CN114957578A - Thienyloxazinyl based covalent organic framework material and preparation method and application thereof - Google Patents
Thienyloxazinyl based covalent organic framework material and preparation method and application thereof Download PDFInfo
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- CN114957578A CN114957578A CN202210705330.5A CN202210705330A CN114957578A CN 114957578 A CN114957578 A CN 114957578A CN 202210705330 A CN202210705330 A CN 202210705330A CN 114957578 A CN114957578 A CN 114957578A
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000012043 crude product Substances 0.000 claims description 13
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- -1 4' -formyl- [1,1 '-biphenyl ] -4-yl Chemical group 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- SNLFYGIUTYKKOE-UHFFFAOYSA-N 4-n,4-n-bis(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 SNLFYGIUTYKKOE-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 7
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 7
- 238000007872 degassing Methods 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 7
- 230000008014 freezing Effects 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 6
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 238000000944 Soxhlet extraction Methods 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 4
- UCCUXODGPMAHRL-UHFFFAOYSA-N 1-bromo-4-iodobenzene Chemical compound BrC1=CC=C(I)C=C1 UCCUXODGPMAHRL-UHFFFAOYSA-N 0.000 claims description 3
- XYBUNINDJPDVKM-UHFFFAOYSA-N 10,10a-dihydro-4ah-phenothiazine Chemical compound S1C2=CC=CC=C2NC2C1C=CC=C2 XYBUNINDJPDVKM-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- UIGXGNUMMVHJKX-UHFFFAOYSA-N (4-formylphenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(C=O)C=C1 UIGXGNUMMVHJKX-UHFFFAOYSA-N 0.000 claims description 2
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000011282 treatment Methods 0.000 claims description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052744 lithium Inorganic materials 0.000 abstract description 9
- 239000000178 monomer Substances 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 125000003172 aldehyde group Chemical group 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 21
- 238000003825 pressing Methods 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 6
- XEKVBIXIBCYLRT-RSAXXLAASA-N [4-[(2e)-2-[3-[(2s)-2-amino-2-carboxyethyl]-6-oxocyclohexa-2,4-dien-1-ylidene]hydrazinyl]phenyl]-trimethylazanium;chloride Chemical compound [Cl-].C1=CC([N+](C)(C)C)=CC=C1N\N=C/1C(=O)C=CC(C[C@H](N)C(O)=O)=C\1 XEKVBIXIBCYLRT-RSAXXLAASA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229960001701 chloroform Drugs 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000022131 cell cycle Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002001 electrolyte material Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- FVIZARNDLVOMSU-UHFFFAOYSA-N ginsenoside K Natural products C1CC(C2(CCC3C(C)(C)C(O)CCC3(C)C2CC2O)C)(C)C2C1C(C)(CCC=C(C)C)OC1OC(CO)C(O)C(O)C1O FVIZARNDLVOMSU-UHFFFAOYSA-N 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 description 1
- 239000013473 2D covalent-organic framework Substances 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000013309 porous organic framework Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
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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
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
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- H01M2300/0065—Solid electrolytes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a covalent organic framework material based on a thiophenecarboxyl group, and a preparation method and application thereof. The structural formula of the covalent organic framework material is synthesized by a solvothermal method after mixing a monomer containing aldehyde group of thiophenecarboxyl and a monomer containing amino group in solution. The lithium battery formed by taking the covalent organic framework material based on the thiophenazine group as the quasi-solid electrolyte has excellent charge-discharge performance, high retention rate and high self-discharge rate, can realize stable and efficient operation of the lithium battery at low temperature, and prolongs the service life of the lithium battery.
Description
Technical Field
The invention belongs to the field of covalent organic framework compounds, and relates to a thiophene oxazinyl based covalent organic framework material and a preparation method and application thereof.
Background
With the development of industrialization and urbanization, batteries are becoming an indispensable part of life and production. To increase electricityThe efficiency of the cell, broadening its use temperature, has made many studies on batteries. Among them, lithium ion batteries having high energy and high power density have received great attention from commercial and research. Since conventional liquid batteries generally have the disadvantages of volatility, insecurity, and the like, the development of solid or quasi-solid electrolytes is urgently needed. Solid inorganic electrolytes are generally rigid and difficult to integrate compactly with the electrodes, severely limiting the overall electrochemical performance of the solid-state battery. Polymer electrolytes can hinder Li at lower temperatures due to their inherent flexibility + Transmission in a full battery system. Therefore, it remains a challenge how to design electrolyte materials that are stable in low temperature chemical properties.
Covalent Organic Frameworks (COFs) materials are porous organic framework materials composed of light elements (C, N, O, etc.). Due to the stability of physicochemical properties, low skeletal density, controllability and designability of the structure of COFs materials, efforts have been made to construct solid electrolytes based on COFs, in particular as solid electrolytes or matrices. Current approaches are mainly through the introduction of lithium-philic organic linkers on the backbone of the framework or as an intrinsic loading of side-chain strategies within the pores, e.g. polyethylene oxide (PEG) chains are incorporated into the internal space of two-dimensional (2D) COFs through post-synthesis modification strategies to facilitate Li + (ACS Applied Energy Materials,2021, 11720-
The functional organic framework structure of the COFs material can avoid the situation that the COFs material is dissolved in organic electrolyte to a great extent, so that the stability of the structure of the porous COFs material is influenced. Single shock reports that a COF material prepared by using a thiophene-based monomer is used as an electrolyte material of a lithium battery, and the specific capacity of the battery is 131.3mAhg after the battery is cycled for 60 circles at 100 DEG C -1 The coulombic efficiency was 92.9%. (chem. mater.2021,33,13, 5058-5066). Yuanweikang prepares a series of COFs containing four imines as hosts, and the specific capacity of the battery is 150.5mAhg after the battery is cycled for 50 circles at 60 DEG C -1 The coulombic efficiency is 98 percent, and the specific capacity after 110 circles is 119.7mAhg -1 The coulombic efficiency was 99%. (Chemical Engineering Journal,2022,433,133749). COF materials produced by the above-described methodsWhen the electrolyte is used as the electrolyte of the lithium battery, the electrolyte can not work normally at a lower temperature.
Disclosure of Invention
The invention aims to provide a covalent organic framework material based on a thiophenecarboxyl group, a preparation method thereof and application thereof as a quasi-solid electrolyte in a lithium battery so as to solve the problem that the lithium battery cannot stably work at low temperature.
The technical scheme for realizing the purpose of the invention is as follows:
thienyloxazinyl based covalent organic framework materials consisting of repeating structural units, each linked by imine linkages, having the general characteristics of crystals, hexagonal topology synthesized by the linkage of 4,4'- (10- (4' -formyl- [1,1 '-biphenyl ] -4-yl) -4a,5a,9a,10 a-tetrahydro-10H-phenothiazine-3, 7-diyl) benzaldehyde (PT-CHO) and two amine groups of an amino compound selected from the group consisting of 5' - (4-aminophenyl) - [1,1':3',1 "-terphenyl ] -4, 4" -diamine (TAPB), N1, N1-bis (4-aminophenyl) benzene-1 to form a-C ═ N-NH-covalent bond, 4-diamine (TAPA) or 4,4',4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine (TAPT), wherein the formula of the covalent organic framework material based on the thiophenecarboxyl group is as follows:
the structural formula of the 4,4' - (10- (4' -formyl- [1,1' -biphenyl ] -4-yl) -4a,5a,9a,10 a-tetrahydro-10H-phenothiazine-3, 7-diyl) benzaldehyde is as follows:
the structural formula of the amino compound is as follows:
the preparation method of the covalent organic framework material based on the thiophenyl group comprises the following steps:
step 2, mixing PT-CHO and 5' - (4-aminophenyl) - [1,1':3', 1' -terphenyl ] -4, 4' -diamine (TAPB) or N1, N1-bis (4-aminophenyl) benzene-1, 4-diamine (TAPA) or 4,4',4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine (TAPT) according to the molar ratio of 1: 1, adding the mixture into a reactor with a volume ratio of 1: 7-7: 1, ultrasonically dissolving in an o-dichlorobenzene/n-butyl alcohol solution, adding acetic acid, ultrasonically dissolving and dispersing again to obtain a suspension, freezing the suspension by using liquid nitrogen, vacuumizing, degassing, sealing a tube by using a flame gun under a vacuum state, reacting for 72-144 h at 120 +/-20 ℃ to obtain a crude product, washing the crude product by using dichloromethane, ethyl acetate, methanol and acetone in sequence, carrying out suction filtration, extracting by using tetrahydrofuran and chloroform Soxhlet, and drying in vacuum to obtain the covalent organic framework material based on the thiophenazine group.
Preferably, in the step 2, the volume ratio of the o-dichlorobenzene to the n-butanol in the o-dichlorobenzene/n-butanol solution is 3: 7.
preferably, in step 2, the number of times of the liquid nitrogen freezing, vacuumizing and degassing treatment is at least 3.
Preferably, in the step 2, the concentration of PT-CHO is 0.3-3 mol/L.
Preferably, in the step 2, the concentration of TAPB, TAPA and TAPT is 0.3-3 mol/L.
Preferably, in the step 2, the concentration of the acetic acid is 3-12 mol/L, and more preferably 6 mol/L.
Preferably, in the step 2, the Soxhlet extraction time is 1-3 days.
Preferably, in step 2, the vacuum drying temperature is 65 ℃ and the time is 12 h.
The present invention provides quasi-solid electrolytes based on the above-described covalent organic framework materials.
Specifically, the quasi-solid electrolyte is prepared by mixing and dispersing a thienylazine-based covalent organic framework material and lithium bistrifluoromethanesulfonimide (LiTFSI) in PEG250, drying and tabletting.
Furthermore, the invention also provides the application of the quasi-solid electrolyte in a lithium battery.
Compared with the prior art, the invention has the following advantages:
according to the covalent organic framework material based on the thienylazine group, the thienylazine group and a surrounding aromatic ring can generate a super pi-conjugation effect, and lone-pair electrons in S and N atoms can be coupled to Li + Take certain action and is beneficial to Li + Conduction of (3). When the covalent organic framework material based on the thiophenazine radical is used as a quasi-solid electrolyte, the electrolyte can stably and efficiently operate at low temperature, and the covalent organic framework material is applied to a lithium battery as the electrolyte material.
Drawings
FIG. 1 is an XRD pattern of NUST-21, NUST-22 and NUST-23;
FIG. 2 is an infrared spectrum of NUST-21, NUST-22 and NUST-23;
FIG. 3 is a thermogravimetric analysis of NUST-21, NUST-22 and NUST-23;
FIG. 4 is a graph of nitrogen adsorption by NUST-21, NUST-22 and NUST-23;
FIG. 5 is a graph of ion conductivity at 0 ℃ of a stainless steel symmetrical cell assembled by doping NUST-21 powder and LiTFSI and pressing into sheets;
FIG. 6 is a graph of ion conductivity at 0 ℃ of a stainless steel symmetrical cell assembled by doping NUST-22 powder and LiTFSI and pressing into sheets;
FIG. 7 is a graph of ion conductivity at 0 ℃ of a stainless steel symmetrical cell assembled by doping NUST-23 powder and LiTFSI and pressing into sheets;
FIG. 8 is a cycle diagram of a lithium ion battery assembled by doping NUST-21 powder and LiTFSI and then pressing into sheets;
FIG. 9 is a cycle diagram of a lithium ion battery assembled by doping NUST-22 powder and LiTFSI and then pressing into sheets;
FIG. 10 is a cycle diagram of a lithium ion battery assembled by doping NUST-23 powder and LiTFSI and then pressing into sheets;
FIG. 11 is a graph of the cycling specific capacity of lithium ion batteries assembled by doping NUST-21 powder and LiTFSI and then pressing into sheets;
FIG. 12 is a graph of the cycling specific capacity of lithium ion batteries assembled by doping NUST-22 powder and LiTFSI and then pressing into sheets;
FIG. 13 is a graph of the cycling specific capacity of lithium ion batteries assembled by doping NUST-23 powder and LiTFSI and then pressing into sheets.
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings.
In the following examples, TAPB, TAPA and TAPT were used and commercially available.
In the following examples, the electrolyte used was formulated by the following steps:
PEG250 and LiTFSI with [ O ]]/[Li]Mixing at a molar ratio of 16:1, stirring at 100 deg.C for 24 hr, transferring the mixed liquid into a glove box, and heating at 25 deg.C for 24 hr to obtain electrolyte (Li) + -PEG)。
In the following examples, the quasi-solid electrolyte used was prepared by the following steps:
an electrolyte (Li) + PEG) and a thienylazine-based covalent organic framework material (NUST-21, NUST-22 or NUST-23) in a mass ratioIs 1: 1 tabletting to obtain the finished product.
Example 1
The specific synthetic route of the preparation method of PT-CHO is as follows:
the method comprises the following specific steps:
(1) compound 3: 5mmol of 1-bromo-4-iodobenzene (Compound 1), 5mmol of 4a,10 a-dihydro-10H-phenothiazine (Compound 2), 5mmol of copper powder and 10mmol of Compound K 2 CO 3 Adding to 100ml of DMF under N 2 Under the protective atmosphere of (1), reacting for 48 hours at 145 ℃, after the reaction is finished, washing with saturated saline, extracting with dichloromethane, drying with anhydrous sodium sulfate, removing the solvent by spinning, and separating with a developing agent column layer to obtain a compound 3(10- (4-bromophenyl) -4a,10 a-dihydro-10H-phenothiazine);
(2) compound 4: dissolving 1mmol of compound 3 in THF, adding NBS four times in a dark environment, adding 2mmol of NBS each time, reacting for 24 hours at normal temperature, washing with saturated saline solution after the reaction is finished, extracting with dichloromethane, drying with anhydrous sodium sulfate, removing the solvent by spin drying, and separating with a developing agent column layer to obtain compound 4;
(3) compound PT-CHO: 2mmol of Compound 4, 8mmol of Compound 5 ((4-formylphenyl) boronic acid), and 0.2mmol of Compound PPH 3 And 16mmol of Compound K 2 CO 3 Adding into a mixed solution of 160ml THF and 40ml oxygen-free water, and adding into a reactor under nitrogen 2 Under the protection atmosphere, reacting for 24 hours at 95 ℃ in a dark place, after the reaction is finished, washing with saturated saline solution, extracting with dichloromethane, drying with anhydrous sodium sulfate, removing the solvent by spinning, and separating with a developing agent column layer to obtain the compound PT-CHO.
Example 2
The specific synthesis method of NUST-21 is as follows:
adding 17.75mg of PT-CHO and 10.63mg of TAPB into a 5ml glass tube, adding 0.6ml of o-dichlorobenzene and 1.4ml of 1,4 n-butanol, carrying out ultrasonic mixing, adding 0.2ml of 6mol/L acetic acid aqueous solution, continuing ultrasonic mixing, sequentially freezing, pumping and unfreezing in liquid nitrogen for three times of degassing, and finally sealing the glass tube and placing the glass tube into an oven at 120 ℃ for 6 days; taking out and cooling to obtain a crude product, washing and filtering the crude product with dichloromethane, ethyl acetate, methanol and acetone sequentially for three times, then performing Soxhlet extraction with tetrahydrofuran and trichloromethane for three days, putting the product into a vacuum drying oven, and drying the product at 65 ℃ for 12 hours to obtain a white solid powder, namely the covalent organic framework material NUST-21 based on the thiophenazine groups, wherein the yield is 93%, and the reaction formula is shown as follows:
example 3
The specific synthesis method of NUST-22 is as follows:
adding 17.75mg of PT-CHO and 8.71mg of TAPA into a 5ml glass tube, adding 0.6ml of o-dichlorobenzene and 1.4ml of 1, 4ml of n-butyl alcohol, carrying out ultrasonic mixing, adding 0.2ml of 6mol/L acetic acid aqueous solution, continuing ultrasonic mixing, sequentially freezing, pumping and unfreezing in liquid nitrogen for three times of degassing, and finally sealing the glass tube and placing the glass tube into an oven with the temperature of 120 ℃ for 6 days; taking out and cooling to obtain a crude product, washing and filtering the crude product with dichloromethane, ethyl acetate, methanol and acetone sequentially for three times, then performing Soxhlet extraction with tetrahydrofuran and trichloromethane for three days, putting the product into a vacuum drying oven, and drying the product at 65 ℃ for 12 hours to obtain a white solid powder, namely the covalent organic framework material NUST-22 based on the thiophenazine groups, wherein the yield is 91%, and the reaction formula is shown as follows:
example 4
The specific synthesis method of NUST-23 is as follows:
adding 17.75mg of PT-CHO and 10.63mg of TAPT into a 5ml glass tube, adding 0.6ml of o-dichlorobenzene and 1.4ml of 1, 4ml of n-butyl alcohol, carrying out ultrasonic mixing, adding 0.2ml of 6mol/L acetic acid aqueous solution, continuing ultrasonic mixing, sequentially freezing, pumping and unfreezing in liquid nitrogen for three times of degassing, and finally sealing the glass tube and placing the glass tube into an oven with the temperature of 120 ℃ for 6 days; taking out and cooling to obtain a crude product, washing and filtering the crude product with dichloromethane, ethyl acetate, methanol and acetone sequentially for three times, soxhlet extracting the crude product with tetrahydrofuran and trichloromethane for three days, putting the crude product into a vacuum drying oven, and drying the crude product at 65 ℃ for 12 hours to obtain white solid powder, wherein the yield is 91%, and the reaction formula is as follows:
example 5
The quasi-solid electrolyte prepared by respectively adopting NUST-21, NUST-22 or NUST-23 materials as the substrate of the quasi-solid electrolyte is added into a stainless steel symmetrical battery in the form of electrolyte, and the battery is assembled in a glove box. The specific implementation method for testing the conductivity curve of the battery is as follows:
the battery was placed in an incubator at 0 ℃ and the impedance curve of the battery was measured using a Biological system.
Example 6
The quasi-solid electrolyte prepared by respectively adopting NUST-21, NUST-22 or NUST-23 materials as the substrate of the quasi-solid electrolyte is added into a lithium ion battery in the form of electrolyte, and the battery assembly is completed in a glove box. The specific implementation method for testing the charge-discharge curve of the battery is as follows:
and (3) placing the battery into a clean constant temperature box, and measuring a charging and discharging curve of the battery by using a blue electricity system. The charge and discharge curves show that the battery has good retention rate.
The use efficiency of the battery is tested, and the specific implementation method is as follows:
the cell was placed in a clean 10 ℃ incubator and the efficiency curve of the cell was measured using a blue-ray system.
FIG. 1 is an XRD pattern of NUST-21, NUST-22 and NUST-23.
FIG. 2 is an infrared spectrum of NUST-21, NUST-22 and NUST-23, showing that NUST-21, NUST-22 and NUST-23 are at 1600cm -l The formation of C ═ N bonds can be confirmed by the infrared absorption peak of (a).
FIG. 3 is a thermogravimetric analysis of NUST-21, NUST-22 and NUST-23 showing that NUST-21, NUST-22 and NUST-23 all have good thermal stability up to 400 ℃.
FIG. 4 is a graph of nitrogen adsorption by NUST-21, NUST-22 and NUST-23. The covalent organic framework film has rich specific surface area, the nitrogen adsorption order is NUST-21 > NUST-23 > NUST-22, and the conduction of lithium ions is greatly facilitated.
FIG. 5 shows the ion conductivity at 0 ℃ of a stainless steel symmetrical cell assembled by doping NUST-21 powder and LiTFSI and pressing into sheets, and the maximum ion conductivity is 5.41 multiplied by 10 -5 S cm -1 。
FIG. 6 shows the ion conductivity at 0 ℃ of a stainless steel symmetrical cell assembled by doping NUST-22 powder and LiTFSI and pressing into a sheet shape, and the ion conductivity is 3.66 multiplied by 10 at the maximum -5 S cm -1 。
FIG. 7 shows the ion conductivity at 0 ℃ of a stainless steel symmetrical cell assembled by doping NUST-23 powder and LiTFSI and pressing into a sheet shape, and the maximum ion conductivity is 7.09 multiplied by 10 -5 S cm -1 。
FIG. 8 is a graph showing the cell cycle efficiency at 10 ℃ of a lithium ion battery assembled by doping NUST-21 powder and LiTFSI and pressing into a sheet, and maintaining 124.6mAg after 60 cycles -1 Specific capacity and coulombic efficiency of 95%.
FIG. 9 is a graph showing the cell cycle efficiency at 10 ℃ of a lithium ion battery assembled by doping NUST-22 powder and LiTFSI and pressing into a sheet, wherein 97.9mAg is maintained after 70 cycles of the battery cycle -1 Specific capacity and coulombic efficiency of 98.49%.
FIG. 10 is a graph showing the cell cycle efficiency at 10 ℃ of a lithium ion battery assembled by doping NUST-23 powder and LiTFSI and pressing into sheets, and after 60 cycles, 126mAg is maintained -1 Specific capacity and coulombic efficiency of 95.22%.
Fig. 11 is a graph of the cycling specific capacity of a lithium ion battery assembled by doping NUST-21 powder and LiTFSI and pressing into a sheet, wherein the battery can stably cycle for more than 60 circles, and the battery has good stability and cyclicity.
Fig. 12 is a graph of the cycling specific capacity of a lithium ion battery assembled by doping NUST-22 powder and LiTFSI and pressing into a sheet, wherein the battery can stably cycle for more than 70 circles, and the battery has good stability and cyclicity.
Fig. 13 is a graph of the cycling specific capacity of a lithium ion battery assembled by doping NUST-23 powder and LiTFSI and pressing into sheets, wherein the battery can stably cycle for more than 60 circles, and the battery has good stability and cyclicity.
Claims (10)
1. A thienylazine-based covalent organic framework material characterized by the following structural formula:
2. the method of preparing a thiophenazine-based covalent organic framework material of claim 1 comprising the steps of:
step 1, adding 1-bromo-4-iodobenzene and 4a,10 a-dihydro-10H-phenothiazine into DMF (dimethyl formamide), and adding copper powder and K 2 CO 3 Reacting for 48-72 hours at 145 +/-5 ℃ by taking the catalyst to obtain 10- (4-bromophenyl) -4a,10 a-dihydro-10H-phenothiazine, adding 10- (4-bromophenyl) -4a,10 a-dihydro-10H-phenothiazine into THF (tetrahydrofuran), adding N-bromosuccinimide in batches under dark conditions, reacting for 24-36 hours, extracting a product, dissolving the product and (4-formylphenyl) boric acid in THF, and adding palladium tetratriphenylphosphine and K 2 CO 3 And water in N 2 Reacting for 24-36 hours at the temperature of 95 +/-5 ℃ in a dark place under the protective atmosphere to obtain 4,4' - (10- (4' -formyl- [1,1' -biphenyl)]-4-yl) -4a,5a,9a,10 a-tetrahydro-10H-phenothiazine-3, 7-diyl) benzaldehyde;
step 2, 4'- (10- (4' -formyl- [1,1 '-biphenyl ] -4-yl) -4a,5a,9a,10 a-tetrahydro-10H-phenothiazine-3, 7-diyl) benzaldehyde and 5' - (4-aminophenyl) - [1,1':3',1 "-terphenyl ] -4, 4" -diamine, N1, N1-bis (4-aminophenyl) benzene-1, 4-diamine or 4,4',4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine are mixed in a molar ratio of 1: 1, adding the mixture into a reactor with a volume ratio of 1: 7-7: 1, ultrasonically dissolving in an o-dichlorobenzene/n-butyl alcohol solution, adding acetic acid, ultrasonically dissolving and dispersing again to obtain a suspension, freezing the suspension by using liquid nitrogen, vacuumizing, degassing, sealing a tube by using a flame gun under a vacuum state, reacting for 72-144 h at 120 +/-20 ℃ to obtain a crude product, washing the crude product by using dichloromethane, ethyl acetate, methanol and acetone in sequence, carrying out suction filtration, extracting by using tetrahydrofuran and chloroform Soxhlet, and drying in vacuum to obtain the covalent organic framework material based on the thiophenazine group.
3. The method according to claim 2, wherein in the step 2, the volume ratio of o-dichlorobenzene to n-butanol in the o-dichlorobenzene/n-butanol solution is 3: 7.
4. the method according to claim 2, wherein the number of the liquid nitrogen freezing, vacuum-pumping and degassing treatments in the step 2 is at least 3.
5. The preparation method according to claim 2, wherein in step 2, the concentration of 4,4' - (10- (4' -formyl- [1,1' -biphenyl ] -4-yl) -4a,5a,9a,10 a-tetrahydro-10H-phenothiazine-3, 7-diyl) benzaldehyde is 0.3 to 3 mol/L; the concentration of 5' - (4-aminophenyl) - [1,1':3', 1' -terphenyl ] -4, 4' -diamine, N1, N1-bis (4-aminophenyl) benzene-1, 4-diamine or 4,4',4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine is 0.3-3 mol/L; the concentration of acetic acid is 3-12 mol/L, and more preferably 6 mol/L.
6. The method according to claim 2, wherein the Soxhlet extraction is performed for 1 to 3 days in step 2.
7. The method according to claim 2, wherein the vacuum drying temperature is 65 ℃ and the time is 12 hours in step 2.
8. Quasi-solid electrolyte based on the covalent organic framework material of claim 1.
9. The quasi-solid electrolyte of claim 8, wherein the quasi-solid electrolyte is prepared by mixing and dispersing the thienylazine-based covalent organic framework material with LiTFSI in PEG250, drying, and tabletting.
10. Use of the quasi-solid electrolyte of claim 9 in a lithium ion battery.
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| US20200185766A1 (en) * | 2017-06-01 | 2020-06-11 | Beijing Institute Of Technology | Quasi-solid-state electrolyte based on ionic liquid for use in lithium battery and preparation method thereof |
| CN112480088A (en) * | 2020-11-27 | 2021-03-12 | 江苏海洋大学 | Thermal activation delayed fluorescence type covalent organic framework material |
| CN113388081A (en) * | 2021-05-31 | 2021-09-14 | 南京理工大学 | Double-chain polyethylene oxide modified covalent organic framework, preparation method and application thereof |
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| US20200185766A1 (en) * | 2017-06-01 | 2020-06-11 | Beijing Institute Of Technology | Quasi-solid-state electrolyte based on ionic liquid for use in lithium battery and preparation method thereof |
| CN112480088A (en) * | 2020-11-27 | 2021-03-12 | 江苏海洋大学 | Thermal activation delayed fluorescence type covalent organic framework material |
| CN113388081A (en) * | 2021-05-31 | 2021-09-14 | 南京理工大学 | Double-chain polyethylene oxide modified covalent organic framework, preparation method and application thereof |
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