 percent. The metal salt is used as a main carrier for ion conduction in the solid electrolyte, and the excessively low purity and excessive impurities are easy to cause the reduction of the electrical and mechanical properties of the solid electrolyte, so that the purity of the oxidant is limited.
In a preferred embodiment of the application, the metal salt is an alkali metal salt.
In a preferred embodiment of the present application, the alkali metal salt is at least one of triflate, sulfate and hydrochloride.
In a preferred embodiment of the present application, the alkali metal salt is at least one of triflate, sulfate and hydrochloride.
In a preferred embodiment of the present application, the metal salt is at least one of lithium triflate, sodium triflate, lithium chloride, sodium chloride, zinc chloride, sodium sulfate, potassium sulfate and zinc sulfate.
In a preferred embodiment of the present application, the polymer-cement-metal salt solid electrolyte has a voltage window of 1 to 4.5V and an ionic conductivity of 5 to 75mS cm -1 Compressive strength of 10-52MPa and pore volume of 10 -4 -10 -1 cm 3 g -1 A specific surface area of 10 -3 -10m 2 g -1 。
The application also provides a preparation method of the polymer-cement-metal salt solid electrolyte, as shown in figures 1-2, the preparation method of the embodiment of the application comprises the following steps: mixing cement, water-based polymer, metal salt and water uniformly; or alternatively, the first and second heat exchangers may be,
uniformly mixing a polymer monomer, metal salt and water to obtain a mixed solution; adding cement into the mixed solution and uniformly mixing to obtain slurry; and adding an oxidant into the slurry, and uniformly mixing.
The application also provides a preferable embodiment of a preparation method of the polymer-cement-metal salt solid electrolyte, which comprises the following steps: (1) Sequentially adding the water-based polymer, the metal salt and water, and uniformly stirring to form a solution; (2) Adding cement into the solution treated in the step (1), and stirring to obtain the polymer-cement-metal salt solid electrolyte or the preparation method of the polymer-cement-metal salt solid electrolyte comprises the following steps: I. uniformly stirring metal salt, water and polymer monomer to form a solution; II, adding cement into the solution treated in the step I, and rapidly stirring to form uniform slurry; and III, adding an oxidant into the slurry obtained by the treatment in the step II, and fully stirring to obtain the polymer-cement-metal salt solid electrolyte.
The application also provides a structural energy storage device, and the structural energy storage device of the embodiment of the application adopts the polymer-cement-metal salt solid electrolyte.
The polymer-cement-metal salt solid electrolyte, the method for preparing the same and the structural energy storage device according to the present application are described in detail below by way of specific examples.
In the following examples: the Portland cement used is 42.5-grade Portland cement;
the aqueous polymer (polyacrylamide (relative molecular weight of acrylamide monomer: 71.08, analytical grade), polyacrylic acid (molecular weight: 3000-5000, analytical grade), sodium polyacrylate (average molecular weight: 500-700, 80 mesh), polyethylene oxide (average molecular weight: 600-600 ten thousand, analytical grade)) is synthesized by polymerizing monomers through an oxidizing agent (ammonium persulfate (molecular weight: 228.20, analytical grade), potassium persulfate (molecular weight: 270.32, purity: 99%), ferric trichloride hexahydrate (relative molecular weight: 270.30, analytical grade), by uniformly stirring in an aqueous solution at room temperature (25 ℃), gradually adding 3g of an oxidizing agent powder (adding time of about 30 s) and magnetically stirring at 400r/min for 30 min, the polymer monomer is commercially available powder polymer monomer (acrylamide, acrylic acid, sodium acrylate, ethylene oxide) and the mass purity is 95% or more.
The water-based polymer (gelatin and xanthan gum) is commercial powder water-based polymer, and the mass purity of the water-based polymer is more than 95%.
The oxidant (ammonium persulfate, potassium persulfate and ferric trichloride hexahydrate) is a commercial powder oxidant, and the mass purity of the oxidant is more than 95%.
The metal salt (lithium sulfate, lithium chloride, lithium triflate, sodium sulfate, sodium chloride, sodium triflate, potassium chloride, potassium sulfate, zinc chloride, aluminum sulfate, aluminum chloride, aluminum nitrate, organomagnesium chloroaluminate and magnesium borate) is commercial powder metal salt, and the mass purity is more than 95%.
Example 1
The polymer-cement-metal salt solid electrolyte of the present embodiment comprises the following raw materials: 42.5 Portland cement 160g, zinc sulfate 15g, water 64g and Water-based Polymer (Polyacrylamide, polyvinyl alcohol, polyacrylic acid, sodium polyacrylate, polyethylene oxide, gelatin, xanthan gum) 32g;
among them, the aqueous polymer was replaced with 32g of polymer monomer (acrylamide, acrylic acid, sodium acrylate, ethylene oxide) and 3g of ammonium persulfate. The details are shown in table 1 below.
Referring to fig. 2, when an aqueous polymer is used as a raw material, the method for preparing a polymer-cement-metal salt solid electrolyte of the present embodiment includes the steps of: (1) Sequentially adding water-based polymer (polyacrylamide, polyvinyl alcohol, polyacrylic acid, sodium polyacrylate, polyethylene oxide, gelatin and xanthan gum), metal salt (zinc sulfate) and water, and stirring uniformly to form a solution; (2) And (3) adding cement (42.5 silicate cement) into the solution treated in the step (1), and rapidly stirring to obtain the polymer-cement-metal salt solid electrolyte.
Referring to fig. 1, when a polymer monomer is used as a raw material, the method for preparing a polymer-cement-metal salt solid electrolyte of the present embodiment includes the steps of: I. uniformly stirring metal salt (zinc sulfate), water and polymer monomer (acrylamide, acrylic acid, sodium acrylate and ethylene oxide) to form a solution; adding cement (42.5 silicate cement) into the solution treated in the step I, and rapidly stirring to form uniform slurry; and III, adding an oxidant (ammonium persulfate) into the slurry obtained by the treatment in the step II, and fully stirring to obtain the polymer-cement-metal salt solid electrolyte.
Curing the polymer-cement-metal salt solid electrolyte of this example: curing for 28 days in an environment (even indoor temperature and humidity) with the relative humidity of more than 95 percent and the temperature of 20+/-2 ℃.
The mechanical properties and electrical properties of the polymer-cement-metal salt solid electrolyte obtained by curing 28d in this example were examined.
Wherein, the voltage window carries out open-circuit voltage test on the solid electrolyte through an electrochemical workstation, and the positive and negative plates adopt MnO loaded by foam nickel 2 And Zn; ion conductivity was tested by ac impedance of the electrochemical workstation; compressive Strength the cement is passed through a cement flexural compression tester at a speed of 2.4kN/sTesting; pore structure and specific surface area were tested by nitrogen adsorption.
The test results are shown in table 1 below:
TABLE 1 influence of aqueous Polymer species on the mechanical/electrical Properties of solid electrolytes
Note that: the "-" in the table is that the experiment fails to stir due to water absorption by the polymer, and that the solid electrolyte material cannot be made nor performance tested.
As can be seen from table 1, the polymer-cement-metal salt solid state electrolyte formed by polymerization of the polymer monomer has higher ionic conductivity and compressive strength than the polymer-cement-metal salt solid state electrolyte formed by directly adding the aqueous polymer. Furthermore, under the same kind of metal salt, oxidant, cement conditions, different kinds of aqueous polymers have a great influence on ionic conductivity and compressive strength, which may be related to the complex interactions of the functional groups carried by the aqueous polymer with cement, metal salt. The difference in pore volume and specific surface area of the electrolyte is due to the difference in polymers, possibly because the influence of the polymers on the cement hydration process is different. The polymer has smaller pore volume and specific surface area than if it were homogeneously contacted with the hydration product via monomer polymerization, possibly because of the heterogeneous coating resulting in more pores and more surface. In addition, in certain positive and negative plates, the voltage of the device is also affected by the electrolyte. And, if decoupling of ion conductivity and compressive strength is taken into consideration, the optimal composition of the raw material of the solid electrolyte of this example is No. 8, that is, the polymer monomer is acrylamide, the mixing amount of 42.5 Portland cement is 160g, the mixing amount of water is 64g, the mass of ammonium persulfate is 3g, and the mass of zinc sulfate is 15g. If the voltage window is considered, the optimal composition of the raw material of the solid electrolyte of this example is No. 11, i.e., the polymer monomer is ethylene oxide, the mixing amount of 42.5 Portland cement is 160g, the mixing amount of water is 64g, the mass of ammonium persulfate is 3g, and the mass of zinc sulfate is 15g. In practical use, the solid electrolyte may be selected according to different requirements.
Example 2
The polymer-cement-metal salt solid electrolyte of this example was prepared from 32g of polymer monomer (acrylamide), 160g of 42.5 Portland cement, 64g of water, 3g of ammonium persulfate and 15g of metal salt.
The polymer-cement-metal salt solid electrolyte of this example was prepared in the same manner as in example 1.
The mechanical/electrical property test method of the polymer-cement-metal salt solid electrolyte prepared by the raw material ratio of the polymer-cement-metal salt solid electrolyte of this example is the same as that of example 1, and the test results are shown in the following table 2:
TABLE 2 mechanical/electrical Properties of Polymer-Cement-Metal salt solid electrolyte prepared with different Metal salts
As can be seen from Table 2, under the same kind of aqueous polymer monomer, oxidant, cement conditions, the influence of different kinds of metal salts on ionic conductivity and compressive strength is great, which may be related to the complex interactions of anions and cations of metal salts with cement, polymers, such as Cl - 、NO 3 - Often causes the compressive strength of cement to be reduced, mg 2+ 、Al 3+ The interactions with the polymer may be weak, resulting in poor ionic conductivity, alkali metal cations Li + 、Na + 、K + In the case where the metal salt is a sodium salt, both the ionic conductivity and the compressive strength are high. The electrolyte has a difference in pore volume and specific surface area due to the different kinds of metal salts, which may be because the influence of metal salts on the cement pore structure is different. And, if decoupling of ionic conductivity and compressive strength is considered, the present embodimentThe optimal composition of the raw materials of the solid electrolyte of the example is No. 9, namely 32g of polymer monomer acrylamide, 160g of 42.5 silicate cement, 64g of water, 3g of ammonium persulfate and 15g of metal salt zinc sulfate. The suboptimal composition of the raw material for the solid electrolyte of this example is number 4. If the voltage window is considered, the optimal composition of the raw material of the solid electrolyte of the embodiment is No. 6, namely, the polymer monomer is acrylamide, the mixing amount of 42.5 silicate cement is 160g, the mixing amount of water is 64g, the mass of ammonium persulfate is 3g, and the mass of sodium triflate is 15g. In practical use, the solid electrolyte may be selected according to different requirements.
Example 3
The polymer-cement-metal salt solid electrolyte of the present embodiment comprises the following raw materials: the mixing amount of the 42.5 Portland cement is 40g, the amount of the water-based polymer polyvinyl alcohol is not fixed, the mixing amount of the water-based polymer polyvinyl alcohol is 0%,0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% and 5% of the Portland cement, the mixing amount of water is 16g, the mass of ammonium persulfate is 0g, and the mass of sodium sulfate is 1g.
The polymer-cement-metal salt solid electrolyte of this example was prepared in the same manner as in example 1.
The positive and negative electrode materials used in this embodiment are NaTi 2 (PO 4 ) 3 The mechanical/electrical property test method of this example is the same as that of example 1 except for the positive and negative electrode materials, and the amounts of each raw material in the polymer-cement-metal salt solid electrolyte of this example and the corresponding mechanical/electrical property data are shown in table 3:
TABLE 3 influence of the amount of aqueous Polymer on the mechanical/electrical Properties of solid electrolyte
Note that: in the table, "-" is that the experiment cannot be carried out because the polymer absorbs water, so that the dissolution of metal salt and the addition of cement are not carried out, and the solid electrolyte material cannot be made, and the performance test cannot be carried out.
As can be seen from table 3, after fixing the kinds of the aqueous polymer, metal salt, oxidant, cement, the added amount of the aqueous polymer has a great influence on the ion conductivity and compressive strength, and as the amount of the aqueous polymer polyvinyl alcohol increases, the ion conductivity tends to increase and decrease first, which may be related to the interaction of the polyvinyl alcohol with cement, metal salt; the compressive strength tends to decrease gradually, probably because polyvinyl alcohol can react with C-S-H gel, ca (OH) in cement 2 Gel interactions, small amounts of polyvinyl alcohol have less impact on the compressive strength of the cement, but excessive amounts of polyvinyl alcohol lead to gradual decreases in strength. The solid electrolyte of this example had excellent raw material properties, and had the compositions of No. 5 and 6, no. 5 being 6.4g of polymer polyvinyl alcohol, 40g of 42.5 Portland cement, 16g of water, 0g of ammonium persulfate, and 1g of sodium sulfate metal salt. No. 6 is 8g of polymer polyvinyl alcohol, the mixing amount of 42.5 silicate cement is 40g, the mixing amount of water is 16g, the mass of ammonium persulfate is 0g, and the mass of metal salt sodium sulfate is 1g.
Example 4
The polymer-cement-metal salt solid electrolyte of the present embodiment comprises the following raw materials: 42.5 Portland cement 40g, water polymer polyvinyl alcohol 3.2g, ammonium persulfate 0g, water 16g, sodium sulfate 0, 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, 2, 3, 4g.
The polymer-cement-metal salt solid electrolyte of this example was prepared in the same manner as in example 1.
The mechanical/electrical property test method of this example is the same as that of example 3, and the amounts of the respective raw materials in the solid electrolyte of this example and the corresponding mechanical/electrical property data are shown in table 4:
TABLE 4 influence of the amount of the metal salt on the mechanical/electrical properties of the solid electrolyte
Note that: because the sodium sulfate is too much, the water is less, the sodium sulfate is easy to separate out, and whether the sodium sulfate is completely dissolved cannot be determined, the influence of the content of the sodium sulfate on the performance cannot be determined
As can be seen from table 4, after fixing the kinds of the aqueous polymer, metal salt, oxidant, cement, the addition amount of the metal salt has a certain influence on the ionic conductivity, compressive strength, voltage, pore structure, and as the metal salt sodium sulfate increases, the ionic conductivity tends to increase first and then to remain almost unchanged, probably because the metal salt is insoluble due to the addition of excessive metal salt, and therefore cannot influence the ionic conductivity beyond a certain limit; likewise, the voltage is kept unchanged after the metal salt is increased continuously; the compressive strength tends to decrease gradually, probably because a small amount of sodium sulfate, although it can be used as an early strength agent, once too much, causes the strength to decrease gradually. The pore structure remains substantially unchanged and then increases gradually, probably because of the influence of the metal salt on the hydration product, resulting in the appearance of more mesopores and micropores. The solid electrolyte of this example had excellent raw material properties of No. 5 to 10, i.e., 3.2g of polymer polyvinyl alcohol, 40g of 42.5 silicate cement, 16g of water, 3.2g of ammonium persulfate, and 0.8 to 1.8g of sodium sulfate as metal salt.
Example 5
The preparation method of the polymer-cement-metal salt solid electrolyte of this example was the same as that of example 3 except for the amounts of acrylamide and sodium sulfate (cement admixture 40g, sodium sulfate admixture 2g, ammonium persulfate admixture 0.75g, water admixture 16 g).
TABLE 5 influence of the amount of aqueous Polymer on the mechanical/electrical Properties of solid electrolyte
Note that: in the table, "-" is that the cement block cannot be completely coagulated after 28 days of curing due to excessive polymer, and the solid electrolyte material cannot be made and the performance test cannot be performed.
As can be seen from table 5, after fixing the kinds of the aqueous polymer, metal salt, oxidant, cement, the added amount of the aqueous polymer has a great influence on the ion conductivity and compressive strength, and as the amount of the acrylamide polymerized in situ increases, the ion conductivity tends to increase and decrease first, which may be related to the interaction of the polyacrylamide with the cement, metal salt; the compressive strength tends to increase and then decrease. The solid electrolyte of this example had excellent raw material properties (voltage, compressive strength, and ion conductivity) and had compositions of No. 4 and 5, no. 4 being 6g of acrylamide, 40g of 42.5 Portland cement, 16g of water, 0.75g of ammonium persulfate, and 2g of sodium sulfate metal salt. No. 5 is 8g of acrylamide, the mixing amount of 42.5 silicate cement is 40g, the mixing amount of water is 16g, the mass of ammonium persulfate is 0.75g, and the mass of sodium sulfate metal salt is 2g.
Example 6
The preparation method of the polymer-cement-metal salt solid electrolyte of this example was the same as that of example 3 except for the amounts of polymer acrylamide and zinc sulfate (42.5 Portland cement 40g, acrylamide 12g, ammonium persulfate 3g, and water 16 g).
TABLE 6 influence of the amount of the metal salt on the mechanical/electrical properties of the solid electrolyte
Note that: in the table, "-" is that the cement block cannot be completely coagulated after 28 days of curing due to excessive polymer, and the solid electrolyte material cannot be made and the performance test cannot be performed.
It can be seen from table 6 that after fixing the kinds of the aqueous polymer, metal salt, oxidant and cement, the added amount of metal salt zinc sulfate has a certain influence on ion conductivity, compressive strength, voltage and pore structure, and is similar to sodium sulfate in law, but the pore structure is basically kept unchanged, and when the amount of zinc sulfate is more than 2g, the cement block cannot be coagulated due to the retarding effect, so that the pore structure cannot be tested. In addition, the excellent raw material performance of the solid electrolyte of the embodiment is provided with the composition of No. 7-11, namely 12g of polymer polyvinyl alcohol, 40g of 42.5 silicate cement, 16g of water, 3g of ammonium persulfate and 1.2-2g of metal salt zinc sulfate.
Example 7
This embodiment differs from embodiment 2 only in that: acrylic acid is used as a monomer; the remaining homogeneous example 2 was kept consistent (32 g of acrylic acid, 160g of 42.5 Portland cement, 64g of water, 3g of ammonium persulfate and 15g of metal salt).
TABLE 7 mechanical/electrical Properties of Polymer-Cement-Metal salt solid electrolyte prepared with different Metal salts
Compared with acrylamide, the acrylic acid has weaker interaction with metal ions, so that the voltage, compressive strength and ionic conductivity of the acrylic acid are lower than those of the electrolyte when the acrylamide is used, but the acrylic acid still has certain interaction with cement and can be combined with the cement through intercalation, and the pore structure and specific surface area of the acrylic acid are similar to those of the electrolyte when the acrylamide is used.
Example 8
This embodiment differs from embodiment 1 only in that: the metal salt is sodium sulfate, and the polymer monomer is acrylamide, acrylic acid and ethylene oxide; the remainder was the same as in example 1 (i.e., the amount of the polymer monomer blended was 32g, the amount of cement blended was 160g, the amount of sodium sulfate blended was 15g, the amount of ammonium persulfate blended was 3g, and the amount of water blended was 64 g).
The results of the mechanical/electrical property test of the polymer-cement-metal salt solid electrolyte prepared in this example are shown in table 8 below.
Comparative example 1
This comparative example differs from example 8 only in that: the order of addition of the oxidizing agent is different; the remainder remained the same as in example 1.
Specifically, the preparation method of the solid electrolyte of the present comparative example includes the steps of: I. uniformly stirring metal salt (sodium sulfate), water and polymer monomer (acrylamide, acrylic acid and ethylene oxide) to form a solution; II, adding an oxidant (ammonium persulfate) into the solution treated in the step I; and III, adding cement into the slurry obtained by the treatment in the step II, and fully stirring to obtain the polymer-cement-metal salt solid electrolyte.
The results of the mechanical/electrical property test of the solid electrolyte prepared in this comparative example are shown in table 8 below.
Table 8 comparison of solid state electrolyte mechanical/electrical properties of example 8 and comparative example 1
As can be seen from Table 8, the order of addition of the oxidizing agent has a certain influence on the ionic conductivity, compressive strength, voltage, and pore structure, and when the oxidizing agent is added first, the conductivity, compressive strength, and voltage of the electrolyte are lower than those of the electrolyte when the oxidizing agent is added later, but the pore volume and specific surface area are higher. Considering the application of the electrolyte in the energy storage field, the later addition of the oxidant is more beneficial to the application of the cement-based solid electrolyte in the energy storage field.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A polymer-cement-metal salt solid electrolyte, characterized in that the polymer-cement-metal salt solid electrolyte comprises the following raw materials: cement, aqueous polymer, metal salt and water;
the aqueous polymer may be replaced with a polymer monomer and an oxidizing agent;
the mass ratio of the cement to the water-based polymer to the metal salt to the water is (20-70): (0.2-35): (0.2-10): (10-50); or alternatively, the first and second heat exchangers may be,
the mass ratio of the cement to the polymer monomer to the oxidant to the metal salt to the water is (20-70), 0.2-35, 0.5-10, 0.2-10 and 10-50.
2. The polymer-cement-metal salt solid electrolyte of claim 1, wherein the cement is portland cement;
the portland cement is at least one of 42.5, 42.5R, 52.5R, 62.5 and 62.5R grade portland cement.
3. The polymer-cement-metal salt solid electrolyte of claim 1, wherein the aqueous polymer is at least one of polyacrylamide, polyvinyl alcohol, polyacrylic acid, sodium polyacrylate, polyethylene oxide, gelatin, and xanthan gum;
the polymer monomer is at least one of acrylamide, acrylic acid, sodium acrylate and ethylene oxide;
the mass purity of the aqueous polymer is more than or equal to 95 percent.
4. The polymer-cement-metal salt solid electrolyte of claim 3, wherein the aqueous polymer is polyvinyl alcohol;
the polymer monomer is acrylamide or acrylic acid.
5. The polymer-cement-metal salt solid electrolyte of claim 1, wherein the oxidant is at least one of ammonium persulfate, potassium persulfate, and ferric trichloride hexahydrate;
the mass purity of the oxidant is more than or equal to 95 percent.
6. The polymer-cement-metal salt solid electrolyte of claim 1, wherein the metal salt is at least one of lithium sulfate, lithium chloride, lithium triflate, sodium sulfate, sodium chloride, sodium triflate, potassium chloride, potassium sulfate, zinc chloride, aluminum sulfate, aluminum chloride, aluminum nitrate, organomagnesium chloroaluminate, and magnesium borate;
the mass purity of the metal salt is more than or equal to 95 percent.
7. The polymer-cement-metal salt solid electrolyte of claim 6, wherein the metal salt is an alkali metal salt;
preferably, the alkali metal salt is at least one of triflate, sulfate and hydrochloride;
more preferably, the metal salt is at least one of lithium triflate, sodium triflate, lithium chloride, sodium chloride, zinc chloride, sodium sulfate, potassium sulfate, and zinc sulfate.
8. The solid state polymer-cement-metal salt electrolyte of any one of claims 1 to 7, wherein the solid state polymer-cement-metal salt electrolyte has a voltage window of 1 to 4.5V and an ionic conductivity of 5 to 75mS cm -1 Compressive strength of 10-52MPa and pore volume of 10 -4 ～10 -1 cm 3 g -1 A specific surface area of 10 -3 ～10m 2 g -1 。
9. The method for producing a polymer-cement-metal salt solid electrolyte according to any one of claims 1 to 8, comprising the steps of: uniformly mixing the cement, the water-based polymer, the metal salt and the water; or alternatively, the first and second heat exchangers may be,
uniformly mixing the polymer monomer, the metal salt and water to obtain a mixed solution; adding cement into the mixed solution and uniformly mixing to obtain slurry; and adding an oxidant into the slurry, and uniformly mixing.
10. A structural energy storage device employing the polymer-cement-metal salt solid state electrolyte of any one of claims 1-8.
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