CN116646593A - All-solid-state polymer electrolyte and preparation method and application thereof - Google Patents
All-solid-state polymer electrolyte and preparation method and application thereof Download PDFInfo
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- CN116646593A CN116646593A CN202310534209.5A CN202310534209A CN116646593A CN 116646593 A CN116646593 A CN 116646593A CN 202310534209 A CN202310534209 A CN 202310534209A CN 116646593 A CN116646593 A CN 116646593A
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 144
- 238000002360 preparation method Methods 0.000 title claims abstract description 61
- 239000011159 matrix material Substances 0.000 claims abstract description 98
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 58
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052796 boron Inorganic materials 0.000 claims abstract description 51
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229920000642 polymer Polymers 0.000 claims abstract description 41
- 238000011065 in-situ storage Methods 0.000 claims abstract description 37
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 25
- 239000002841 Lewis acid Substances 0.000 claims abstract description 3
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims description 96
- 239000012528 membrane Substances 0.000 claims description 69
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 62
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- 239000002131 composite material Substances 0.000 claims description 29
- 239000003365 glass fiber Substances 0.000 claims description 25
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- -1 polyethylene terephthalate Polymers 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 238000001291 vacuum drying Methods 0.000 claims description 19
- 238000007731 hot pressing Methods 0.000 claims description 16
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 15
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- BODYVHJTUHHINQ-UHFFFAOYSA-N (4-boronophenyl)boronic acid Chemical compound OB(O)C1=CC=C(B(O)O)C=C1 BODYVHJTUHHINQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910020808 NaBF Inorganic materials 0.000 claims description 4
- 229910021201 NaFSI Inorganic materials 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- XIXNSLABECPEMI-VURMDHGXSA-N (z)-2-[2-[(2-methylpropan-2-yl)oxycarbonylamino]-1,3-thiazol-4-yl]pent-2-enoic acid Chemical compound CC\C=C(/C(O)=O)C1=CSC(NC(=O)OC(C)(C)C)=N1 XIXNSLABECPEMI-VURMDHGXSA-N 0.000 claims description 2
- PIEUWWVYSBWVRR-UHFFFAOYSA-N OBOBO.C1=CC=CC=C1C1=CC=CC=C1 Chemical compound OBOBO.C1=CC=CC=C1C1=CC=CC=C1 PIEUWWVYSBWVRR-UHFFFAOYSA-N 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- JJFQTKHGJJWAJZ-UHFFFAOYSA-N 2-benzylsulfanyl-5-(trifluoromethyl)benzoic acid Chemical compound OC(=O)C1=CC(C(F)(F)F)=CC=C1SCC1=CC=CC=C1 JJFQTKHGJJWAJZ-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 33
- 238000013508 migration Methods 0.000 abstract description 28
- 230000005012 migration Effects 0.000 abstract description 28
- 239000003792 electrolyte Substances 0.000 abstract description 24
- 230000006872 improvement Effects 0.000 abstract description 5
- 230000001360 synchronised effect Effects 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 description 49
- 230000000052 comparative effect Effects 0.000 description 31
- 239000000835 fiber Substances 0.000 description 31
- 238000012360 testing method Methods 0.000 description 19
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 description 18
- 239000013474 COF-1 Substances 0.000 description 16
- 239000002808 molecular sieve Substances 0.000 description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 13
- 239000000725 suspension Substances 0.000 description 13
- 238000000527 sonication Methods 0.000 description 12
- 239000012456 homogeneous solution Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 238000010998 test method Methods 0.000 description 7
- 230000010287 polarization Effects 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920006380 polyphenylene oxide Polymers 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- CHQMXRZLCYKOFO-UHFFFAOYSA-H P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F Chemical compound P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F CHQMXRZLCYKOFO-UHFFFAOYSA-H 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- WFSRWJJESXWWSH-UHFFFAOYSA-N [O-2].[Fe+2].[Mn+2].[Ni+2].[Na+] Chemical compound [O-2].[Fe+2].[Mn+2].[Ni+2].[Na+] WFSRWJJESXWWSH-UHFFFAOYSA-N 0.000 description 1
- CUNAJIREFWUWGY-UHFFFAOYSA-N [Sb].[C] Chemical compound [Sb].[C] CUNAJIREFWUWGY-UHFFFAOYSA-N 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YPPMLCHGJUMYPZ-UHFFFAOYSA-L sodium;iron(2+);sulfate Chemical compound [Na+].[Fe+2].[O-]S([O-])(=O)=O YPPMLCHGJUMYPZ-UHFFFAOYSA-L 0.000 description 1
- KXNAKBRHZYDSLY-UHFFFAOYSA-N sodium;oxygen(2-);titanium(4+) Chemical compound [O-2].[Na+].[Ti+4] KXNAKBRHZYDSLY-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses an all-solid-state polymer electrolyte and a preparation method and application thereof, and relates to the field of sodium ion batteries, and the all-solid-state polymer electrolyte is characterized by comprising a functional matrix, a polymer matrix and sodium salt, wherein the functional matrix comprises a boron-containing organic structure and a porous support body, the functional matrix is obtained by growing the boron-containing organic structure on the surface of the porous support body in situ, and the boron-containing organic structure has rich Lewis acid sites; the invention provides an all-solid-state polymer electrolyte which realizes synchronous improvement of comprehensive performances such as ionic conductivity, sodium ion migration number, electrochemical stability and the like, has unique composition and structure, can simultaneously enhance interface stability of an anode/electrolyte interface and a cathode/electrolyte interface, and has good multiplying power performance and circulation stability.
Description
Technical Field
The invention relates to the field of sodium ion batteries, in particular to an all-solid-state polymer electrolyte, and a preparation method and application thereof.
Background
The development of efficient and cost-effective energy storage equipment is one of the most effective ways to solve the current energy shortage and low utilization rate problems. Throughout the many energy storage devices, lithium batteries have been widely studied as typical secondary batteries, but at the same time, the development thereof is severely limited by the continual increase in cost of lithium batteries due to scarce lithium resources. And the sodium of the same main group as lithium has similar physical and chemical properties as lithium, and the sodium ion battery formed by the sodium ion battery not only has high safety and adaptability, but also has research to show that the sodium ion battery also has excellent high and low temperature performance. Sodium ion batteries, which benefit from a broad distribution of sodium resources and low cost, are also expected to find wider and deeper applications in certain fields, particularly in the field of large-scale energy storage. However, the sodium ion battery reported at present mainly uses flammable and volatile organic electrolyte, and serious safety accidents are easy to occur due to thermal runaway in the use process of the battery; on the other hand, the organic electrolyte has a narrow electrochemical window, is unstable to sodium metal, is difficult to match with a high-voltage positive electrode and a high-voltage negative electrode, and severely limits the improvement of the energy density of the sodium ion battery.
The solid electrolyte is adopted to replace organic electrolyte, so that the solvent-free all-solid sodium ion battery can be constructed, the problems can be solved, and the stable contact interface can widen the selection range of the anode material, so that the sodium ion battery with high safety and high energy density is selected. However, all-solid-state sodium ion batteries still face the problems of low ion conductivity, small sodium ion migration number, poor cycling stability and the like. Therefore, developing a high performance all-solid-state electrolyte is a significant technical challenge in achieving commercial sodium ion battery applications.
Disclosure of Invention
In view of the above, a first aspect of the present invention is to provide an all-solid polymer electrolyte having high ionic conductivity, high sodium ion migration number, excellent mechanical properties, and good stability against metallic sodium at the same time.
The technical scheme adopted by the invention is as follows:
an all-solid-state polymer electrolyte is characterized by comprising a functional matrix, a polymer matrix and sodium salt, wherein the functional matrix comprises a boron-containing organic structure and a porous support, and the boron-containing organic structure has rich Lewis acid sites.
The further arrangement is that:
the polymer matrix comprises ethoxy groups, and after the polymer matrix is combined with sodium salt, the polymer matrix is infused into the functional matrix.
The polymer matrix is preferably an ether polymer, and particularly preferably the polymer is at least one of polyethylene oxide PEO and polyphenylene oxide PPO.
The sodium salt is selected to be a sodium salt of an ether electrolyte, and particularly preferably, the sodium salt is selected to be NaClO 4 、NaPF 6 、NaFSI、NaTFSI、NaBF 4 At least one of them.
The functional matrix is a porous support body modified by a boron-containing organic structure, and is obtained by growing the boron-containing organic structure on the surface of the porous support body in situ.
The porous support is selected from porous supports rich in fiber continuous pores, preferably at least one of a glass fiber film, a polyimide film, a cellulose nonwoven film, a polyethylene terephthalate film and a polyimide film.
The boron-containing organic structure is selected from any one of compounds having the structural formula shown in the specification:
a second aspect of the present invention is to provide a method for producing the above all-solid polymer electrolyte, characterized by: and taking the porous support as a substrate, preparing the functional matrix by a solution in-situ polymerization method, pouring the mixed solution of the polymer matrix and sodium salt into the functional matrix, and finally obtaining the all-solid polymer electrolyte by vacuum hot-pressing drying treatment.
Further:
the preparation method of the all-solid-state polymer electrolyte is characterized by comprising the following steps of:
(1) Preparing a functional matrix:
mixing a boron-containing monomer and a ligand into a solvent to form a precursor mixed solution, immersing the porous support in the precursor mixed solution, and performing in-situ polymerization to obtain a porous support modified by a boron-containing organic structure, namely a functional matrix;
(2) Preparing a composite all-solid polymer electrolyte membrane:
preparing a polymer matrix and sodium salt into a solution according to a certain proportion, and filling the solution into the functional matrix obtained in the step (1) by adopting a solution filling method to obtain a composite all-solid polymer electrolyte membrane;
(3) Vacuum hot pressing and drying treatment:
and (3) placing the composite all-solid polymer electrolyte membrane prepared in the step (2) in a buckle type die, and carrying out vacuum drying treatment to obtain the all-solid polymer electrolyte.
The inventor finds that the physical property and the electrochemical property of the all-solid-state polymer electrolyte can be further regulated and controlled by regulating the proportion of the precursor mixed solution, the in-situ polymerization reaction time and/or the temperature during the in-situ polymerization reaction, the proportion of the polymer matrix and sodium salt, the vacuum hot-pressing load and/or the temperature and the like, and the physical property and the electrochemical property are specifically as follows:
In the step (1), the boron-containing monomer is selected from any one of 1, 4-phenyldiboronic acid (BDBA), biphenyl diboronic acid (BPDA), 1, 3, 5-benzene tricarboxylic acid (BTBA) and 1, 3, 5-phenyl ester (4-phenylboronic acid) (BTPA).
In the step (1), the ligand is selected from any one of 1, 4-benzenediboronic acid (BDBA), 2,3,6,7,10, 11-hexahydroxytriphenyl (HHTP).
In the step (1), the solvent is a mixed solution of m-trimethylbenzene and 1, 4-dioxane, wherein the volume ratio of m-trimethylbenzene to 1, 4-dioxane is 0.5-1.5:0.5-1.5, preferably 0.8-1.2:0.8-1.2, and more preferably 1:1.
In step (1), the reaction temperature of the in-situ polymerization is 100℃to 150℃and more preferably 120 ℃.
In the step (1), the time of the in-situ polymerization reaction is 24 to 96 hours, more preferably 72 hours.
In the step (1), the product obtained by the in-situ polymerization reaction is sealed and preserved after washing, activating and vacuum drying. The washing solvent is anhydrous acetone or anhydrous acetonitrile, preferably anhydrous acetone, and the washing times are 1-4 times, preferably 3 times; the activating organic solvent is anhydrous acetone, and the activating time is 12-36h, preferably 24h; the temperature of vacuum drying is 100-150 ℃, preferably 120 ℃, and the time of vacuum drying is 12-36h, preferably 24h. The prepared functional matrix is stored in a sealed manner in an inert atmosphere to prevent the hydrolysis of the functional matrix.
In step (2), the polymer matrix is PEO or PPO, preferably PEO.
In the step (2), the sodium salt is NaClO 4 、NaPF 6 NaFSI, naTFSI or NaBF 4 NaTFSI is preferred.
In step (2), the ratio of the polymer matrix to the sodium salt is 8-20:1, preferably 16:1.
In the step (3), the load pressure of the button die is 5-50N, preferably 20N, and the vacuum drying temperature is 50-80 ℃, preferably 60 ℃.
A third aspect of the present invention is directed to the use of the above all-solid polymer electrolyte for the preparation of all-solid sodium ion batteries. The method comprises the following steps: an all-solid sodium ion battery comprises a positive electrode, a negative electrode and the all-solid polymer electrolyte.
In the present invention, the positive electrode and the negative electrode of the all-solid sodium ion battery are not particularly limited, and positive electrode materials and negative electrode materials known in the art may be used. Illustratively, the positive electrode includes at least one of sodium vanadium phosphate, sodium nickel iron manganese oxide, prussian blue, sodium ion fluorophosphate, sodium iron sulfate, sodium vanadium fluorophosphate. Illustratively, the negative electrode contains at least one of metallic sodium, molybdenum disulfide, hard carbon, sodium titanium oxide, nickel cobalt oxide, antimony carbon composite material, and the like.
The invention has the beneficial effects that:
(1) The invention provides an all-solid-state polymer electrolyte, which realizes the synchronous improvement of the comprehensive performances of ion conductivity, sodium ion migration number, electrochemical stability and the like, and meets the practical application requirements of all-solid-state sodium ion batteries. Through experiments and detection analysis, the all-solid-state polymer electrolyte provided by the invention has good electrochemical performance: (1) Ion conductivity of 2X 10 -4 ～6×10 -4 S cm -1 Preferably 5X 10 -4 ～6×10 -4 S cm -1 The method comprises the steps of carrying out a first treatment on the surface of the (2) sodium ion migration number greater than 0.28, preferably 0.5 to 0.9; (3) Electrochemical window greater than 3.8v vs. na + Na, preferably 5.0V to 6.0V vs. Na + Na, and the all-solid polymer electrolyte has good stability to metallic sodium.
The reason for this analysis is: on one hand, the electrolyte can utilize the capture effect of the boron-containing organic structure on anions, promote dissociation of sodium salt, effectively improve migration number of sodium ions, reduce concentration polarization formed by charge transfer in the electrolyte, and stabilize sodium deposition and stripping processes of a negative electrode/electrolyte contact interface; on the other hand, an in-situ growth strategy is adopted to maximize and uniformly distribute a boron-containing organic structure on a porous support body with a regular fiber skeleton, and a rapid sodium ion transmission channel is also constructed while the functionality of the porous support body is fully exerted, so that the all-solid-state sodium ion battery has good cycle stability and rate capability.
(2) The invention provides a preparation method of an all-solid-state polymer electrolyte, wherein a main material (mainly composed of a boron-containing organic structure and a porous support) of the all-solid-state polymer electrolyte is low in price and cost, and the all-solid-state polymer electrolyte is simple in preparation process, good in safety and environment-friendly.
(3) The invention provides an application of an all-solid-state polymer electrolyte in preparing an all-solid-state sodium ion battery, the all-solid-state polymer electrolyte has unique composition and structure, the electrolyte can simultaneously enhance the interface stability of an anode/electrolyte interface and a cathode/electrolyte interface, and the assembled all-solid-state sodium ion battery has good multiplying power performance and circulation stability.
The invention is further described below with reference to the drawings and detailed description.
Drawings
FIG. 1 shows a scanning electron micrograph (a) of B-GF prepared in example 1 and a B-GF micrograph (B) after ultrasonic stripping.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the electrolyte SCPE prepared in example 1.
FIG. 3 is an Energy Dispersive Spectrometer (EDS) diagram of electrolyte SCPE prepared in example 1.
Fig. 4 is an X-ray diffractometer (XRD) of electrolyte SCPE prepared in example 1.
FIG. 5 is a Fourier infrared spectrometer (FT-IR) of the electrolyte SCPE prepared in example 1.
Fig. 6 is an impedance spectrum of an ion conductivity test of the electrolyte SCPE prepared in example 1.
Fig. 7 is an electrochemical window test of electrolyte SCPE prepared in example 1.
Fig. 8 shows the dc polarization curve (a) and the impedance spectrum (b) of the sodium ion mobility test of the electrolyte SCPE1 prepared in example 1.
FIG. 9 is a scanning electron microscope image of B-GF prepared in example 2.
FIG. 10 is a scanning electron microscope image of B-GF prepared in example 3.
FIG. 11 is a scanning electron micrograph of B-GF prepared in example 4.
FIG. 12 is a scanning electron microscope image of B-GF prepared in example 5.
FIG. 13 is a scanning electron micrograph of B-GF prepared in comparative example 2.
FIG. 14 is a scanning electron micrograph of B-GF prepared in comparative example 3.
FIG. 15 is a scanning electron micrograph of B-GF prepared in comparative example 4.
FIG. 16 is a scanning electron micrograph of B-GF prepared in comparative example 5.
Fig. 17 is a charge-discharge curve of the all-solid-state sodium ion battery of application example 1.
Fig. 18 is a cycle performance chart of the all solid state sodium ion battery of application example 1.
Fig. 19 is a charge-discharge curve of the all solid state sodium ion battery of comparative example 2.
Fig. 20 is a graph of the cycling performance of the all solid state sodium ion battery of comparative example 2.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1: preparation of all solid Polymer electrolyte SCPE
The preparation method of the all-solid-state polymer electrolyte SCPE comprises the following steps:
(1) Preparation of functional matrix film B-GF:
0.1g glass fiber film GF, 0.25g BDBA and 10mL m-trimethylbenzene in a volume ratio of 1:1: 1, 4-Dioxahexacyclic ring solution was sealed in Schlenk bottles andultrasonic treatment is carried out for 60 minutes at room temperature; the resulting suspension was then subjected to a reaction at 77K (LN 2 Bath) and vacuum were applied, after which the mixture was thawed by sonication, and the above procedure was repeated twice to completely remove the residual air. The prepared mixture is placed at 120 ℃ for 72 hours to obtain a fiber film with in-situ growth COF-1, the fiber film is washed by anhydrous acetone (treated by a molecular sieve), the obtained fiber film is activated by the anhydrous acetone for 24 hours, and then the fiber film is dried in a vacuum oven at 120 ℃ for 12 hours to obtain the functional matrix film B-GF. The resulting functional matrix film B-GF was stored in a glove box in a sealed manner for use to prevent hydrolysis.
(2) Preparation of composite all-solid polymer electrolyte membrane ex-SCPE:
first, the polymers PEO (0.064 mol) and NaTFSI (0.004 mol) were dissolved in 20mL of anhydrous acetonitrile to form a clear homogeneous solution, EO/Na + The molar ratio of (2) is controlled to be 16:1. And (2) then placing the functional matrix film B-GF synthesized in the step (1) into a polytetrafluoroethylene mould, injecting the solution into the functional matrix film B-GF, waiting for acetonitrile to volatilize naturally, thus obtaining the composite all-solid polymer electrolyte film ex-SCPE, and storing in an inert atmosphere.
(3) Preparation of all solid polymer electrolyte SCPE:
and (3) in a glove box, placing the composite all-solid polymer electrolyte membrane ex-SCPE prepared in the step (2) in a button polytetrafluoroethylene mould, applying a load of 20N on the mould, transferring the mould into a vacuum drying oven, and hot-pressing and drying the mould at 60 ℃ for 12 hours to finally obtain the all-solid polymer electrolyte SCPE.
And (3) detecting a product:
1. morphology and composition structure of product
The microscopic morphology of the functional matrix B-GF was observed using a Scanning Electron Microscope (SEM), and as a result, the boron-containing organic structure COF-1 showed a close-packed structure on the surface of the glass fiber as shown in fig. 1 a. And can be seen from fig. 1 b: COF-1 appears to be layered and distributed adjacent to the glass fibers, demonstrating successful in situ growth of the boron-containing organic structure COF-1 on the fiber surface of the porous support GF.
The microscopic morphology of the all-solid-state polymer electrolyte SCPE was observed using a Scanning Electron Microscope (SEM), and the result is shown in FIG. 2, in which the all-solid-state polymer electrolyte SCPE exhibited a smooth and uniform surface.
The structural composition of the all solid polymer electrolyte SCPE was observed using an Energy Dispersive Spectrometer (EDS) and the results are shown in FIG. 3, wherein the C, N, O, naTFSI contained in the polymer PEO, the Na, F, S and the B, si contained in the B-GF were uniformly distributed on the cross section of the prepared all solid polymer electrolyte SCPE, indicating good recombination of the polymers PEO, naTFSI and B-GF.
The structural composition of the all solid polymer electrolyte SCPE was investigated using X-ray diffractometer (XRD), and the results are shown in fig. 4: the characteristic peaks of the polymer PEO, naTFSI and the boron-containing organic structure COF-1 appear in the all-solid-state polymer electrolyte SCPE, which proves that the all-solid-state polymer electrolyte SCPE is formed by compounding the polymer PEO, naTFSI and the boron-containing organic structure COF-1.
The structural composition of the all solid polymer electrolyte SCPE was verified using fourier infrared spectrometer (FT-IR), and the results are shown in fig. 5: FIG. 5a shows that grown in situ on B-GF is the boron-containing organic structure COF-1. As can be seen from fig. 5b, the boron-containing organic structure COF-1 is grown in situ on the porous support GF. And it can be seen from fig. 5c, 5d that the polymer PEO is present in the all solid polymer electrolyte SCPE.
2. Electrical property detection of all-solid-state polymer electrolyte SCPE
2.1 ionic conductivity of all solid polymer electrolyte SCPE:
the electrolyte SCPE prepared in this example was sandwiched between two stainless steel sheets, assembled in a 2032-type battery case, and subjected to electrochemical alternating current impedance spectroscopy using an electrochemical workstation. The ionic conductivity of the electrolyte was calculated by the following formula:
wherein L is the thickness of the all-solid polymer electrolyte, S is the facing area of the stainless steel sheet, R b For the measurement of the electrolysisA mass body impedance. As a result of the test, as shown in FIG. 6, the electrolyte SCPE of example 1 had an ion conductivity of 5.48X10 at 60 ℃ -4 S cm -1 。
1.2 electrochemical window of all solid polymer electrolyte SCPE:
all-solid-state polymer electrolyte SCPE is clamped between a stainless steel sheet and a sodium sheet and is assembled in a 2032 type battery shell, an electrochemical window is measured by linear voltammetry scanning through an electrochemical workstation, and the test conditions are as follows: the initial potential was 2V, the highest potential was 6.5V, and the scan rate was 5mV/s. The results are shown in FIG. 7, the electrochemical window of the dual function gel polymer electrolyte of example 1 is 5.98V vs. Na + /Na。
1.3 Na of all solid Polymer electrolyte SCPE + Number of migration
The Na/SCPE/Na symmetrical battery is assembled in 2032 battery shell by clamping all-solid-state polymer electrolyte SCPE between two sodium sheets, and sodium ion migration number is tested by adopting alternating current impedance and potentiostatic chronoamperometryWherein the polarization voltage is 10mV. The migration number of sodium ions can be calculated by the following formula:
wherein I is 0 And I S Current values before and after polarization, R 0 And R is S The interface impedance, deltaV, obtained by testing before and after polarization, respectively, is the applied polarization voltage value. The results of the test are shown in FIG. 8, and the sodium ion migration number of the all solid polymer electrolyte prepared in example 1 is 0.62.
Example 2
The preparation method of the all-solid-state polymer electrolyte SCPE comprises the following steps:
(1) Preparation of functional matrix film B-GF:
0.1g of glass fiber film GF, 0.25g of BDBA and 10mL of m-trimethylbenzene in a volume ratio of 1:1: the 1, 4-dioxane solution was sealed in a Schlenk flask and sonicated at room temperature for 60 minutes. The resulting suspension was then subjected to a reaction at 77K (LN 2 Bath) and vacuum were applied, after which the mixture was thawed by sonication, and the above procedure was repeated twice to completely remove the residual air. The prepared mixture was left at 100℃for 72 hours to give a 3D fibrous skeleton with in-situ grown COF-1, and washed with anhydrous acetone (treated with molecular sieves). The resulting fibrous membrane was activated with anhydrous acetone for 24 hours, and then dried in a vacuum oven at 100 ℃ for 12 hours to obtain a functional matrix membrane. The resulting white fibrous membrane (i.e., B-GF) was stored in a glove box in a sealed manner for use to prevent hydrolysis.
(2) Preparation of composite all-solid polymer electrolyte membrane ex-SCPE:
first, the polymers PEO (0.064 mol) and NaTFSI (0.004 mol) were dissolved in 20mL of anhydrous acetonitrile to form a clear homogeneous solution, EO/Na + The molar ratio of (2) is controlled to be 16:1. And (2) then placing the functional matrix B-GF synthesized in the step (1) into a polytetrafluoroethylene mould, injecting the solution into the B-GF, waiting for acetonitrile to volatilize naturally, thus obtaining a preliminary all-solid polymer electrolyte membrane ex-SCPE and storing in an inert atmosphere.
(3) Vacuum hot pressing drying treatment is carried out to prepare the all-solid polymer electrolyte SCPE:
and (3) in a glove box, placing the ex-SCPE prepared in the step (2) in a button polytetrafluoroethylene mould, applying a load of 20N on the mould, transferring the mould into a vacuum drying oven, and hot-pressing and drying the mould at 60 ℃ for 12 hours to finally obtain the all-solid polymer electrolyte SCPE.
And (3) detecting products:
as shown in FIG. 9, the B-GF prepared in example 2 can well grow the boron-containing organic structure on the surface of the glass fiber in situ, but the boron-containing organic structure presents irregular and uneven morphology.
The ionic conductivity, electrochemical window and electrochemical window of the all solid polymer electrolyte SCPE prepared in example 2 were tested using the test method in example 1 Sodium ion migration number. The ionic conductivity of the all solid polymer electrolyte SCPE prepared in example 2 was 3.42×10 at 60deg.C -4 S cm -1 Electrochemical window 5.68V vs. Na + Na, sodium ion migration number was 0.52.
Example 3
The preparation method of the all-solid-state polymer electrolyte SCPE comprises the following steps:
(1) Preparation of functional matrix film B-GF:
0.1g glass fiber film GF, 0.25g BDBA and 10mL m-trimethylbenzene in a volume ratio of 1:1: the 1, 4-dioxane solution was sealed in a Schlenk flask and sonicated at room temperature for 60 minutes. The resulting suspension was then subjected to a reaction at 77K (LN 2 Bath) and vacuum were applied, after which the mixture was thawed by sonication, and the above procedure was repeated twice to completely remove the residual air. The prepared mixture was left at 150℃for 72 hours to give a 3D fibrous skeleton with in-situ grown COF-1, and washed with anhydrous acetone (treated with molecular sieves). The resulting fibrous membrane was activated with anhydrous acetone for 24 hours, and then dried in a vacuum oven at 150 ℃ for 12 hours to obtain a functional matrix membrane. The resulting white fibrous membrane (i.e., B-GF) was stored in a glove box in a sealed manner for use to prevent hydrolysis.
(2) Preparation of composite all-solid polymer electrolyte membrane ex-SCPE:
First, the polymers PEO (0.064 mol) and NaTFSI (0.004 mol) were dissolved in 20mL of anhydrous acetonitrile to form a clear homogeneous solution, EO/Na + The molar ratio of (2) is controlled to be 16:1. And (2) then placing the functional matrix B-GF synthesized in the step (1) into a polytetrafluoroethylene mould, injecting the solution into the B-GF, waiting for acetonitrile to volatilize naturally, thus obtaining a preliminary all-solid polymer electrolyte membrane ex-SCPE and storing in an inert atmosphere.
(3) Vacuum hot pressing drying treatment is carried out to prepare the all-solid polymer electrolyte SCPE:
and (3) placing the ex-SCPE prepared in the step (2) in a buckle type polytetrafluoroethylene mould in a glove box, applying a load of 20N on the mould, transferring the mould into a vacuum drying oven, and hot-pressing and drying the mould at 60 ℃ for 12 hours to finally obtain the all-solid polymer electrolyte SCPE.
And (3) detecting products:
as shown in FIG. 10, the boron-containing organic structure grown on the B-GF surface prepared in example 3 shows a relatively uniform distribution, but the morphology is not independently regular.
The ionic conductivity, electrochemical window and sodium ion migration number of the all solid polymer electrolyte prepared in example 3 were tested using the test method in example 1. The ionic conductivity of the all-solid polymer electrolyte prepared in example 3 was tested to be 2.98X10 at 60 ℃ -4 S cm -1 Electrochemical window 5.38V vs. Na + Na, sodium ion migration number was 0.57.
Comparative example 2
The preparation method of the all-solid-state polymer electrolyte SCPE comprises the following steps:
(1) Preparation of functional matrix film B-GF:
0.1g glass fiber film GF, 0.25g BDBA and 10mL m-trimethylbenzene in a volume ratio of 1:1: the 1, 4-dioxane solution was sealed in Schlenk flask and shaken well with mixing. The resulting suspension was then subjected to a reaction at 77K (LN 2 Bath) and vacuum were applied, after which the mixture was thawed by sonication, and the above procedure was repeated twice to completely remove the residual air. The prepared mixture was left at 180℃for 72 hours and washed with anhydrous acetone (treated with molecular sieves). The resulting fibrous membrane was activated with anhydrous acetone for 24 hours and then dried in a vacuum oven at 180 ℃ for 12 hours.
The product prepared in comparative example 2 was observed by a scanning electron microscope, as shown in fig. 13, and the prepared B-GF surface could not grow the boron-containing organic structure in situ due to the excessively high reaction temperature.
Subsequent preparation and testing was not performed due to the failure to successfully prepare the functional matrix film B-GF with the boron-containing organic structure.
Comparative example 3:
the preparation method of the all-solid-state polymer electrolyte SCPE comprises the following steps:
(1) Preparation of functional matrix film B-GF:
0.1g glass fiber film GF, 0.25g BDBA and 10mL m-trimethylbenzene in a volume ratio of 1:1: 1The 4-dioxane solution was sealed in Schlenk flask and shaken well with mixing. The resulting suspension was then subjected to a reaction at 77K (LN 2 Bath) and vacuum were applied, after which the mixture was thawed by sonication, and the above procedure was repeated twice to completely remove the residual air. The prepared mixture was left at 90℃for 72 hours and washed with anhydrous acetone (treated with molecular sieves). The resulting fibrous membrane was activated with anhydrous acetone for 24 hours and then dried in a vacuum oven at 90 ℃ for 12 hours.
The product prepared in comparative example 3 was observed by a scanning electron microscope, as shown in fig. 14, and the prepared B-GF surface could not grow the boron-containing organic structure in situ due to the excessively low reaction temperature.
Subsequent preparation and testing was not performed due to the failure to successfully prepare the functional matrix film B-GF with the boron-containing organic structure.
The small knot:
(1) By comparing example 1 with example 2 and example 3, it can be found that: the reaction temperature in the step (1) is controlled between 100 and 150 ℃ and the reaction time is 72 hours, the boron-containing organic structure can be grown on the surface of the glass fiber in situ, and the functional matrix film B-GF with the boron-containing organic structure is prepared, wherein the temperature is controlled at 120 ℃, the boron-containing polymer can be grown on the surface of the glass fiber in situ well and presents a compact stacking structure on the surface of the glass fiber, and the prepared B-GF can also be grown on the surface of the glass fiber in situ well at 100 ℃ and 150 ℃, but the boron-containing organic structure presents an irregular morphology. Meanwhile, the electrochemical window, the ion conductivity and the sodium ion migration number are respectively detected, and the optimal reaction temperature is 120 ℃.
(2) By comparing example 1 with comparative example 2, comparative example 3, it can be found that: in comparative example 2, the reaction temperature was too high, and the prepared B-GF surface could not grow the boron-containing organic structure in situ. In comparative example 3, the reaction temperature was lowered to 90 ℃, and also, a functional matrix film B-GF having a boron-containing organic structure could not be prepared.
Example 4
The preparation method of the all-solid-state polymer electrolyte SCPE comprises the following steps:
(1) Preparation of functional matrix film B-GF:
0.1g glass fiber film GF, 0.25g BDBA and 10mL m-trimethylbenzene in a volume ratio of 1:1: the 1, 4-dioxane solution was sealed in a Schlenk flask and sonicated at room temperature for 60 minutes. The resulting suspension was then subjected to a reaction at 77K (LN 2 Bath) and vacuum were applied, after which the mixture was thawed by sonication, and the above procedure was repeated twice to completely remove the residual air. The prepared mixture is placed at 120 ℃ for 24 hours to obtain a fiber membrane with in-situ growth COF-1, the fiber membrane is washed by anhydrous acetone (treated by a molecular sieve), the obtained fiber membrane is activated by the anhydrous acetone for 24 hours, and then the fiber membrane is dried in a vacuum oven at 120 ℃ for 12 hours to obtain the functional matrix membrane B-GF. The resulting functional matrix film B-GF was stored in a glove box in a sealed manner for use to prevent hydrolysis.
(2) Preparation of composite all-solid polymer electrolyte membrane ex-SCPE:
first, the polymers PEO (0.064 mol) and NaTFSI (0.004 mol) were dissolved in 20mL of anhydrous acetonitrile to form a clear homogeneous solution, EO/Na + The molar ratio of (2) is controlled to be 16:1. And (2) then placing the functional matrix film B-GF synthesized in the step (1) into a polytetrafluoroethylene mould, injecting the solution into the functional matrix film B-GF, waiting for acetonitrile to volatilize naturally, thus obtaining the composite all-solid polymer electrolyte film ex-SCPE, and storing in an inert atmosphere.
(3) Preparation of all solid polymer electrolyte SCPE:
and (3) in a glove box, placing the composite all-solid polymer electrolyte membrane ex-SCPE prepared in the step (2) in a button polytetrafluoroethylene mould, applying a load of 20N on the mould, transferring the mould into a vacuum drying oven, and hot-pressing and drying the mould at 60 ℃ for 12 hours to finally obtain the all-solid polymer electrolyte SCPE.
And (3) detecting products:
as shown in FIG. 11, the boron-containing organic structure grown on the B-GF surface prepared in example 4 shows a regular morphology, but the distribution is sparse and discontinuous.
The all solid polymer electrolyte prepared in example 4 was tested using the test method in example 1Ion conductivity, electrochemical window, and sodium ion transport number of the mass. The ionic conductivity of the all-solid polymer electrolyte prepared in example 4 was 3.86X 10 at 60℃as tested -4 S cm -1 Electrochemical window 5.56V vs. Na + Na, sodium ion migration number was 0.53.
Example 5
The preparation method of the all-solid-state polymer electrolyte SCPE comprises the following steps:
(1) Preparation of functional matrix film B-GF:
0.1g glass fiber film GF, 0.25g BDBA and 10mL m-trimethylbenzene in a volume ratio of 1:1: the 1, 4-dioxane solution was sealed in a Schlenk flask and sonicated at room temperature for 60 minutes. The resulting suspension was then subjected to a reaction at 77K (LN 2 Bath) and vacuum were applied, after which the mixture was thawed by sonication, and the above procedure was repeated twice to completely remove the residual air. The prepared mixture is placed at 120 ℃ for 96 hours to obtain a fiber membrane with in-situ growth COF-1, the fiber membrane is washed by anhydrous acetone (treated by a molecular sieve), the obtained fiber membrane is activated by the anhydrous acetone for 24 hours, and then the fiber membrane is dried in a vacuum oven at 120 ℃ for 12 hours to obtain the functional matrix membrane B-GF. The resulting functional matrix film B-GF was stored in a glove box in a sealed manner for use to prevent hydrolysis.
(2) Preparation of composite all-solid polymer electrolyte membrane ex-SCPE:
first, the polymers PEO (0.064 mol) and NaTFSI (0.004 mol) were dissolved in 20mL of anhydrous acetonitrile to form a clear homogeneous solution, EO/Na + The molar ratio of (2) is controlled to be 16:1. And (2) then placing the functional matrix film B-GF synthesized in the step (1) into a polytetrafluoroethylene mould, injecting the solution into the functional matrix film B-GF, waiting for acetonitrile to volatilize naturally, thus obtaining the composite all-solid polymer electrolyte film ex-SCPE, and storing in an inert atmosphere.
(3) Preparation of all solid polymer electrolyte SCPE:
and (3) in a glove box, placing the composite all-solid polymer electrolyte membrane ex-SCPE prepared in the step (2) in a button polytetrafluoroethylene mould, applying a load of 20N on the mould, transferring the mould into a vacuum drying oven, and hot-pressing and drying the mould at 60 ℃ for 12 hours to finally obtain the all-solid polymer electrolyte SCPE.
And (3) detecting products:
as shown in FIG. 12, the boron-containing organic structure grown on the B-GF surface prepared in example 5 is of a regular morphology, but exhibits an excessive packing distribution.
The ionic conductivity, electrochemical window and sodium ion migration number of the all solid polymer electrolyte prepared in example 5 were tested using the test method in example 1. The ionic conductivity of the all-solid polymer electrolyte prepared in example 5 was tested to be 4.13X 10 at 60 ℃ -4 S cm -1 Electrochemical window 5.93V vs. Na + Na, sodium ion migration number was 0.61.
Comparative example 4:
(1) Preparation of functional matrix film B-GF:
0.1g glass fiber film GF, 0.25g BDBA and 10mL m-trimethylbenzene in a volume ratio of 1:1: the 1, 4-dioxane solution was sealed in Schlenk flask and shaken well with mixing. The resulting suspension was then subjected to a reaction at 77K (LN 2 Bath) and vacuum were applied, after which the mixture was thawed by sonication, and the above procedure was repeated twice to completely remove the residual air. The prepared mixture was left at 120℃for 12 hours and washed with anhydrous acetone (treated with molecular sieves). The resulting fibrous membrane was activated with anhydrous acetone for 24 hours and then dried in a vacuum oven at 120 ℃ for 12 hours.
The product prepared in comparative example 4 was observed by a scanning electron microscope, as shown in fig. 15, the reaction time was too short, the boron-containing organic structure grown on the surface of the prepared B-GF was extremely sparse, and could not meet the actual preparation requirements, and the subsequent preparation and testing were not performed.
Comparative example 5:
the preparation method of the all-solid-state polymer electrolyte SCPE comprises the following steps:
(1) Preparation of functional matrix film B-GF:
0.1g glass fiber film GF, 0.25g BDBA and 10mL m-trimethylbenzene in a volume ratio of 1:1: the 1, 4-dioxane solution was sealed in Schlenk flask and shaken well with mixing. The resulting suspension was then subjected to a reaction at 77K (LN 2 Bath) and vacuum were applied, after which the mixture was thawed by sonication, and the above procedure was repeated twice to completely remove the residual air. The prepared mixture was left at 120℃for 108 hours and washed with anhydrous acetone (treated with molecular sieves). The resulting fibrous membrane was activated with anhydrous acetone for 24 hours and then dried in a vacuum oven at 120 ℃ for 12 hours.
The product prepared in comparative example 5 was observed by a scanning electron microscope, as shown in fig. 16, the reaction time was too long, the boron-containing organic structure grown on the surface of the prepared B-GF was destroyed, the actual preparation requirements could not be satisfied, and the subsequent preparation and testing were not performed.
The small knot:
(1) By comparing example 1 with example 4 and example 5, it can be found that: the reaction temperature in the step (1) is controlled at 120 ℃, the reaction time is 24-96 hours, the boron-containing organic structure can be grown on the surface of the glass fiber in situ, the functional matrix film B-GF with the boron-containing organic structure is prepared, the electrochemical window, the ion conductivity and the sodium ion migration number of the functional matrix film B-GF are detected respectively, and the optimal reaction time is 72 hours.
(2) By comparing example 1 with comparative examples 4 and 5, it can be found that: in comparative example 4, the reaction time is too short, and the boron-containing organic structure grown on the surface of the prepared B-GF is extremely sparse and cannot meet the actual preparation requirements. In contrast, in comparative example 5, the reaction time was prolonged to 108 hours, and the boron-containing organic structure grown on the surface of the prepared B-GF was destroyed due to the excessively long reaction time.
Example 6
The preparation method of the all-solid-state polymer electrolyte SCPE comprises the following steps:
(1) Preparation of functional matrix film B-GF:
0.1g glass fiber film GF, 0.25g BDBA and 10mL m-trimethylbenzene in a volume ratio of 1:1: the 1, 4-dioxane solution was sealed in a Schlenk flask and sonicated at room temperature for 60 minutes. The resulting suspension was then subjected to a reaction at 77K (LN 2 Bath) and vacuum were applied, after which the mixture was thawed by sonication, and the above procedure was repeated twice to completely remove the residual air. Will be put onThe prepared mixture is placed at 120 ℃ for 72 hours to obtain a fiber membrane for in-situ growth of COF-1, the fiber membrane is washed by anhydrous acetone (treated by a molecular sieve), the obtained fiber membrane is activated by the anhydrous acetone for 24 hours, and then the fiber membrane is dried in a vacuum oven at 120 ℃ for 12 hours to obtain the functional matrix membrane B-GF. The resulting functional matrix film B-GF was stored in a glove box in a sealed manner for use to prevent hydrolysis.
(2) Preparation of composite all-solid polymer electrolyte membrane ex-SCPE:
first, polymer PEO (0.064 mol) and NaTFSI (0.008 mol) were dissolved in 20mL anhydrous acetonitrile to form a clear homogeneous solution, EO/Na + The molar ratio of (2) is controlled to be 8:1. And (2) then placing the functional matrix film B-GF synthesized in the step (1) into a polytetrafluoroethylene mould, injecting the solution into the functional matrix film B-GF, waiting for acetonitrile to volatilize naturally, thus obtaining the composite all-solid polymer electrolyte film ex-SCPE, and storing in an inert atmosphere.
(3) Preparation of all solid polymer electrolyte SCPE:
and (3) in a glove box, placing the composite all-solid polymer electrolyte membrane ex-SCPE prepared in the step (2) in a button polytetrafluoroethylene mould, applying a load of 20N on the mould, transferring the mould into a vacuum drying oven, and hot-pressing and drying the mould at 60 ℃ for 12 hours to finally obtain the all-solid polymer electrolyte SCPE.
And (3) detecting products:
the ionic conductivity, electrochemical window and sodium ion migration number of the all solid polymer electrolyte prepared in example 6 were tested using the test method in example 1. The ionic conductivity of the all-solid polymer electrolyte prepared in example 6 was tested to be 6.02X10 at 60 ℃ -4 S cm -1 Electrochemical window 5.64V vs. Na + Na, sodium ion migration number was 0.42.
Example 7
The preparation method of the all-solid-state polymer electrolyte SCPE comprises the following steps:
(1) Preparation of functional matrix film B-GF:
0.1g glass fiber film GF, 0.25g BDBA and 10mL m-trimethylbenzene in a volume ratio of 1:1: 1, 4-dioxane solution sealIn Schlenk flask and sonicated at room temperature for 60 minutes. The resulting suspension was then subjected to a reaction at 77K (LN 2 Bath) and vacuum were applied, after which the mixture was thawed by sonication, and the above procedure was repeated twice to completely remove the residual air. The prepared mixture is placed at 120 ℃ for 72 hours to obtain a fiber membrane with in-situ growth COF-1, the fiber membrane is washed by anhydrous acetone (treated by a molecular sieve), the obtained fiber membrane is activated by the anhydrous acetone for 24 hours, and then the fiber membrane is dried in a vacuum oven at 120 ℃ for 12 hours to obtain the functional matrix membrane B-GF. The resulting functional matrix film B-GF was stored in a glove box in a sealed manner for use to prevent hydrolysis.
(2) Preparation of composite all-solid polymer electrolyte membrane ex-SCPE:
first, polymer PEO (0.064 mol) and NaTFSI (0.0032 mol) were dissolved in 20mL of anhydrous acetonitrile to form a clear homogeneous solution, EO/Na + The molar ratio of (2) is controlled at 20:1. And (2) then placing the functional matrix film B-GF synthesized in the step (1) into a polytetrafluoroethylene mould, injecting the solution into the functional matrix film B-GF, waiting for acetonitrile to volatilize naturally, thus obtaining the composite all-solid polymer electrolyte film ex-SCPE, and storing in an inert atmosphere.
(3) Preparation of all solid polymer electrolyte SCPE:
and (3) in a glove box, placing the composite all-solid polymer electrolyte membrane ex-SCPE prepared in the step (2) in a button polytetrafluoroethylene mould, applying a load of 20N on the mould, transferring the mould into a vacuum drying oven, and hot-pressing and drying the mould at 60 ℃ for 12 hours to finally obtain the all-solid polymer electrolyte SCPE.
And (3) detecting products:
the ionic conductivity, electrochemical window and sodium ion migration number of the all solid polymer electrolyte prepared in example 7 were tested using the test method in example 1. The ionic conductivity of the all-solid polymer electrolyte prepared in example 7 was tested to be 2.68X10 at 60 ℃ -4 S cm -1 Electrochemical window was 5.38V vs.Na + Na, sodium ion migration number was 0.55.
Comparative example 6
The preparation method of the all-solid-state polymer electrolyte SCPE comprises the following steps:
(1) Preparation of functional matrix film B-GF:
0.1g glass fiber film GF, 0.25g BDBA and 10mL m-trimethylbenzene in a volume ratio of 1:1: the 1, 4-dioxane solution was sealed in a Schlenk flask and sonicated at room temperature for 60 minutes. The resulting suspension was then subjected to a reaction at 77K (LN 2 Bath) and vacuum were applied, after which the mixture was thawed by sonication, and the above procedure was repeated twice to completely remove the residual air. The prepared mixture is placed at 120 ℃ for 72 hours to obtain a fiber membrane with in-situ growth COF-1, the fiber membrane is washed by anhydrous acetone (treated by a molecular sieve), the obtained fiber membrane is activated by the anhydrous acetone for 24 hours, and then the fiber membrane is dried in a vacuum oven at 120 ℃ for 12 hours to obtain the functional matrix membrane B-GF. The resulting functional matrix film B-GF was stored in a glove box in a sealed manner for use to prevent hydrolysis.
(2) Preparation of composite all-solid polymer electrolyte membrane ex-SCPE:
first, polymer PEO (0.064 mol) and NaTFSI (0.016 mol) were dissolved in 20mL of anhydrous acetonitrile to form a clear homogeneous solution, EO/Na + The molar ratio of (2) is controlled to be 4:1. Subsequently, the functional matrix film B-GF synthesized in the step (1) is placed into a polytetrafluoroethylene mold, and the solution is injected into the functional matrix film B-GF. During the experiment, the following steps are found: because the electrolyte membrane is not self-supporting due to the excessively high sodium salt proportion, the composite all-solid polymer electrolyte membrane ex-SCPE cannot be prepared, and therefore, the subsequent preparation and testing steps are not performed.
Comparative example 7
The preparation method of the all-solid-state polymer electrolyte SCPE comprises the following steps:
(1) Preparation of functional matrix film B-GF:
0.1g glass fiber film GF, 0.25g BDBA and 10mL m-trimethylbenzene in a volume ratio of 1:1: the 1, 4-dioxane solution was sealed in a Schlenk flask and sonicated at room temperature for 60 minutes. The resulting suspension was then subjected to a reaction at 77K (LN 2 Bath) and vacuum-pumping, thawing the mixture by ultrasonic treatment, repeating the above steps twice to completely remove the residual air. The prepared mixture is placed at 120 ℃ for 72 hours to obtain a fiber membrane with in-situ growth COF-1, the fiber membrane is washed by anhydrous acetone (treated by a molecular sieve), the obtained fiber membrane is activated by the anhydrous acetone for 24 hours, and then the fiber membrane is dried in a vacuum oven at 120 ℃ for 12 hours to obtain the functional matrix membrane B-GF. The resulting functional matrix film B-GF was stored in a glove box in a sealed manner for use to prevent hydrolysis.
(2) Preparation of composite all-solid polymer electrolyte membrane ex-SCPE:
first, polymers PEO (0.064 mol) and NaTFSI (0.00256 mol) were dissolved in 20mL anhydrous acetonitrile to form a clear homogeneous solution, EO/Na + The molar ratio of (2) is controlled at 25:1. Subsequently, the functional matrix film B-GF synthesized in the step (1) is placed into a polytetrafluoroethylene mold, and the solution is injected into the functional matrix film B-GF. During the experiment, the following steps are found: due to the too low sodium salt ratio, the polymer phase viscosity is too high to be fully infused into the prepared B-GF functional matrix film, so that a composite all-solid polymer electrolyte film ex-SCPE cannot be obtained, and subsequent preparation and testing steps are not performed any more.
The small knot:
(1) By comparing example 1 with example 6 and example 7, it can be found that: EO/Na in step (2) + The molar ratio has a significant effect on the product performance, and in general, under the condition of lower sodium salt proportion (example 7), the electrochemical window, the ion conductivity and the sodium ion migration number of the prepared all-solid-state polymer electrolyte are reduced compared with those of example 1, and with the increase of the sodium salt proportion, the electrochemical window, the ion conductivity and the sodium ion migration number are improved to a certain extent, and when EO/Na + When the molar ratio reaches 8:1 (example 6), it exhibits higher ionic conductivity, but the electrochemical window and sodium ion transfer number are reduced, and in combination, the optimal EO/Na ratio is + The molar ratio was 16:1.
(2) By comparing example 1 with comparative examples 6 and 7, it can be found that: too low a sodium salt ratio results in too high a polymer phase viscosity to be sufficiently impregnated into the prepared B-GF functional matrix membrane to obtain a uniform solid electrolyte membrane, and toMeets the requirements of practical application. When the sodium salt ratio is too high (EO/Na + The molar ratio reaches 4:1), the prepared solid electrolyte membrane has no self-supporting property and cannot meet the requirements of practical application.
Comparative example 1: preparation of all-solid Polymer electrolyte CPE
The preparation method of the all-solid-state polymer electrolyte CPE comprises the following steps:
(1) Preparation of composite all-solid polymer electrolyte membrane ex-CPE:
first, the polymers PEO (0.064 mol) and NaTFSI (0.04 mol) were dissolved in 20mL of anhydrous acetonitrile to form a clear homogeneous solution, EO/Na + The molar ratio of (2) is controlled to be 16:1. Then, the pure glass fiber film GF is put into a polytetrafluoroethylene mold, the solution is injected into GF, and acetonitrile is waited for natural volatilization, thus obtaining a preliminary all-solid polymer electrolyte film ex-CPE and storing in an inert atmosphere.
(2) Vacuum hot pressing drying treatment is carried out to prepare the all-solid-state polymer electrolyte CPE:
and (3) placing the ex-SCPE prepared in the step (1) in a buckle type polytetrafluoroethylene mould in a glove box, applying a load of 20N on the mould, transferring the mould into a vacuum drying oven, and hot-pressing and drying the mould at 60 ℃ for 12 hours to finally obtain the all-solid polymer electrolyte CPE.
Performance test:
the ionic conductivity, electrochemical window and sodium ion migration number of the all solid polymer electrolyte prepared in comparative example 1 were tested using the test method in example 1. The electrolyte has a room temperature ionic conductivity of 1.12X10 as tested -4 S cm -1 Electrochemical window was 5.75V vs. Na + Na, sodium ion migration number was 0.22.
Application example 1
This example employs the all-solid polymer electrolyte prepared in example 1, an all-solid sodium ion battery was assembled, and the electrochemical performance of the battery was tested, as follows:
(1) Preparing a positive electrode plate: sodium vanadium phosphate Na 3 V 2 (PO 4 ) 3 Positive electrode active material powder, conductive agent Super P and binder PVDFUniformly mixing according to the mass ratio of 80:10:10, adding a proper amount of N-methyl pyrrolidone (NMP) solution, preparing uniform slurry by stirring and ultrasonic in a room temperature drying environment, coating the slurry on a dry and smooth aluminum foil, transferring to a vacuum drying oven for drying, and finally cutting according to the size for later use.
(2) Preparing a negative electrode plate: sodium metal was used as the negative electrode.
Na prepared in step (1) 3 V 2 (PO 4 ) 3 The positive electrode was made, the negative electrode was made of sodium metal, and the full solid polymer electrolytic SCPE prepared in example 1 was used as an electrolyte, and a 2032 button cell was assembled in a glove box and was designated as cell 1.
Performance test: the battery charge and discharge test was performed at room temperature with a test voltage range of 2.5V to 3.8V, and the test results are shown in fig. 13 and 14. FIG. 13 shows the battery 1 at a current density of 100mA g -1 As can be seen from the charge-discharge curves of the following 1 st turn and 100 th turn, the initial turn discharge specific capacity of the battery 1 is 114.3mAh g -1 The coulombic efficiency was 97.4%, and the capacity retention after 100 cycles was 94.9%, indicating that the battery had good reversibility and cycling stability.
Application example 2
This example employs the all-solid polymer electrolyte prepared in comparative example 1, an all-solid sodium ion battery was assembled, and the electrochemical performance of the battery was tested, as follows:
(1) Preparing a positive electrode plate: sodium vanadium phosphate Na 3 V 2 (PO 4 ) 3 The anode active material powder is uniformly mixed with a conductive agent Super P and a binder PVDF according to the mass ratio of 80:10:10, a proper amount of N-methyl pyrrolidone NMP solution is added, the mixture is ground and stirred into uniform slurry in a room temperature drying environment, the slurry is coated on a dry and flat aluminum foil, the aluminum foil is transferred into a vacuum drying box for drying, and finally, the aluminum foil is cut according to the size for standby.
(2) Preparing a negative electrode plate: sodium metal was used as the negative electrode.
Na prepared in step (1) 3 V 2 (PO 4 ) 3 As positive electrode, metallic sodium as negative electrode, prepared in comparative example 1All solid polymer electrolyte CPE of (2) was used as electrolyte and assembled into 2032 button cell in a glove box, designated as cell 2.
Performance test: and (3) performing battery charge and discharge test at room temperature, wherein the test voltage range is 2.5-3.8V. The test shows that the battery has a current density of 100mA g -1 The discharge specific capacity of the lower first turn is only 104.0mAh g -1 The coulombic efficiency was 93.1% and the capacity retention after 100 cycles was only 77%.
Analysis:
(1) Comparing example 1 with comparative example 1, it can be found that:
in comparative example 1, the glass fiber membrane with the boron-containing organic structure which is not grown in situ is used as a perfusion skeleton, and the prepared all-solid-state polymer electrolyte is found to have poorer electrochemical performance, such as obviously reduced electrochemical window, ion conductivity, sodium ion migration number and the like, compared with example 1.
(2) Comparing application example 1 with application example 2, it can be found that:
the battery 1 prepared using the all-solid polymer electrolyte prepared in example 1 has a remarkable improvement in battery charge-discharge performance, cycle performance, etc., as compared to the battery 2 prepared using the all-solid polymer electrolyte prepared in comparative example 1.
The above description has been given of exemplary embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, or the like, which are within the spirit and principles of the present invention, should be made by those skilled in the art, and are intended to be included within the scope of the present invention.
Claims (18)
1. An all-solid polymer electrolyte characterized by: the all-solid-state polymer electrolyte comprises a functional matrix, a polymer matrix and sodium salt, wherein the functional matrix comprises a boron-containing organic structure and a porous support, and the boron-containing organic structure has rich Lewis acid sites.
2. An all-solid-state polymer electrolyte according to claim 1, characterized in that: the polymer matrix comprises ethoxy groups, and after the polymer matrix is combined with sodium salt, the polymer matrix is infused into the functional matrix.
3. An all-solid-state polymer electrolyte according to claim 1, characterized in that: the polymer matrix is at least one selected from polyethylene oxide PEO and polyphenyl ether PPO.
4. An all-solid-state polymer electrolyte according to claim 1, characterized in that: the sodium salt selects NaClO 4 、NaPF 6 、NaFSI、NaTFSI、NaBF 4 At least one of them.
5. An all-solid-state polymer electrolyte according to claim 1, characterized in that: the functional matrix is a porous support body modified by a boron-containing organic structure, and is obtained by growing the boron-containing organic structure on the surface of the porous support body in situ.
6. An all-solid-state polymer electrolyte according to claim 1, characterized in that: the porous support is at least one selected from glass fiber film, polyimide film, cellulose nonwoven film, polyethylene terephthalate film and polyimide film.
7. An all-solid-state polymer electrolyte according to claim 1, characterized in that: the boron-containing organic structure is selected from any one of compounds having the structural formula shown in the specification:
8. a method of preparing the all-solid-state polymer electrolyte of claim 1, wherein: and taking the porous support as a substrate, preparing the functional matrix by a solution in-situ polymerization method, pouring the mixed solution of the polymer matrix and sodium salt into the functional matrix, and finally obtaining the all-solid polymer electrolyte by vacuum hot-pressing drying treatment.
9. The method for preparing an all-solid-state polymer electrolyte according to claim 8, comprising the steps of:
(1) Preparing a functional matrix:
mixing a boron-containing monomer and a ligand into a solvent to form a precursor mixed solution, immersing the porous support in the precursor mixed solution, and performing in-situ polymerization to obtain a porous support modified by a boron-containing organic structure, namely a functional matrix;
(2) Preparing a composite all-solid polymer electrolyte membrane:
preparing a polymer matrix and sodium salt into a solution according to a certain proportion, and filling the solution into the functional matrix obtained in the step (1) by adopting a solution filling method to obtain a composite all-solid polymer electrolyte membrane;
(3) Vacuum hot pressing and drying treatment:
and (3) placing the composite all-solid polymer electrolyte membrane prepared in the step (2) in a buckle type die, and carrying out vacuum drying treatment to obtain the all-solid polymer electrolyte.
10. The method for preparing an all-solid-state polymer electrolyte according to claim 9, wherein: in the step (1), the boron-containing monomer is selected from any one of 1, 4-phenyldiboronic acid BDBA, biphenyl diboronic acid BPDA,1, 3, 5-phenyltricarbonic acid BTBA,1, 3, 5-phenyl ester (4-phenylboronic acid) BTPA.
11. The method for preparing an all-solid-state polymer electrolyte according to claim 9, wherein: in the step (1), the ligand is selected from any one of 1, 4-phenyldiboronic acid BDBA,2,3,6,7,10, 11-hexahydroxytriphenyl HHTP.
12. The method for preparing an all-solid-state polymer electrolyte according to claim 9, wherein: in the step (1), the solvent is a mixed solution of m-trimethylbenzene and 1, 4-dioxane, and the volume ratio of the m-trimethylbenzene to the 1, 4-dioxane is 0.5-1.5:0.5-1.5.
13. The method for preparing an all-solid-state polymer electrolyte according to claim 9, wherein: in the step (1), the reaction temperature of the in-situ polymerization is 100-150 ℃.
14. The method for preparing an all-solid-state polymer electrolyte according to claim 9, wherein: in the step (1), the time of the in-situ polymerization reaction is 24-96 hours.
15. The method for preparing an all-solid-state polymer electrolyte according to claim 9, wherein: in the step (1), the product obtained by the in-situ polymerization reaction is sealed and preserved after washing, activating and vacuum drying; the washing solvent is anhydrous acetone or anhydrous acetonitrile, and the washing times are 1-4 times; the activating organic solvent is anhydrous acetone, and the activating time is 12-36 h; vacuum drying at 100-150 deg.c for 12-36 hr, and sealing and preserving the prepared functional matrix in inert atmosphere to prevent hydrolysis.
16. The method for preparing an all-solid-state polymer electrolyte according to claim 9, wherein: in the step (2), the polymer matrix is PEO or PPO, and the sodium salt is NaClO 4 、NaPF 6 NaFSI, naTFSI or NaBF 4 The ratio of the polymer matrix to the sodium salt is 8-20:1.
17. The method for preparing an all-solid-state polymer electrolyte according to claim 9, wherein: in the step (3), the load pressure of the button die is 5-50N, and the vacuum drying temperature is 50-80 ℃.
18. Use of an all-solid-state polymer electrolyte according to claim 1 for the preparation of an all-solid-state sodium ion battery.
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