CN112072170B - Polyaluminium/borate solid electrolyte and battery - Google Patents
Polyaluminium/borate solid electrolyte and battery Download PDFInfo
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- CN112072170B CN112072170B CN202010716669.6A CN202010716669A CN112072170B CN 112072170 B CN112072170 B CN 112072170B CN 202010716669 A CN202010716669 A CN 202010716669A CN 112072170 B CN112072170 B CN 112072170B
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- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 33
- -1 alkali metal salt Chemical class 0.000 claims abstract description 26
- 239000003446 ligand Substances 0.000 claims abstract description 24
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 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
- 238000000034 method Methods 0.000 claims description 22
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 19
- 229910052796 boron Inorganic materials 0.000 claims description 18
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 13
- 239000004327 boric acid Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000003495 polar organic solvent Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Chemical group 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 2
- 238000010494 dissociation reaction Methods 0.000 abstract description 39
- 230000005593 dissociations Effects 0.000 abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 31
- 150000001450 anions Chemical class 0.000 abstract description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 32
- 229910052744 lithium Inorganic materials 0.000 description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 238000004458 analytical method Methods 0.000 description 13
- 238000012512 characterization method Methods 0.000 description 13
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 13
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 13
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 238000002390 rotary evaporation Methods 0.000 description 9
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 8
- 229910003002 lithium salt Inorganic materials 0.000 description 8
- 159000000002 lithium salts Chemical class 0.000 description 8
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 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 6
- 229910017073 AlLi Inorganic materials 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000004645 aluminates Chemical class 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- 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
- 150000001721 carbon Chemical group 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 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 3
- 125000003373 pyrazinyl group Chemical group 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LLBCORSXWFNZTJ-UHFFFAOYSA-N 2,5-dihydroxy-3,6-dioxocyclohexa-1,4-diene-1,4-disulfonic acid Chemical compound OC1=C(S(O)(=O)=O)C(=O)C(O)=C(S(O)(=O)=O)C1=O LLBCORSXWFNZTJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000004057 DFT-B3LYP calculation Methods 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
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CYCSKUSVYWLWTQ-UHFFFAOYSA-L [O-]C(C(C(O)=C1)=CC(C([O-])=O)=C1O)=O.[Li+].[Li+] Chemical compound [O-]C(C(C(O)=C1)=CC(C([O-])=O)=C1O)=O.[Li+].[Li+] CYCSKUSVYWLWTQ-UHFFFAOYSA-L 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- RTHVZRHBNXZKKB-UHFFFAOYSA-N pyrazine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=NC(C(O)=O)=C(C(O)=O)N=C1C(O)=O RTHVZRHBNXZKKB-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000348 solid-phase epitaxy Methods 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- 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 1
- QFSYADJLNBHAKO-UHFFFAOYSA-N 2,5-dihydroxy-1,4-benzoquinone Chemical compound OC1=CC(=O)C(O)=CC1=O QFSYADJLNBHAKO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NZNWEZSBNXMTHN-UHFFFAOYSA-N 5,6-dihydroxy-1,4-dihydropyrazine-2,3-dione Chemical compound OC=1NC(=O)C(=O)NC=1O NZNWEZSBNXMTHN-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
- 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 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- UYQMSQMCIYSXOW-UHFFFAOYSA-N benzene-1,2,4,5-tetrol Chemical compound OC1=CC(O)=C(O)C=C1O UYQMSQMCIYSXOW-UHFFFAOYSA-N 0.000 description 1
- UOILWQFXCNATKR-UHFFFAOYSA-N boric acid;pyrazine Chemical compound OB(O)O.C1=CN=CC=N1 UOILWQFXCNATKR-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000004200 deflagration Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material 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
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 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
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
- H01M10/052—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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
Abstract
本发明公开了一种聚铝/硼酸盐固态电解质和一种电池，所述聚铝/硼酸盐固态电解质为至少一个配体Ar与配位原子M形成配位化合物的碱金属盐，所述配体Ar的结构式为所述聚铝/硼酸盐固态电解质的结构式为其中N表示碱金属元素，n表示聚合度，X1、X2各自独立地选自SO2、CO或不存在，Y选自或且Y被选自‑OH、‑COOH、‑SO3H中的取代基的至少2个取代。本发明使用具有强吸电子能力且共轭的苯环类单体配体，使阴离子的负电荷离域到整个主链上，有利于锂离子沿主链迁移，从而降低锂离子离解能并提高锂离子电导率，在电池领域具有较好的应用前景。The invention discloses a polyaluminum/borate solid electrolyte and a battery. The polyaluminum/borate solid electrolyte is an alkali metal salt in which at least one ligand Ar and a coordination atom M form a coordination compound. The structural formula of the ligand Ar is The structural formula of the polyaluminum/borate solid electrolyte is wherein N represents an alkali metal element, n represents the degree of polymerization, X 1 and X 2 are each independently selected from SO 2 , CO or absent, and Y is selected from or And Y is substituted with at least 2 substituents selected from -OH, -COOH, and -SO 3 H. The invention uses a conjugated benzene ring monomer ligand with strong electron withdrawing ability, so that the negative charge of the anion is delocalized to the entire main chain, which is beneficial to the migration of lithium ions along the main chain, thereby reducing the dissociation energy of lithium ions and improving Lithium-ion conductivity has good application prospects in the field of batteries.
Description
Technical Field
The present invention relates to solid electrolytes, and more particularly to a polyaluminium/borate solid electrolyte and a 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, all-solid-state lithium ion batteries (ASS) are prepared using solid-state electrolytes (SSE)LIB) is one of the solutions. ASSLIB has no flammable liquid solvent, so that the inherent safety of ASSLIB is higher than that of a 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.
Organic solid electrolytes have the advantages of easy molding, easy formation of good interface contact and the like, and become one of the 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 SLIC-SPE is widely concerned in a battery, and the performance of the SLIC-SPE in a dual-ion solid electrolyte is equal to or more than 10 times of the conductivity. 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 are divided into a large number of classes, the most common SLIC-SPEs refer to the immobilization of anions on a polymer backbone by covalent bonds, which anions can be grafted onto the backbone or be present directly 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, thus becoming 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 boric acid/aluminate negative ion has insufficient negative charge delocalization and high corresponding lithium ion dissociation energy due to the fact that the adopted ligand is a ligand 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, and the ionic conductivity of the current solid electrolyte still needs to be improved.
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 polyaluminium/borate solid electrolyte and the battery, and the series of polyaluminium/borate solid electrolytes have lower dissociation energy, so that the polyaluminium/borate solid electrolytes have higher ionic conductivity and better application prospect in the field of batteries.
The technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, there is provided a polyaluminium/borate solid electrolyte, which is an alkali metal salt of a coordination compound formed by at least one ligand Ar and a coordination atom M, wherein the ligand Ar has a formula of
The structural formula of the 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 substitutions of substituents in 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.
Examples of the alkali metal element represented by N include lithium, sodium, and potassium, and the polyaluminium/borate solid electrolyte formed correspondingly includes lithium salt, sodium salt, and potassium salt.
According to some embodiments of the invention, Y is selected from
When, X1、X2At least one of them being SO2Or X1、 X2None are present.
According to some embodiments of the invention, the ligand Ar is a centrosymmetric structure.
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 polyaluminium/borate solid state electrolyte is selected from
Wherein the coordinating atom M (boron atom or aluminum atom) is in a 4-coordinate configuration, similar to a spiro carbon atom.
In a second aspect of the present invention, there is provided a method for preparing the polyaluminium/borate solid 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 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. The polycondensation reaction of the aluminum/borate solid electrolyte is a reversible dehydration reaction, and the aluminum/borate solid electrolyte can be polymerized along with the evaporation of water in the aqueous solution reaction, and the polycondensation is more facilitated in the 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 the polyaluminium/borate solid electrolyte described above.
The embodiment of the invention has the beneficial effects that:
the embodiment of the invention provides a polyaluminium/borate solid electrolyte, which uses conjugated benzene ring ligands with strong electron-withdrawing capability to delocalize negative charges of anions to the whole main chain, and is beneficial to the migration of lithium ions along the main chain, thereby reducing the dissociation energy of the lithium ions and improving the conductivity of the lithium ions. The series polyaluminium/borate solid electrolytes provided by the embodiment of the invention have lower dissociation energy, can be as low as 105kcal/mol, and is far lower than 146kcal/mol and LiPF of lithium tartrate borate6137 kcal/mol, even less than 111kcal/mol of lithium bis (oxalato) borate, and the solid electrolyte is superior to the reported polyborate solid electrolyte and has better application prospect in the field of batteries.
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 other embodiments obtained by those skilled in the art without inventive efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
This example provides a poly (lithium tetrahydroxybenzoquinone) borate
M is boron atom) according to the following steps:
adding 17.20 g of tetrahydroxybenzoquinone into 200 g of water
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 reddish brown solution, and the solution is subjected to rotary evaporation to obtain the lithium poly (tetrahydroxybenzoquinone) borate which is reddish brown powder.
Structural characterization:13the C nmr spectrum showed formants at chemical shifts 138.5 and 169.0ppm, corresponding to the hydroxyl and carbonyl carbons, respectively. The analysis result of the carbon, hydrogen and nitrogen elements is C: 38.43% and polymer formula (C)6O6BLi) n corresponds to a close theoretical carbon content (38.71%), thus proving the correct structure of the resulting lithium polytetrahydroxybenzoquinone borate.
Calculating dissociation energy: adopting a density functional method, and simulating a prepared poly-tetrahydroxybenzoquinone lithium borate structure by using Gaussian09 (Vision B.01) software, wherein MO is formed by a ligand and a boron atom2C2Five-membered ring, calculating the dissociation energy E of lithium ion from the 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 (tetrahydroxybenzoquinone) borate is calculated to be 122 kcal/mol.
Example 2
This example provides a poly (lithium tetrahydroxybenzoquinone) aluminate
M is aluminum atom) according to the following steps:
adding 17.20 g of tetrahydroxybenzoquinone, 7.800 g of aluminum hydroxide 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 poly-tetrahydroxybenzoquinone lithium aluminate.
Structural characterization:13the C nmr spectrum showed formants at chemical shifts of 143.2 and 175.3ppm, corresponding to the hydroxyl and carbonyl carbons, respectively. The analysis result of the carbon, hydrogen and nitrogen elements is C: 35.18% of a polymer of the formula (C)6O6The theoretical carbon content (35.64%) corresponding to AlLi) n is close, thus proving that the structure of the obtained lithium polyhydroxybenzoquinone aluminate is correct.
Calculating dissociation energy: the dissociation energy of the poly-tetrahydroxybenzoquinone lithium aluminate calculated by a density functional method is 124 kcal/mol.
Example 3
This example provides a poly (lithium 4, 6-dihydroxy-1, 3-benzenedicarboxylate) borate
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-phthalic acid borate.
Structural characterization:13the C nuclear magnetic resonance spectrum has resonance peaks at chemical shifts of 103.1, 105.1, 136.1, 155.1 and 159.6ppm, and the analysis result of hydrocarbon 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-4, 6-dihydroxy-1, 3-benzenedicarboxylate borate was demonstrated.
Calculating dissociation energy: the poly 4, 6-dihydroxy-1, 3-benzenediol is prepared by adopting a density functional method and simulating with Gaussian09 (Vision B.01) softwareThe lithium formate-borate structure, ligand and boron atom form MO2C3Six-membered ring, calculating the lithium ion dissociation energy E from the 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 to be 130kcal/mol by adopting a density functional function method.
Example 4
This example provides a poly (lithium 4, 6-dihydroxy-1, 3-benzenedicarboxylate) aluminate
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 spectrum showed peaks at chemical shifts of 105.2, 113.1, 134.5, 161.4 and 174.3 ppm. 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.
Example 5
This example provides a lithium poly (2, 5-dihydroxy-p-benzoquinone) -3, 6-disulfonate borate
M is boron atom) according to the following steps:
33.20 g of 2, 5-dihydroxy-p-benzoquinone-3, 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-2, 5-dihydroxy-p-benzoquinone-3, 6-disulfonate borate.
Structural characterization:13the C nmr spectrum showed formants at chemical shifts of 121.3, 157.8 and 169.8ppm, corresponding to the hydroxy carbon, the carbon directly attached to the sulfonic acid group and the carbonyl carbon, respectively. The analysis result of the carbon, hydrogen and nitrogen elements is C: 22.52% of the formula (C) with polymer6S2O10BLi)nThe corresponding theoretical carbon contents (22.93%) are close, thus proving that the structure of the obtained lithium poly-2, 5-dihydroxy-p-benzoquinone-3, 6-disulfonate borate is correct.
Calculating dissociation energy: adopting a density functional method, simulating and preparing a lithium poly-2, 5-dihydroxy-p-benzoquinone-3, 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 sum of the anion energy and the lithium ion energy, and then the lithium salt energy is subtracted), the dissociation energy of the poly-2, 5-dihydroxy-p-benzoquinone-3, 6-disulfonic acid lithium borate is calculated by adopting a density-function method and is 119 kcal/mol.
Example 6
This example provides a poly (lithium 2, 5-dihydroxy-p-benzoquinone) -3, 6-disulfonate aluminate
M is aluminum atom) according to the following steps:
33.20 g of 2, 5-dihydroxy p-benzoquinone-3, 6-disulfonic acid, 7.800 g of aluminum hydroxide and 4.196 g of lithium hydroxide monohydrate are added into 200 g of N-methylpyrrolidone, and the mixture is stirred and reacted for 6 hours under the condition of 100 ℃ to obtain a light yellow solution, and the light yellow solution is subjected to rotary evaporation to obtain the poly-2, 5-dihydroxy p-benzoquinone-3, 6-disulfonic acid lithium aluminate.
Structural characterization:13the C nmr spectrum showed the appearance of formants at chemical shifts of 124.5, 159.4 and 171.3ppm, corresponding to the hydroxyl carbon, the carbon directly attached to the sulfonic acid group and the carbonyl carbon, respectively. Analysis of carbon, hydrogen and nitrogen elementsThe results are C: 21.61% of formula (C) with polymer6S2O10AlLi)nThe corresponding theoretical carbon contents (21.82%) are close, thus proving that the structure of the obtained lithium poly-2, 5-dihydroxy-p-benzoquinone-3, 6-disulfonate aluminate is correct.
Calculating dissociation energy: the dissociation energy of the poly-2, 5-dihydroxy-p-benzoquinone-3, 6-disulfonic acid lithium aluminate obtained by the density functional method is 113 kcal/mol.
Example 7
This example provides a lithium polypyrazine tetracarboxylic acid borate (lithium borate: (lithium borate)
M is boron atom) according to the following steps:
adding 25.61 g pyrazine tetracarboxylic dianhydride into 200 g ethanol
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 colorless solution, and the colorless solution is subjected to rotary evaporation to obtain the lithium polypyrazine tetracarboxylic acid borate.
Structural characterization:13the C nmr spectrum showed formants at chemical shifts of 144.6, and 160.2ppm, corresponding to the carbon and carboxyl carbon, respectively, in the pyrazine ring. The analysis result of the carbon, hydrogen and nitrogen elements is C: 35.27%, N: 10.19% of a polymer of the formula (C)8N2O8BLi)nThe corresponding theoretical carbon content (35.56%) was close, thus demonstrating that the structure of the resulting lithium polypyrazine tetracarboxylic borate was correct.
Calculating dissociation energy: adopting a density functional method, and simulating a prepared polypyrazine tetracarboxylic acid lithium borate structure by using Gaussian09(Revision B.01) software, wherein MO is formed by a ligand and a boron atom2C4Seven-membered ring, calculating the dissociation energy E of lithium ion from the optimized configurationd(EdEqual to the anion energy plus the lithium ion energy minus the lithium salt energy), and the dissociation energy of the polypyrazine tetracarboxylic acid lithium borate is calculated by adopting a density functional method to be 119 kcal/mol.
Example 8
This example provides a lithium aluminate polypyrazine tetracarboxylic acid
M is boron atom) according to the following steps:
adding 25.61 g of pyrazine tetracarboxylic dianhydride, 7.800 g of aluminum hydroxide and 4.196 g of lithium hydroxide monohydrate into 200 g of N-methylpyrrolidone, stirring and reacting for 6 hours at 100 ℃ to obtain colorless solution, and performing rotary evaporation to obtain the lithium polypyrazine tetracarboxylic aluminate.
Structural characterization:13the C nmr spectrum showed formants at chemical shifts of 148.2 and 163.3ppm, corresponding to the hydroxyl and carbonyl carbons, respectively. The analysis result of the carbon, hydrogen and nitrogen elements is C: 33.15%, N: 9.79% of a polymer of the formula (C)8N2O8ALLi)nThe corresponding theoretical carbon content (33.57%) was close, thus demonstrating that the structure of the resulting lithium polypyrazine tetraacetate aluminate was correct.
Calculating dissociation energy: the dissociation energy of the polypyrazine tetracarboxylic acid lithium aluminate calculated by a density functional method is 117 kcal/mol.
Example 9
This example provides a lithium polytetrahydroxypyrazine borate
M is a boron atom) prepared according to the following steps:
14.416 g of tetrahydroxypyrazine are added to 200 g of N, N-dimethylformamide
6.183 g of boric acid and 4.196 g of lithium hydroxide monohydrate are stirred at 60 ℃ to react for 6 hours, and then the reaction product is subjected to rotary evaporation to obtain the poly-tetra-hydroxypyrazine lithium borate.
Structural characterization:13the C NMR spectrum showed a resonance peak at a chemical shift of 138.6ppm, corresponding to the carbon atom in the pyrazine ring. The analysis result of the carbon, hydrogen and nitrogen elements is C: 30.17%, N: 17.61% of formula (C) with polymer4N2O4BLi)nThe corresponding theoretical carbon content (30.38%) and nitrogen content (17.72%) were close, thus demonstrating that the structure of the resulting lithium polytetrahydroxypyrazine borate is correct.
Calculating dissociation energy: adopting a density functional method, and simulating a prepared poly-tetrahydroxypyrazine lithium borate structure by using Gaussian09(Revision B.01) software, wherein MO is formed by a ligand and a boron atom2C2Five-membered ring, calculating the dissociation energy E of lithium ion from the optimized configurationd(EdEqual to the anion energy plus the lithium ion energy minus the lithium salt energy), and the dissociation energy of the poly (tetrahydroxybenzoquinone) calculated by adopting a density functional function method is 128 kcal/mol.
Example 10
This example provides poly (lithium 2, 5-dihydroxy-1, 4-dicarboxylate-pyrazinoborate (II))
M is a boron atom) according to the following steps:
20.03 g of 2, 5-dihydroxy-1, 4-dicarboxylic acid pyrazine were added to 200 g of dimethyl sulfoxide
6.183 g of boric acid and 4.196 g of lithium hydroxide monohydrate are stirred and reacted for 6 hours at 40 ℃, and then the reaction product is rotated and evaporated to obtain the poly-2, 5-dihydroxy-1, 4-pyrazine borate.
Structural characterization:13the C nmr spectrum showed formants at chemical shifts of 130.1, 147.2 and 151.4ppm, corresponding to the carbon atom directly attached to the carboxyl group, the carbon atom directly attached to the hydroxyl group and the carboxyl carbon in the pyrazine ring. The analysis result of the carbon, hydrogen and nitrogen elements is C: 33.25%, N: 12.91% of a polymer of the formula (C)6N2O6BLi)nThe corresponding theoretical carbon content (33.64%) and nitrogen content (13.08%) were close, thus demonstrating that the structure of the resulting lithium poly-2, 5-dihydroxy-1, 4-dicarboxylate pyrazine borate was correct.
Calculating dissociation energy: the poly 2, 5-dihydroxy-5 is prepared by a density functional method and simulated by Gaussian09 (Vision B.01) software1, 4-dimethyl pyrazine lithium borate structure, and MO formed by ligand and 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), and the dissociation energy of the poly-2, 5-dihydroxy-1, 4-pyrazine lithium borate is calculated by a density functional function method to be 108 kcal/mol.
Example 11
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.
Example 12
This example provides a lithium poly (3, 5-dihydroxy-p-benzoquinone) -2, 6-disulfonate borate
M is a 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 gBoric 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 then the light yellow solution is rotated and evaporated to obtain the lithium poly-3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonate borate.
Structural characterization:13c nuclear magnetic resonance spectrum shows resonance peaks at chemical shifts of 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 polymer6S2O10BLi)nThe corresponding theoretical carbon content (22.93%) is close, which proves that the structure of the obtained lithium poly-3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonate borate is 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 sum of the anion energy and the lithium ion energy minus the lithium salt energy), and the dissociation energy of the poly-3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonic acid lithium borate is calculated by adopting a density-function method to be 115 kcal/mol.
Example 13
This example provides a lithium poly (3, 5-dihydroxy-p-benzoquinone) -2, 6-disulfonate aluminate
M is aluminum atom) according to the following steps:
33.20 g of 3, 5-dihydroxy p-benzoquinone-2, 6-disulfonic acid, 7.800 g of aluminum hydroxide and 4.196 g of lithium hydroxide monohydrate are added into 200 g of N-methylpyrrolidone, a light yellow solution is obtained after stirring and reaction for 6 hours at 100 ℃, and lithium poly-3, 5-dihydroxy p-benzoquinone-2, 6-disulfonate aluminate is obtained after rotary evaporation.
Structural characterization:13the C nuclear magnetic resonance spectrum showed that resonance peaks 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 appeared at chemical shifts of 125.8, 151.1, and 174.3ppm, respectively. Carbon, hydrogen and nitrogen elementThe analysis result is C: 21.61% of formula (C) with polymer6S2O10AlLi)nThe corresponding theoretical carbon contents (21.82%) are close, which proves that the structure of the obtained lithium aluminate poly-3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonate is correct.
Calculating dissociation energy: the dissociation energy of the poly-3, 5-dihydroxy-p-benzoquinone-2, 6-disulfonic acid lithium aluminate obtained by calculation by a density functional method is 111 kcal/mol.
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