CN114957578B - Covalent organic framework material based on thienyl and oxazinyl, and preparation method and application thereof - Google Patents
Covalent organic framework material based on thienyl and oxazinyl, and preparation method and application thereof Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 36
- -1 oxazinyl Chemical group 0.000 title claims abstract description 18
- 125000001544 thienyl group Chemical group 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 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 24
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 22
- 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 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 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
- 239000012043 crude product Substances 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 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
- 238000000944 Soxhlet extraction Methods 0.000 claims description 4
- 238000007872 degassing Methods 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
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 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
- 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 3
- 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 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
- DVHMNNDTZJAONX-UHFFFAOYSA-N 2-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1C1=CC(N)=CC=C1N DVHMNNDTZJAONX-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000011282 treatment Methods 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 1
- CTVOZMQHGVBXNM-UHFFFAOYSA-N IC1=CC=CC=C1.[Br] Chemical compound IC1=CC=CC=C1.[Br] CTVOZMQHGVBXNM-UHFFFAOYSA-N 0.000 claims 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 claims 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052744 lithium Inorganic materials 0.000 abstract description 12
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 125000003277 amino group Chemical group 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
- 239000003792 electrolyte Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 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 description 6
- 230000001351 cycling effect Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 150000002500 ions Chemical class 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
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- 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
- 229940126214 compound 3 Drugs 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000002001 electrolyte material Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- UCCUXODGPMAHRL-UHFFFAOYSA-N 1-bromo-4-iodobenzene Chemical compound BrC1=CC=C(I)C=C1 UCCUXODGPMAHRL-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 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
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 239000013473 2D covalent-organic framework Substances 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
- 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
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 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
- 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
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000011160 research Methods 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
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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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- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a covalent organic framework material based on a thienyl and a preparation method and application thereof. The structural formula of the covalent organic framework material is synthesized by a solvothermal method after a monomer containing a thienyl and oxazinyl aldehyde group and a monomer containing an amino group are mixed by a solution. The lithium battery formed by taking the covalent organic framework material based on the thiophenyl and the oxazinyl as the quasi-solid electrolyte has excellent charge and discharge performance, high retention rate and higher 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 city, batteries are becoming an integral part of life production. In order to increase the efficiency of the battery and widen the use temperature thereof, many studies have been made on the battery. Among them, lithium ion batteries having high energy and high power density are receiving great attention from businesses and research. Since conventional liquid batteries generally have drawbacks of volatility, safety, etc., the development of solid or quasi-solid electrolytes is urgent. Solid inorganic electrolytes are generally rigid, difficult to form a compact integration with the electrodes, severely limiting the overall electrochemical performance of the solid state battery. Polymer electrolytes, due to their inherent flexibility, can hinder Li at lower temperatures + Transmission in a full battery system. Therefore, how to design electrolyte materials that are stable in low temperature chemical properties remains a challenge.
Covalent Organic Framework (COFs) materials are porous organic framework materials composed of light weight elements (C, N, O, etc.). Due to the physicochemical stability, low skeletal density, controllability and designability of the structure of COFs materials, efforts have been made to construct COFs-based solid electrolytes, in particular as solid electrolytes or matrices.The current approach is mainly to promote Li by introducing a lithium-philic organic linker on the backbone of the framework or intrinsic loading within the pores as a side-chain strategy, e.g., polyethylene oxide (PEG) chains are incorporated into the internal space of two-dimensional (2D) COFs by post-synthesis modification strategies + Fast transmission (ACS Applied Energy Materials,2021,11720-11725)
The functional organic framework structure of the COFs material can avoid self-dissolution in organic electrolyte to a great extent, thereby influencing the stability of the structure of the porous COFs material. Shan Zhen reports a COF material prepared from thienyl monomers as an electrolyte material for lithium batteries, and the specific capacity of the battery was 131.3mAhg after 60 cycles at 100 DEG C -1 The coulombic efficiency was 92.9%. (chem. Mater.2021,33,13,5058-5066). Yuan Weikang A series of cells containing four Immine COFs as hosts were prepared and the specific capacity was 150.5mAhg after 50 cycles of cycling at 60 DEG C -1 The coulomb efficiency is 98%, the specific capacity after 110 circles is 119.7mAhg -1 The coulombic efficiency was 99%. (Chemical Engineering Journal,2022,433,133749). However, when the COF material prepared by the method is used as an electrolyte of a lithium battery, the COF material cannot work normally at a lower temperature.
Disclosure of Invention
The invention aims to provide a covalent organic framework material based on a thienyl and oxazinyl group, a preparation method thereof and application of the covalent organic framework material as a quasi-solid electrolyte in a lithium battery, so as to solve the problem that the lithium battery cannot work stably at low temperature.
The technical scheme for realizing the purpose of the invention is as follows:
a thiophene-zinyl-based covalent organic framework material consisting of repeating structural units, each of which is linked by an imine bond and has the general characteristics of a crystal, being a hexagonal topology synthesized from 4,4' - (10- (4 ' -formyl- [1,1' -biphenyl ] -4-yl) -4a,5a,9a,10 a-tetrahydro-10H-phenothiazine-3, 7-diyl) dibenzoaldehyde (PT-CHO) and two amine groups of an amino compound selected from 5' - (4-aminophenyl) - [1,1':3',1 "-terphenyl ] -4,4" -diamine (TAPB), N1-bis (4-aminophenyl) benzene-1, 4-diamine (TAPA) or 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine (TAPT), said thiophene-zinyl-based covalent organic framework material having the following structural formula:
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) dibenzoaldehyde disclosed by the invention 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 thiophen-oxazinyl comprises the following steps:
step 1, 1-bromo-4-iodobenzene and 4a,10 a-dihydro-10H-phenothiazine are added to N, N-Dimethylformamide (DMF) with copper powder and potassium carbonate (K 2 CO 3 ) Reacting at 145+ -5 ℃ for 48-72 hours to obtain 10- (4-bromophenyl) -4a,10 a-dihydro-10H-phenothiazine, adding 10- (4-bromophenyl) -4a,10 a-dihydro-10H-phenothiazine into Tetrahydrofuran (THF), adding N-bromosuccinimide (NBS) in batches under the condition of avoiding light, reacting for 24-36 hours, extracting the product, dissolving the product and (4-formylphenyl) boric acid into THF, and adding tetra-triphenylphosphine palladium (PPH) 3 ) Potassium carbonate (K) 2 CO 3 ) And water, at N 2 The mixture reacts for 24 to 36 hours in the protection atmosphere at the temperature of 95 plus or minus 5 ℃ in the dark to obtain 4,4' - (10- (4 ' -formyl- [1,1' -biphenyl)]-4-yl) -4a,5a,9a,10 a-tetrahydro-10H-phenothiazin-3, 7-diyl) dibenzoaldehyde (PT-CHO);
step 2, PT-CHO was reacted with 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' - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine (TAPT) in a molar ratio of 1:1 is added into the mixture in a volume ratio of 1: 7-7: 1, adding acetic acid into o-dichlorobenzene/n-butanol solution, ultrasonically dissolving again, dispersing into suspension, freezing the suspension with liquid nitrogen, vacuumizing, degassing, sealing the tube by using a flame gun under vacuum state, reacting for 72-144 hours at 120+/-20 ℃ to obtain a crude product, washing the crude product with dichloromethane, ethyl acetate, methanol and acetone in sequence, performing suction filtration, performing Soxhlet extraction with tetrahydrofuran and chloroform, and performing vacuum drying to obtain the covalent organic framework material based on the thiophenazine group.
Preferably, in the step 2, in the o-dichlorobenzene/n-butanol solution, the volume ratio of the o-dichlorobenzene to the n-butanol is 3:7.
preferably, in step 2, the number of freezing, vacuuming and degassing treatments of liquid nitrogen is at least 3.
Preferably, in step 2, the concentration of PT-CHO is 0.3 to 3mol/L.
Preferably, in step 2, the concentration of TAPB, TAPA, TAPT is 0.3 to 3mol/L.
Preferably, in step 2, the acetic acid concentration is 3 to 12mol/L, more preferably 6mol/L.
Preferably, in step 2, the Soxhlet extraction time is 1 to 3 days.
Preferably, in step 2, the vacuum drying temperature is 65 ℃ and the time is 12 hours.
The present invention provides a quasi-solid electrolyte based on the covalent organic framework material.
Specifically, the quasi-solid electrolyte is prepared by mixing and dispersing covalent organic framework materials based on thienyl and oxazinyl and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) in PEG250, drying and tabletting.
Further, the invention also provides application of the quasi-solid electrolyte in a lithium battery.
Compared with the prior art, the invention has the following advantages:
the covalent organic framework material based on the thiophenzinyl of the invention, whereinThe thienyl and the surrounding aromatic ring can generate super strong pi conjugated effect, and the lone pair electrons in the S and N atoms can pair Li + Takes a certain effect, is favorable for Li + Is a conductive material. When the covalent organic framework material based on the thiophenyl-oxazinyl is used as a quasi-solid electrolyte, stable and efficient operation of the electrolyte at low temperature can be realized, and the covalent organic framework material is used as the electrolyte material in a lithium battery, so that the formed lithium battery has good charge-discharge curve circularity, good retention rate and higher self-discharge rate, can realize stable and efficient operation of the lithium battery at low temperature, and widens the use temperature range of the lithium battery.
Drawings
FIG. 1 is an XRD pattern for 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 nitrogen adsorption diagram for NUST-21, NUST-22, and NUST-23;
FIG. 5 is an ion conductivity graph at 0deg.C for a stainless steel symmetrical cell assembled from NUST-21 powder and LiTFSI doped and pressed into sheets;
FIG. 6 is an ion conductivity graph at 0deg.C for a stainless steel symmetrical cell assembled from NUST-22 powder and LiTFSI doped and pressed into sheets;
FIG. 7 is an ion conductivity graph at 0deg.C for a stainless steel symmetrical cell assembled from NUST-23 powder and LiTFSI doped and pressed into sheets;
FIG. 8 is a cycle chart of a lithium ion battery assembled from NUST-21 powder and LiTFSI doped and compressed into a sheet;
FIG. 9 is a cycle chart of a lithium ion battery assembled from NUST-22 powder and LiTFSI doped and compressed into a sheet;
FIG. 10 is a cycle chart of a lithium ion battery assembled from NUST-23 powder and LiTFSI doped and compressed into a sheet;
FIG. 11 is a graph of the cycling specific capacity of a lithium ion battery assembled from NUST-21 powder and LiTFSI doped and compressed into a sheet;
FIG. 12 is a graph of the cycling specific capacity of a lithium ion battery assembled from NUST-22 powder and LiTFSI doped and compressed into a sheet;
fig. 13 is a graph of the cyclic specific capacity of a lithium ion battery assembled from NUST-23 powder and LiTFSI doped and pressed into a sheet.
Detailed Description
The invention will be described in further detail with reference to specific embodiments and drawings.
In the examples described below, TAPB, TAPA, TAPT was used and was commercially available.
In the following examples, the electrolyte used was formulated by the following steps:
PEG250 and LiTFSI were combined with [ O]/[Li]Mixing at a molar ratio of 16:1, stirring at 100deg.C for 24 hr, transferring the mixed liquid into a glove box, and heating at 25deg.C for 24 hr to obtain electrolyte (Li) + -PEG)。
In the following examples, the quasi-solid state electrolyte used was prepared by the following steps:
electrolyte (Li) + -PEG) with a thiophenzinyl based covalent organic framework material (NUST-21, NUST-22 or NUST-23) in a mass ratio of 1:1 tabletting.
Example 1
The preparation method of PT-CHO comprises the following specific synthetic route:
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 Added to 100ml DMF at N 2 After the reaction is finished, washing the mixture with saturated saline, extracting the mixture with dichloromethane, drying the mixture with anhydrous sodium sulfate, spin-drying the mixture to remove the solvent, and separating the mixture by using a developing solvent column layer to obtain a compound 3 (10- (4-bromophenyl) -4a,10 a-dihydro-10H-phenothiazine);
(2) Compound 4: dissolving 1mmol of the compound 3 in THF, adding NBS in a light-proof environment for four times, adding 2mmol of NBS each time, reacting for 24 hours at normal temperature, washing with saturated saline solution, extracting with dichloromethane, drying with anhydrous sodium sulfate, spin-drying to remove the solvent, and separating with a developer column layer to obtain a compound 4;
(3) Compound PT-CHO: 2mmol of Compound 4, 8mmol of Compound 5 ((4-formylphenyl) boric acid), 0.2mmol of Compound PPH 3 And 16mmol of compound K 2 CO 3 To a mixed solution of 160ml THF and 40ml oxygen-free water in N 2 After the reaction, washing with saturated saline solution, extracting with dichloromethane, drying with anhydrous sodium sulfate, spin-drying to remove solvent, and separating with a developer column layer to obtain the compound PT-CHO.
Example 2
The specific synthesis method of NUST-21 is as follows:
17.75mg of PT-CHO and 10.63mg of TAPB are added into a 5ml glass tube, 0.6ml of o-dichlorobenzene, 1.4ml of 1, 4-n-butanol are added, ultrasonic mixing is carried out, 0.2ml of 6mol/L acetic acid aqueous solution is added, ultrasonic mixing is continued, then the mixture is sequentially frozen, pumped, thawed and degassed three times in liquid nitrogen, and finally the glass tube is sealed and placed 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 for three times in sequence, extracting the crude product with tetrahydrofuran and chloroform for three days in a Soxhlet manner, putting the crude product into a vacuum drying oven, and drying the dried product at 65 ℃ for 12 hours to obtain a white solid powder of a thiophene-zinyl-based covalent organic framework material NUST-21, wherein the yield is 93%, and the reaction formula is as follows:
example 3
The specific synthesis method of NUST-22 is as follows:
17.75mg of PT-CHO and 8.71mg of TAPA are added into a 5ml glass tube, 0.6ml of o-dichlorobenzene, 1.4ml of 1, 4-n-butanol are added, ultrasonic mixing is carried out, 0.2ml of 6mol/L acetic acid aqueous solution is added, ultrasonic mixing is continued, then the mixture is sequentially frozen, pumped, thawed and degassed three times in liquid nitrogen, and finally the glass tube is sealed and placed 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 for three times in sequence, extracting the crude product with tetrahydrofuran and chloroform for three days in a Soxhlet manner, putting the crude product into a vacuum drying oven, and drying the dried product at 65 ℃ for 12 hours to obtain a white solid powder of a thiophene oxazinyl-based covalent organic framework material NUST-22, wherein the yield is 91%, and the reaction formula is as follows:
example 4
The specific synthesis method of NUST-23 is as follows:
17.75mg of PT-CHO and 10.63mg of TAPT are added into a 5ml glass tube, 0.6ml of o-dichlorobenzene, 1.4ml of 1, 4-n-butanol are added, ultrasonic mixing is carried out, 0.2ml of 6mol/L acetic acid aqueous solution is added, ultrasonic mixing is continued, then the mixture is sequentially frozen, pumped, thawed and degassed three times in liquid nitrogen, and finally the glass tube is sealed and placed 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 for three times in sequence, extracting the crude product with tetrahydrofuran and chloroform for three days, and drying the crude product in a vacuum drying oven at 65 ℃ for 12 hours to obtain white solid powder with the yield of 91 percent, wherein the reaction formula is as follows:
example 5
The quasi-solid electrolyte prepared by taking NUST-21, NUST-22 or NUST-23 materials as substrates 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 of the conductivity curve of the test battery is as follows:
the cell was placed in an incubator at 0℃and impedance curves of the cell were measured using a Biological system.
Example 6
The quasi-solid electrolyte prepared by taking NUST-21, NUST-22 or NUST-23 materials as substrates of the quasi-solid electrolyte is added into a lithium ion battery in the form of electrolyte, and the battery is assembled in a glove box. The battery charge-discharge curve is tested, and the specific implementation method is as follows:
and placing the battery into a clean constant temperature box, and measuring the charge-discharge curve of the battery by using a blue electric system. The charge-discharge curve shows that the battery has good retention rate.
The service efficiency of the battery is tested, and the specific implementation method is as follows:
the cells were placed in a clean 10 ℃ incubator and the efficiency profile of the cells was measured using a blue electric system.
FIG. 1 is an XRD pattern for 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, which shows that NUST-21, NUST-22, and NUST-23 all have good thermal stability before 400 ℃.
FIG. 4 is a nitrogen adsorption diagram for NUST-21, NUST-22 and NUST-23. The covalent organic framework membrane has rich specific surface area, and the size sequence of nitrogen adsorption is NUST-21 > NUST-23 > NUST-22, which is very beneficial to the conduction of lithium ions.
FIG. 5 shows the ion conductivity of a NUST-21 powder and LiTFSI doped and pressed into a sheet to form a stainless steel symmetrical cell assembled at 0deg.C, up to 5.41×10 -5 S cm -1 。
FIG. 6 shows the ion conductivity of a NUST-22 powder and LiTFSI doped stainless steel symmetrical cell assembled in sheet form at 0deg.C, up to 3.66×10 -5 S cm -1 。
FIG. 7 shows the ion conductivity at 0deg.C of a stainless steel symmetrical cell assembled from NUST-23 powder and LiTFSI doped and pressed into a sheet, up to 7.09×10 -5 S cm -1 。
FIG. 8 is a graph of battery cycle efficiency at 10deg.C for a lithium ion battery assembled from NUST-21 powder and LiTFSI doped and compressed into a sheet, which remains 124.6mAg after 60 cycles -1 And a coulombic efficiency of 95%.
FIG. 9 is a graph of battery cycle efficiency at 10deg.C for a lithium ion battery assembled from NUST-22 powder and LiTFSI doped and compressed into a sheet, which remains 97.9mAg after 70 cycles -1 And a coulombic efficiency of 98.49%.
FIG. 10 is a graph of battery cycle efficiency at 10deg.C for a lithium ion battery assembled from NUST-23 powder and LiTFSI doped and compressed into a sheet, which remains 126mAg after 60 cycles -1 And a coulombic efficiency of 95.22%.
Fig. 11 is a graph of the cycling specific capacity of a lithium ion battery assembled by pressing into sheets after doping of NUST-21 powder and LiTFSI, which can be stably cycled for more than 60 cycles, demonstrating good stability and cyclicity.
Fig. 12 is a graph of the cycling specific capacity of a lithium ion battery assembled by pressing the NUST-22 powder and LiTFSI doped into a sheet, which can be stably cycled for more than 70 cycles, indicating good stability and cyclicity.
Fig. 13 is a graph of the cycling specific capacity of a lithium ion battery assembled by pressing into sheets after doping of NUST-23 powder and LiTFSI, which can be stably cycled for more than 60 cycles, indicating good stability and cyclicity.
Claims (11)
1. Covalent organic framework materials based on thiophenzinyl, characterized by the following structural formula:
2. the method for preparing a thienyl group based covalent organic framework material as claimed in claim 1, comprising the steps of:
step 1, 1-Adding bromine-4-iodobenzene and 4a,10 a-dihydro-10H-phenothiazine into DMF, and mixing with copper powder and K 2 CO 3 Reacting for 48-72 hours at 145+ -5 ℃ to obtain 10- (4-bromophenyl) -4a,10 a-dihydro-10H-phenothiazine, adding 10- (4-bromophenyl) -4a,10 a-dihydro-10H-phenothiazine into THF, adding N-bromosuccinimide in batches under the condition of avoiding light, reacting for 24-36 hours, extracting a product, dissolving the product and (4-formylphenyl) boric acid into THF, and adding triphenylphosphine palladium and K 2 CO 3 And water, at N 2 The mixture reacts for 24 to 36 hours in the protection atmosphere at the temperature of 95 plus or minus 5 ℃ in the dark to obtain 4,4' - (10- (4 ' -formyl- [1,1' -biphenyl)]-4-yl) -4a,5a,9a,10 a-tetrahydro-10H-phenothiazin-3, 7-diyl-dibenzoaldehyde;
step 2, 4' - (10- (4 ' -formyl- [1,1' -biphenyl ] -4-yl) -4a,5a,9a,10 a-tetrahydro-10H-phenothiazine-3, 7-diyl) dibenzoaldehyde is reacted with 5' - (4-aminophenyl) - [1,1':3',1 "-terphenyl ] -4,4" -diamine, N1-bis (4-aminophenyl) benzene-1, 4-diamine, or 4,4' - (1, 3, 5-triazine-2, 4, 6-diyl) triphenylamine in a molar ratio of 1:1 is added into the mixture in a volume ratio of 1: 7-7: 1, adding acetic acid into o-dichlorobenzene/n-butanol solution, ultrasonically dissolving again, dispersing into suspension, freezing the suspension with liquid nitrogen, vacuumizing, degassing, sealing the tube by using a flame gun under vacuum state, reacting for 72-144 hours at 120+/-20 ℃ to obtain a crude product, washing the crude product with dichloromethane, ethyl acetate, methanol and acetone in sequence, performing suction filtration, performing Soxhlet extraction with tetrahydrofuran and chloroform, and performing vacuum drying to obtain the covalent organic framework material based on the thiophenazine group.
3. The preparation method according to claim 2, wherein in the step 2, in the o-dichlorobenzene/n-butanol solution, the volume ratio of the o-dichlorobenzene to the n-butanol is 3:7.
4. the method according to claim 2, wherein in step 2, the number of freezing, evacuating and degassing treatments with liquid nitrogen is at least 3.
5. The process 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) dibenzoaldehyde is 0.3 to 3mol/L; the concentration of 5'- (4-aminophenyl) - [1,1':3', 1' -terphenyl ] -4,4 '-diamine, N1-bis (4-aminophenyl) benzene-1, 4-diamine or 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine is from 0.3 to 3mol/L; the concentration of acetic acid is 3-12 mol/L.
6. The method according to claim 2, wherein in the step 2, the acetic acid concentration is 6mol/L.
7. The method according to claim 2, wherein the Soxhlet extraction time is 1 to 3 days in step 2.
8. The method according to claim 2, wherein in step 2, the vacuum drying temperature is 65 ℃ for 12 hours.
9. A quasi-solid electrolyte based on the covalent organic framework material of claim 1.
10. The quasi-solid electrolyte according to claim 9, wherein the quasi-solid electrolyte is prepared by mixing and dispersing a thiophene-zinyl based covalent organic framework material with LiTFSI in PEG250, drying and tabletting.
11. Use of the quasi-solid electrolyte according to claim 10 in a lithium ion battery.
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