CN111934006B - Intrinsically microporous polyaluminum/borate solid electrolytes and batteries - Google Patents
Intrinsically microporous polyaluminum/borate solid electrolytes and batteries Download PDFInfo
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- CN111934006B CN111934006B CN202010718049.6A CN202010718049A CN111934006B CN 111934006 B CN111934006 B CN 111934006B CN 202010718049 A CN202010718049 A CN 202010718049A CN 111934006 B CN111934006 B CN 111934006B
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 53
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000003446 ligand Substances 0.000 claims abstract description 42
- -1 alkali metal salt Chemical class 0.000 claims abstract description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 125000001424 substituent group Chemical group 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 37
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 14
- 229910052796 boron Inorganic materials 0.000 claims description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004327 boric acid Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Chemical group 0.000 claims description 4
- 239000003495 polar organic solvent Substances 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 37
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 34
- 229910001416 lithium ion Inorganic materials 0.000 description 34
- 238000010494 dissociation reaction Methods 0.000 description 29
- 230000005593 dissociations Effects 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 150000001450 anions Chemical class 0.000 description 12
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 12
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 12
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 239000012634 fragment Substances 0.000 description 7
- 229910003002 lithium salt Inorganic materials 0.000 description 7
- 159000000002 lithium salts Chemical class 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 229910017073 AlLi Inorganic materials 0.000 description 5
- AHLBNYSZXLDEJQ-FWEHEUNISA-N orlistat Chemical compound CCCCCCCCCCC[C@H](OC(=O)[C@H](CC(C)C)NC=O)C[C@@H]1OC(=O)[C@H]1CCCCCC AHLBNYSZXLDEJQ-FWEHEUNISA-N 0.000 description 5
- DGQOCLATAPFASR-UHFFFAOYSA-N tetrahydroxy-1,4-benzoquinone Chemical compound OC1=C(O)C(=O)C(O)=C(O)C1=O DGQOCLATAPFASR-UHFFFAOYSA-N 0.000 description 5
- OHLSHRJUBRUKAN-UHFFFAOYSA-N 2,3-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1O OHLSHRJUBRUKAN-UHFFFAOYSA-N 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 4
- 150000004645 aluminates Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 4
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 3
- RBPSHALMJKDEIL-UHFFFAOYSA-N 2,6-dihydroxycyclohexa-2,5-diene-1,4-dione Chemical compound OC1=CC(=O)C=C(O)C1=O RBPSHALMJKDEIL-UHFFFAOYSA-N 0.000 description 3
- UDKMUSGWGWZJBZ-UHFFFAOYSA-N 3,6-dihydroxyphthalic acid Chemical compound OC(=O)C1=C(O)C=CC(O)=C1C(O)=O UDKMUSGWGWZJBZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229920005570 flexible polymer Polymers 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- MZGVIIXFGJCRDR-UHFFFAOYSA-N 4,6-dihydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(O)C=C1O MZGVIIXFGJCRDR-UHFFFAOYSA-N 0.000 description 2
- 244000114635 Dombeya acutangula Species 0.000 description 2
- OZXYEUNMZNYMDD-UHFFFAOYSA-N OC(C(C(O)=C(C1=O)S(O)(=O)=O)=O)=C1S(O)(=O)=O Chemical compound OC(C(C(O)=C(C1=O)S(O)(=O)=O)=O)=C1S(O)(=O)=O OZXYEUNMZNYMDD-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000348 solid-phase epitaxy Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- UKFMEOHAOCKDOL-UHFFFAOYSA-N 3,4-dihydroxycyclohexa-1,5-diene-1,4-dicarboxylic acid Chemical compound OC1C=C(C(O)=O)C=CC1(O)C(O)=O UKFMEOHAOCKDOL-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- RIUNEBYJXQAXKP-UHFFFAOYSA-N [Li+].B([O-])(O)O.C(C(O)C(O)C(=O)O)(=O)O Chemical compound [Li+].B([O-])(O)O.C(C(O)C(O)C(=O)O)(=O)O RIUNEBYJXQAXKP-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004200 deflagration Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M2300/0088—Composites
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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)
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Abstract
The invention discloses an inherent microporous polyaluminium/borate solid electrolyte and a battery, wherein the inherent microporous polyaluminium/borate solid electrolyte is at least one ligandAr and a coordination atom M form an alkali metal salt of a coordination compound, and the structural formula of a ligand Ar is shown in the specification
At least one ligand Ar is a non-centrosymmetric structure, and the structural formula of the polyaluminium/borate solid electrolyte is shown in the specification
Wherein N represents an alkali metal element, N represents a degree of polymerization, and X represents1、X2Each independently selected from SO2CO or absent, Y is selected from
And Y is selected from-OH, -COOH, -SO3At least 2 substitutions of substituents in H. The non-centrosymmetric ligand is adopted, the structure of the polyaluminium/borate solid electrolyte formed by the ligand is a highly twisted one-dimensional molecular chain, and the molecular chain cannot be tightly stacked in a three-dimensional space, so that inherent micropores are formed, the performance improvement in multiple aspects can be realized by introducing the inherent micropores, and the non-centrosymmetric ligand has a better application prospect in the field of batteries.
Description
Technical Field
The present invention relates to solid electrolytes, and more particularly to an inherently microporous polyaluminium/borate solid electrolyte and battery.
Background
Lithium ion batteries are widely used in smart phones, notebook computers, and electric vehicles due to their excellent properties such as high energy density, long life, and high voltage. With the development of smart phones and notebook computers, such as light weight, thinness, multifunctionality, and large screen, and electric vehicles, the requirements for energy density and safety of batteries are increasing. However, over the last thirty years, the energy density of conventional lithium ion batteries based on liquid electrolytes and intercalation compounds has approached their limits and the space for lift is very limited. Moreover, the conventional liquid electrolyte contains a large amount of combustible solvent, and can cause serious safety problems such as deflagration and even explosion under abnormal conditions.
In order to further improve the energy density and safety of lithium ion batteries, the preparation of all-solid-state lithium ion batteries (ASSLIB) using solid-state electrolytes (SSE) is one of the solutions. ASSLIB is not availableThe liquid solvent of the fuel has the inherent safety higher than that of the traditional liquid electrolyte lithium ion battery, and at least no electrolyte leakage accident occurs. And because no liquid solvent exists, the packaging requirement of ASSLIB is correspondingly lower than that of the traditional liquid electrolyte lithium ion battery, so that the weight proportion of the packaging material in the battery can be reduced, and the energy density of the battery can be improved through phase transformation. Moreover, the SSE has a wide electrochemical stability window, which may exceed 5V, so that ASSLIB can adopt a lithium metal negative electrode with higher specific capacity and more negative potential, and the positive electrode can adopt LiNi with a voltage platform close to 5V0.5Mn1.5O4And the same high voltage positive electrode material, thereby improving the energy density of the battery.
An organic solid electrolyte has the advantages of easy molding, easy formation of good interface contact and the like, and becomes one of research hotspots, wherein the transference number of lithium ions of a single lithium ion conducting solid polymer electrolyte (SLIC-SPE) is close to 1, and the problems of concentration polarization and the like caused by anion accumulation are avoided, so that the performance of the SLIC-SPE in a battery is enough to be comparable to that of a double-ion solid electrolyte with the conductivity more than 10 times, and the organic solid electrolyte is widely concerned. SLIC-SPE refers to SPE in which anions are fixed on a macromolecular skeleton and cannot move, and only lithium ions migrate in a polymer matrix, and the conduction current of the SPE is almost completely borne by the lithium ions. SLIC-SPEs fall into a wide variety of categories, the most common SLIC-SPEs refer to an anion covalently immobilized on a polymer backbone, which anion can be grafted onto or directly present in the backbone. The anion in such SLIC-SPE is usually sulfonimide anion (-SO)2N(－)SO2-) and their derivatives and tetra-coordinated boron/aluminate anions, etc. Wherein the negative charge of the sulfonimide anion can be delocalized over four oxygens and one nitrogen, and thus becomes the most interesting solid electrolyte. However, compared with the four-coordination boric acid/aluminate anions, the sulfonimide anions are difficult to synthesize, so that the synthesis process cost is increased. The tetra-coordinated boric acid/aluminate negative ion has wide research prospect due to the advantages of easily obtained synthetic raw materials, simple process, high thermal stability and the like.
However, the reported tetra-coordinated borate/aluminate anions have insufficient negative charge delocalization and high corresponding lithium ion dissociation energy due to the fact that the adopted ligands are ligands with weak electron-withdrawing ability such as pentaerythritol, tartaric acid and the like, wherein even lithium tartrate borate with low dissociation energy has the dissociation energy of up to 146kcal/mol, and the high dissociation energy means low ionic conductivity.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides the inherent microporous polyaluminium/borate solid electrolyte and the battery, compared with the conventional lithium polyborate, the solid electrolyte can obviously reduce the dissociation energy of lithium ions so as to improve the conductivity of the lithium ions.
The technical scheme adopted by the invention is as follows:
in a first aspect of the invention, there is provided an inherently microporous polyaluminium/borate solid electrolyte which is an alkali metal salt of a coordination compound formed by at least one ligand Ar and a coordinating atom M, wherein the ligand Ar has the formula
At least one ligand Ar is a non-centrosymmetric structure, and the structural formula of the inherent microporous polyaluminium/borate solid electrolyte is shown in the specification
Wherein M represents boron or aluminum, N represents an alkali metal element, N represents a degree of polymerization, and X represents1、X2Each independently selected from SO2CO or absent, Y is selected from
And Y is selected from-OH, -COOH, -SO3At least 2 substituents of H.
n represents the degree of polymerization and can be adjusted according to the ratio of the raw materials added. In some embodiments, n is an integer selected from 1 to 10000. In some embodiments, n is an integer selected from 100 to 10000.
According to some embodiments of the invention, the ligand Ar is selected from
According to some embodiments of the invention, the ligand Ar and the coordinating atom M can form a five-membered ring, a six-membered ring or a seven-membered ring.
According to some embodiments of the invention, the ligand Ar forms MO with the coordinating atom M2C2Five-membered ring, MO2C3Six-membered ring, MO2SC2Six-membered rings or MO2C4A seven-membered ring.
According to some embodiments of the invention, the intrinsically microporous polyaluminium/borate solid state electrolyte is selected from
According to some embodiments of the invention, the alkali metal element is any one of lithium, sodium, and potassium.
In a second aspect of the present invention, there is provided a process for the preparation of the above-described inherently microporous polyaluminium/borate solid state electrolyte, comprising the steps of:
and adding the ligand Ar, boric acid or aluminum hydroxide and alkali into a polar solvent, stirring for reaction, and evaporating to obtain the inherent microporous polyaluminium/borate solid electrolyte.
Examples of the base to be added in the above-mentioned production step include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like.
According to some embodiments of the invention, the polar solvent comprises water or a polar organic solvent.
According to some embodiments of the invention, the polar organic solvent is selected from any one of methanol, ethanol, N-methylpyrrolidone, dimethylsulfoxide, N-dimethylformamide.
In a third aspect of the invention, there is provided a battery comprising an inherently microporous polyaluminium/borate solid state electrolyte as described above.
The embodiment of the invention has the beneficial effects that:
the embodiment of the invention provides an inherent microporous polyaluminium/borate solid electrolyte, wherein a conjugated benzene ring ligand with strong electron-withdrawing capability is selected, so that negative charges of anions are delocalized to the whole main chain, lithium ions are favorably migrated along the main chain, the lithium ion dissociation energy is reduced, and the lithium ion conductivity is improved. Meanwhile, a non-centrosymmetric ligand is adopted, the structure of the formed polyaluminium/borate solid electrolyte is a highly twisted one-dimensional molecular chain, and the molecular chain cannot be tightly stacked in a three-dimensional space, so that inherent micropores are formed.
The introduction of inherent micropores in inherent micropore polyaluminium/borate solid electrolyte (abbreviated as PLAIM/PLBIM) realizes the improvement of various performances. First, the inherent microporosity improves the solubility of the polyaluminum/lithium borate in that the solvents that can dissolve the pliim/PLBIM are more numerous and more soluble. The solubility is a necessary condition for preparing an electrolyte membrane by adopting a solution casting method, and the biggest advantage that the organic solid electrolyte is easy to form is reserved due to the solubility of the PLAIM/PLBIM. Second, the introduction of intrinsic micropores increases the ionic conductivity. Third, the incorporation of intrinsic micropores suppresses crystallization of PLAIM/PLBIM and phase separation problems during film formation. When the PLAIM/PLBIM is mixed with a flexible matrix (such as PEO and the like) to form a membrane, on one hand, the rigid twisted chain segments of the PLAIM/PLBIM prevent the crystallization of the PLAIM/PLBIM, and on the other hand, the inherent micropores can contain PEO and inhibit the crystallization of PEO, so that the influence of the crystallization of PEO on the conductivity of lithium ion is relieved, and the ion conductivity is effectively improved.
Drawings
Fig. 1 is a molecular structure and three-dimensional configuration diagram of solid electrolytes of example 1 and comparative example 1;
fig. 2 is a molecular structure and three-dimensional configuration diagram of solid electrolytes of example 5 and comparative example 2;
fig. 3 is a diagram showing the molecular structure and three-dimensional configuration of the solid electrolytes of example 7 and comparative example 3.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
This example provides a solid electrolyte of lithium poly (2, 3-dihydroxy-1, 4-benzenedicarboxylate borate), (
M is boron atom) according to the following steps:
to 200 g of dimethyl sulfoxide was added 19.80 g of 2, 3-dihydroxy-1, 4-benzenedicarboxylic acid
6.183 g of boric acid and 4.196 g of lithium hydroxide monohydrate are stirred and reacted for 6 hours at room temperature to obtain a pale yellow solution, and the pale yellow solution is subjected to rotary evaporation to obtain the lithium poly-2, 3-dihydroxy-1, 4-phthalate borate.
Structural characterization: the 13C nmr spectra showed formants at chemical shifts of 113.7, 118.0, 143.6 and 156.6ppm, corresponding to carbon on the benzene ring linked to the carboxyl group, carbon on the benzene ring linked to hydrogen, carbon on the benzene ring linked to the straight chain of hydroxyl groups, and carbon on the carboxyl group, respectively. The analysis result of the carbon, hydrogen and nitrogen elements is C: 45.15% and polymer formula (C)8O6BLi) n corresponds to a close theoretical carbon content (45.28%) and thus, the structural correctness of the resulting lithium poly-2, 3-dihydroxy-1, 4-benzenedicarboxylate borate is demonstrated.
Calculating dissociation energy: adopting a density functional method, and simulating a prepared poly-2, 3-dihydroxy-1, 4-phthalic acid lithium borate structure by Gaussian09 (Vision B.01) software, wherein MO is formed by a ligand and a boron atom2C3Six-membered ring, calculating lithium ion dissociation energy E from optimized configurationd(EdEqualing yinAdding lithium ion energy into the ion energy and then subtracting lithium salt energy), wherein B3LYP/6-31+ G (d) is adopted as the optimized configuration, B3LYP/6-311+ G (2df) is adopted as the energy of the optimized configuration, and the dissociation energy of the lithium poly-2, 3-dihydroxy-1, 4-benzene dicarboxylate borate is calculated to be 117 kcal/mol.
Comparative example 1: comparative example 1 use of a centrosymmetric ligand 2, 5-dihydroxyterephthalic acid
Synthesizing a solid electrolyte of the lithium polyborate according to the following steps: adding 19.80 g of 2, 5-dihydroxy terephthalic acid, 6.183 g of boric acid and 4.196 g of lithium hydroxide monohydrate into 200 g of dimethyl sulfoxide, stirring and reacting for 6 hours at room temperature to obtain a light yellow solution, and performing rotary evaporation to obtain the lithium polyborate solid electrolyte.
Simulating the three-dimensional molecular configurations of the lithium poly-2, 3-dihydroxy-1, 4-benzenedicarboxylate borate prepared in example 1 and the lithium polyborate solid electrolyte prepared in comparative example 1 by using gaussian software, simulating the accumulation of molecular chains in a three-dimensional space by using a molecular fragment containing 6 repeating units and taking a benzene ring as a terminal group as a structural model, the molecular structure fragment and the three-dimensional configuration schematic diagram are shown in figure 1, wherein white spheres, gray spheres, red spheres, pink spheres, yellow spheres and purple spheres represent hydrogen, carbon, oxygen, boron, sulfur and lithium ions respectively, while comparative example 1 uses a centrosymmetric ligand to form a linear polymer (as shown in a of fig. 1), example 1 uses a non-centrosymmetric ligand to form a structural segment that is highly twisted and cannot be densely packed in three-dimensional space, thereby forming intrinsic micropores (as shown in B of fig. 1).
In the prior art, when polyaluminium acid/lithium borate is used as a solid electrolyte alone, the problems of poor film forming performance, low ionic conductivity and the like exist, and in order to improve the problems, the polyaluminium acid/lithium borate is usually required to be blended with some flexible polymers to form a composite film, wherein common flexible polymers comprise polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (PTFE-HFP) and the like. However, the solid electrolyte has poor compatibility with these flexible polymers, and there are problems such as crystallization and phase separation during film formation, and it is difficult to form a solid electrolyte membrane having a uniform molecular level. The inherent micropore polyaluminium/borate solid electrolyte provided by the embodiment of the invention has no problems of crystallization, phase separation and the like when being compounded with a substrate such as PEO and the like to form a film due to the introduction of the inherent micropore, and can form a solid electrolyte film with uniform molecular level by adopting a simple solution mixing method, thereby having obvious advantages.
Example 2
This example provides a lithium poly (2, 3-dihydroxy-1, 4-benzenedicarboxylate) aluminate solid electrolyte
M is aluminum atom) according to the following steps:
to 200 g of dimethyl sulfoxide was added 19.80 g of 2, 3-dihydroxy-1, 4-benzenedicarboxylic acid
7.800 g of aluminum hydroxide and 4.196 g of lithium hydroxide monohydrate are stirred and reacted for 6 hours at 100 ℃ to obtain light yellow solution, and the light yellow solution is rotated and evaporated to obtain the poly-2, 3-dihydroxy-1, 4-phthalic acid lithium aluminate.
Structural characterization: the 13C nmr spectra showed formants at chemical shifts 118.4, 143.9, and 175.8ppm, corresponding to the benzene ring carbon, the benzene ring carbon that is linear with the hydroxyl group, and the carboxyl group carbon, respectively. The analysis result of the carbon, hydrogen and nitrogen elements is C: 42.05% and polymer formula (C)8O6The theoretical carbon content (42.11%) corresponding to AlLi) n is close, thus proving that the structure of the obtained lithium aluminate poly-2, 3-dihydroxy-1, 4-benzenedicarboxylate is correct.
Calculating dissociation energy: adopting a density functional method, simulating the prepared poly-2, 3-dihydroxy-1, 4-phthalic acid lithium aluminum acid structure by Gaussian09 (Vision B.01) software, wherein MO is formed by a ligand and an aluminum atom2C3Six-membered ring, calculating lithium ion dissociation energy E from optimized configurationd(EdEqual to the energy of the anion plus the energy of the lithium ion minus the energy of the lithium salt), wherein B3LYP/6-31+ G (d) is adopted for optimizing the configuration, B3LYP/6-311+ G (2df) is adopted for calculating the energy of the optimized configuration, and the lithium aluminate of the poly-2, 3-dihydroxy-1, 4-phthalic acid is obtained by calculationThe dissociation energy was 121 kcal/mol.
Example 3
This example provides a solid electrolyte of lithium poly (3, 6-dihydroxy-1, 2-benzenedicarboxylate borate), (
M is boron atom) according to the following steps:
to 200 g of dimethyl sulfoxide was added 19.80 g of 3, 6-dihydroxy-1, 2-benzenedicarboxylic acid
6.183 g of boric acid and 4.196 g of lithium hydroxide monohydrate are stirred and reacted for 6 hours at room temperature to obtain a pale yellow solution, and the pale yellow solution is subjected to rotary evaporation to obtain the lithium poly-3, 6-dihydroxy-1, 2-phthalate borate.
Structural characterization: the 13C nuclear magnetic resonance spectrum shows formants at chemical shifts of 108.2, 124.4, 149.9 and 162.7ppm, corresponding to carbon linked to carboxyl on the benzene ring, carbon linked to hydrogen on the benzene ring, carbon linked to a straight chain of hydroxyl on the benzene ring, and carboxyl carbon, respectively. The analysis result of the carbon, hydrogen and nitrogen elements is C: 45.15% and polymer formula (C)8O6BLi) n corresponds to a close theoretical carbon content (45.28%) and thus, the structural correctness of the resulting lithium poly-3, 6-dihydroxy-1, 2-benzenedicarboxylate borate is demonstrated.
Calculating dissociation energy: adopting a density functional method, and simulating a prepared poly-3, 6-dihydroxy-1, 2-phthalic acid lithium borate structure by Gaussian09 (Vision B.01) software, wherein MO is formed by a ligand and a boron atom2C3Six-membered ring, calculating lithium ion dissociation energy E from optimized configurationd(EdEqual to the anion energy plus the lithium ion energy minus the lithium salt energy), wherein B3LYP/6-31+ G (d) is adopted as the optimized configuration, B3LYP/6-311+ G (2df) is adopted as the energy of the optimized configuration, and the dissociation energy of the lithium poly-3, 6-dihydroxy-1, 2-phthalate borate is calculated to be 116 kcal/mol.
Example 4
This example provides a solid lithium poly (3, 6-dihydroxy-1, 2-benzenedicarboxylate) electrolyte
M is aluminum atom) according to the following steps:
to 200 g of dimethyl sulfoxide was added 19.80 g of 3, 6-dihydroxy-1, 2-benzenedicarboxylic acid
7.800 g of aluminum hydroxide and 4.196 g of lithium hydroxide monohydrate are stirred and reacted for 6 hours at 100 ℃ to obtain light yellow solution, and the light yellow solution is rotated and evaporated to obtain the poly-3, 6-dihydroxy-1, 2-phthalic acid lithium aluminate.
Structural characterization: the 13C nuclear magnetic resonance spectrum shows formants at chemical shifts of 115.2, 126.5, 151.3 and 179.7ppm, corresponding to carbon linked to carboxyl on the benzene ring, carbon linked to hydrogen on the benzene ring, carbon linked to a straight chain of hydroxyl on the benzene ring, and carboxyl carbon, respectively. The analysis result of the carbon, hydrogen and nitrogen elements is C: 42.05% and polymer formula (C)8O6The theoretical carbon content (42.11%) corresponding to AlLi) n is close, thus proving that the structure of the obtained lithium aluminate poly-3, 6-dihydroxy-1, 2-benzenedicarboxylate is correct.
Calculating dissociation energy: adopting a density functional method, and simulating and preparing the poly-lithium 3, 6-dihydroxy-1, 2-benzene dicarboxylic acid aluminate by Gaussian09 (Vision B.01) software, wherein MO is formed by a ligand and an aluminum atom2C3Six-membered ring, calculating lithium ion dissociation energy E from optimized configurationd(EdEqual to the anion energy plus the lithium ion energy minus the lithium salt energy), wherein B3LYP/6-31+ G (d) is adopted as the optimized configuration, B3LYP/6-311+ G (2df) is adopted as the energy of the optimized configuration, and the dissociation energy of the poly-3, 6-dihydroxy-1, 2-phthalic acid lithium aluminate is calculated to be 124 kcal/mol.
Example 5
This example provides a solid electrolyte of lithium poly (3, 5-dihydroxy-p-benzoquinone) -2, 6-disulfonate borate (II)
M is boron atom) according to the following steps:
33.20 g of 3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonic acid are added to 200 g of methanol
6.183 g of boric acid and 4.196 g of lithium hydroxide monohydrate are stirred and reacted for 6 hours at room temperature to obtain a light yellow solution, and the light yellow solution is rotated and evaporated to obtain the lithium poly-3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonate borate.
Structural characterization: the 13C nmr spectra showed formants at chemical shifts 123.2, 149.5 and 175.3ppm, corresponding to the carbon attached to the sulfonic acid group, the carbon attached to the hydroxyl group and the carbonyl carbon on the benzene ring, respectively. The analysis result of the carbon, hydrogen and nitrogen elements is C: 22.52% of the formula (C) with polymer6S2O10The theoretical carbon content (22.93%) corresponding to BLi) n was close, thus confirming that the structure of the obtained lithium poly-3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonate borate was correct.
Calculating dissociation energy: adopting a density functional method, simulating and preparing a lithium poly-3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonate borate structure by using Gaussian09(Revision B.01) software, wherein MO is formed by a ligand and a boron atom2SC2Six-membered ring, calculating lithium ion dissociation energy E from optimized configurationd(EdEqual to the energy of anions plus the energy of lithium ions minus the energy of lithium salts), wherein B3LYP/6-31+ G (d) is adopted for optimizing the configuration, B3LYP/6-311+ G (2df) is adopted for calculating the energy of the optimized configuration, and the dissociation energy of the lithium poly-3, 5-dihydroxy p-benzoquinone-2, 6-disulfonate borate is calculated to be 115 kcal/mol.
Comparative example 2: comparative example 2 use of the centrosymmetric ligand 2, 5-dihydroxy-p-benzoquinone-4, 6-disulfonic acid
Synthesizing a solid electrolyte of the lithium polyborate according to the following steps: 33.20 g of 2, 5-dihydroxy p-benzoquinone-4, 6-disulfonic acid, 6.183 g of boric acid and 4.196 g of lithium hydroxide monohydrate are added into 200 g of dimethyl sulfoxide, stirred and reacted for 6 hours at room temperature to obtain a light yellow solution, and the light yellow solution is subjected to rotary evaporation to obtain the lithium polyborate solid electrolyte.
Simulating the three-dimensional molecular configuration of the lithium poly-3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonate borate prepared in example 5 and the lithium polyborate solid electrolyte prepared in comparative example 2 by using gaussian software, selecting B3LYP/6-31+ G (d) functional and group, using a molecular fragment containing 6 repeating units and taking a benzene ring as a terminal group as a structural model, simulating the accumulation of molecular chains in a three-dimensional space, wherein the molecular structural fragment and the three-dimensional configuration schematic diagram are shown in FIG. 2, white balls, gray balls, red balls, pink balls, yellow balls and purple balls in the figure represent hydrogen, carbon, oxygen, boron, sulfur and lithium ions respectively, a centrosymmetric ligand is used in comparative example 2 to form a linear polymer (shown as C in FIG. 2), while the structural fragment formed by a non-centrosymmetric ligand in example 6 is highly twisted and cannot be tightly accumulated in the three-dimensional space, thereby forming intrinsic micropores (as shown at D in fig. 2).
Example 6
This example provides a lithium poly (3, 5-dihydroxy-p-benzoquinone) -2, 6-disulfonate aluminate solid electrolyte
M is aluminum atom) according to the following steps:
33.20 g of 3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonic acid are added to 200 g of N-methylpyrrolidone
7.800 g of aluminum hydroxide and 4.196 g of lithium hydroxide monohydrate are stirred and reacted for 6 hours at the temperature of 100 ℃ to obtain light yellow solution, and the light yellow solution is rotated and evaporated to obtain the poly-3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonic acid lithium aluminate.
Structural characterization:13c nuclear magnetic resonance spectrum shows formants at chemical shifts of 125.8, 151.1 and 174.3ppm, corresponding to the carbon attached to the sulfonic acid group, the carbon attached to the hydroxyl group and the carbonyl carbon on the benzene ring, respectively. The analysis result of the carbon, hydrogen and nitrogen elements is C: 21.61% of formula (C) with polymer6S2O10The theoretical carbon content (21.82%) corresponding to AlLi) n is close, thus proving that the structure of the obtained lithium aluminate poly-3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonate is correct.
Calculating dissociation energy: the 3, 5-dihydroxy p-benzoquinone is prepared by adopting a density functional method and simulating with Gaussian09 (Vision B.01) softwareLithium aluminate 2, 6-disulfonate, the ligand forming with the aluminum atom MO2SC2Six-membered ring, calculating lithium ion dissociation energy E from optimized configurationd(EdEqual to the energy of anions plus the energy of lithium ions minus the energy of lithium salts), wherein B3LYP/6-31+ G (d) is adopted for optimizing the configuration, B3LYP/6-311+ G (2df) is adopted for calculating the energy of the optimized configuration, and the dissociation energy of the poly-3, 5-dihydroxy p-benzoquinone-2, 6-disulfonic acid lithium aluminate is calculated to be 111 kcal/mol.
Example 7
This example provides a copolymer solid electrolyte, synthesized according to the following steps:
to 200 g of N-methylpyrrolidone was added 8.60 g of tetrahydroxybenzoquinone (A)
Symmetrical ligand), 9.90 g of 2, 3-dihydroxy-1, 4-benzenedicarboxylic acid
7.800 g of aluminum hydroxide and 4.196 g of lithium hydroxide monohydrate are stirred and reacted for 6 hours under the condition of 100 ℃ to obtain a reddish brown solution, and the solution is rotated and evaporated to obtain the lithium copolyoaluminate.
Structural characterization: the 13C nmr spectrum showed formants at chemical shifts 115.1, 118.2, 126.3, 143.7, 151.1, 175.8, 179.7 ppm. The analysis result of the carbon, hydrogen and nitrogen elements is C: 36.01% of a polymer of the formula (C)7O6The theoretical carbon content (36.27%) for AlLi) n is close, and therefore the resulting polymer is a copolymer, rather than a mixture of two polymers.
Comparative example 3: comparative example 3 use of a centrosymmetric ligand tetrahydroxybenzoquinone
Synthesizing a solid electrolyte of the lithium polyborate according to the following steps: adding 17.20 g of tetrahydroxybenzoquinone, 6.183 g of boric acid and 4.196 g of lithium hydroxide monohydrate into 200 g of water, stirring and reacting for 6 hours at room temperature to obtain a reddish brown solution, and performing rotary evaporation to obtain the lithium polyborate solid electrolyte.
Simulating three-dimensional molecular configurations of the copolymer solid electrolyte prepared in example 7 and the lithium polyborate solid electrolyte prepared in comparative example 3 by using gaussian software, selecting B3LYP/6-31+ G (d) functional and group, using a molecular fragment containing 6 repeating units and taking a benzene ring as a terminal group as a structural model, simulating the accumulation of a molecular chain in a three-dimensional space, wherein the schematic diagram of the molecular structure fragment and the three-dimensional configuration is shown in FIG. 3, white balls, gray balls, red balls, pink balls, yellow balls and purple balls in the figure represent hydrogen, carbon, oxygen, boron, sulfur and lithium ions respectively, the molecular structure of the lithium polyborate solid electrolyte of comparative example 3 is shown in A in FIG. 3, and a linear polymer (see B in FIG. 3) is formed by using a centrosymmetric ligand such as tetrahydroxybenzoquinone in comparative example 3, and is generally a dense and non-porous polymer; on the other hand, as shown in fig. 3C, when asymmetric monomers such as o-dihydroxy terephthalic acid and tetrahydroxybenzoquinone are copolymerized, the obtained polymer is a highly twisted molecular chain, and cannot be tightly packed in a three-dimensional space, so that intrinsic micropores are formed (see fig. 3D). The result shows that the asymmetric ligand and the symmetric ligand are copolymerized, the regular molecular configuration formed by the symmetric ligand can be inhibited, and the inherent microporous polymer solid electrolyte is formed.
Example 8
This example provides a solid electrolyte of lithium poly (4, 6-dihydroxy-1, 3-benzenedicarboxylate borate), (b
M is boron atom) according to the following steps:
to 200 g of dimethyl sulfoxide was added 19.80 g of 4, 6-dihydroxy-1, 3-benzenedicarboxylic acid
6.183 g of boric acid and 4.196 g of lithium hydroxide monohydrate are stirred and reacted for 6 hours at room temperature to obtain a pale yellow solution, and the pale yellow solution is subjected to rotary evaporation to obtain the lithium poly-4, 6-dihydroxy-1, 3-phthalate borate.
Structural characterization:13c nuclear magnetic resonance spectrum at chemical shifts of 103.1, 105.1, 136.1, 155.1 and 1596ppm presents a resonance peak, and the analysis result of the hydrocarbon nitrogen element is C: 45.15% and polymer formula (C)8O6BLi) n corresponds to a close theoretical carbon content (45.28%) and thus, the structural correctness of the resulting lithium poly-4, 6-dihydroxy-1, 3-benzenedicarboxylate borate is demonstrated.
Calculating dissociation energy: adopting a density functional method, and simulating a prepared poly-4, 6-dihydroxy-1, 3-phthalic acid lithium borate structure by Gaussian09 (Vision B.01) software, wherein MO is formed by a ligand and a boron atom2C3Six-membered ring, calculating lithium ion dissociation energy E from optimized configurationd(EdEqual to the anion energy plus the lithium ion energy minus the lithium salt energy), the dissociation energy of the poly-4, 6-dihydroxy-1, 3-phthalic acid lithium borate is calculated by a density functional function method to be 130 kcal/mol.
Example 9
This example provides a lithium poly (4, 6-dihydroxy-1, 3-benzenedicarboxylate) solid electrolyte
M is aluminum atom) according to the following steps:
adding 19.80 g of 4, 6-dihydroxy-1, 3-phthalic acid, 7.800 g of aluminum hydroxide and 4.196 g of lithium hydroxide monohydrate into 200 g of dimethyl sulfoxide, stirring and reacting for 6 hours at 100 ℃ to obtain a light yellow solution, and performing rotary evaporation to obtain the lithium aluminate poly-4, 6-dihydroxy-1, 3-phthalic acid.
Structural characterization:13the C nmr spectra showed peaks at chemical shifts 105.2, 113.1, 134.5, 161.4 and 174.3ppm, which are assigned as shown. The analysis result of the carbon, hydrogen and nitrogen elements is C: 42.05% and polymer formula (C)8O6The theoretical carbon content (42.11%) corresponding to AlLi) n was close, thus demonstrating that the structure of the resulting lithium poly-4, 6-dihydroxy-1, 3-benzenedicarboxylate aluminate was correct.
Calculating dissociation energy: the dissociation energy of the poly-4, 6-dihydroxy-1, 3-phthalic acid lithium aluminate calculated by a density functional method is 144 kcal/mol.
Claims (10)
1. Inherent micropore polyaluminiumThe inherent microporous polyaluminium/borate solid electrolyte is characterized in that the inherent microporous polyaluminium/borate solid electrolyte is an alkali metal salt of a coordination compound formed by at least one ligand Ar and a coordination atom M, and the structural formula of the ligand Ar is shown in the specification
At least one of the ligands Ar is a non-centrosymmetric structure,
the inherent micropore polyaluminium/borate solid electrolyte has a structural formula
Wherein M represents boron or aluminum, N represents an alkali metal element, N represents a degree of polymerization, and X represents1、X2Each independently selected from SO2CO or absent, Y is selected from
And Y is selected from-OH, -COOH, -SO3At least 2 substituents of H; n is an integer selected from 1 to 10000.
2. The intrinsically microporous polyaluminum/borate solid state electrolyte of claim 1, wherein the ligand Ar is selected from the group consisting of
3. The intrinsically microporous polyaluminium/borate solid state electrolyte of claim 1, wherein the ligand Ar and the coordinating atom M are capable of forming a five-, six-or seven-membered ring.
4. The intrinsically microporous polyaluminum/borate solid-state electrolyte of claim 3, wherein the ligand Ar forms MO with the coordinating atom M2C2Five-membered ring, MO2C3Six-membered ring, MO2SC2Six-membered rings or MO2C4A seven-membered ring.
5. The inherently microporous polyaluminum/borate solid-state electrolyte of claim 4, wherein said inherently microporous polyaluminum/borate solid-state electrolyte is selected from the group consisting of
6. The intrinsically microporous polyaluminium/borate solid state electrolyte of claim 1, wherein the alkali metal element is any one of lithium, sodium, and potassium.
7. A method of making the inherently microporous polyaluminium/borate solid state electrolyte of any of claims 1 to 6 comprising the steps of:
and adding the ligand Ar, boric acid or aluminum hydroxide and alkali into a polar solvent, stirring for reaction, and evaporating to obtain the inherent microporous polyaluminium/borate solid electrolyte.
8. The method of making an inherently microporous polyaluminium/borate solid state electrolyte of claim 7 wherein the polar solvent comprises water or a polar organic solvent.
9. The method of claim 8, wherein the polar organic solvent is selected from any one of methanol, ethanol, N-methylpyrrolidone, dimethylsulfoxide, and N, N-dimethylformamide.
10. A battery comprising the inherently microporous polyaluminium/borate solid state electrolyte of any of claims 1 to 6.
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