CN115312966B - Covalent organic framework-based semi-solid electrolyte composite diaphragm, preparation method and application thereof - Google Patents
Covalent organic framework-based semi-solid electrolyte composite diaphragm, preparation method and application thereof Download PDFInfo
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- CN115312966B CN115312966B CN202210996987.1A CN202210996987A CN115312966B CN 115312966 B CN115312966 B CN 115312966B CN 202210996987 A CN202210996987 A CN 202210996987A CN 115312966 B CN115312966 B CN 115312966B
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000012528 membrane Substances 0.000 claims abstract description 41
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 19
- -1 polyethylene Polymers 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000000967 suction filtration Methods 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000004698 Polyethylene Substances 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 229920000573 polyethylene Polymers 0.000 claims abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000002135 nanosheet Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical group [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- WQGWDDDVZFFDIG-UHFFFAOYSA-N trihydroxybenzene Natural products OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000007872 degassing Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 3
- ANQZVBBNFRKDMX-UHFFFAOYSA-N OC1=C(C(=C(C(=C1C=O)C=O)C=O)O)O Chemical compound OC1=C(C(=C(C(=C1C=O)C=O)C=O)O)O ANQZVBBNFRKDMX-UHFFFAOYSA-N 0.000 claims description 2
- 238000000944 Soxhlet extraction Methods 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 7
- 230000005764 inhibitory process Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 5
- 239000003708 ampul Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- PHDIJLFSKNMCMI-ITGJKDDRSA-N (3R,4S,5R,6R)-6-(hydroxymethyl)-4-(8-quinolin-6-yloxyoctoxy)oxane-2,3,5-triol Chemical compound OC[C@@H]1[C@H]([C@@H]([C@H](C(O1)O)O)OCCCCCCCCOC=1C=C2C=CC=NC2=CC=1)O PHDIJLFSKNMCMI-ITGJKDDRSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 1
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000013309 porous organic framework Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
- 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
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
-
- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/497—Ionic conductivity
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention discloses a covalent organic framework-based semi-solid electrolyte composite membrane, a preparation method and application thereof. The covalent organic frame-based semi-solid electrolyte composite membrane is prepared by compounding covalent organic frame materials modified by long alkyl chains on two sides of a polyethylene base membrane by adopting a vacuum suction filtration process, and then coating polyvinylidene fluoride-hexafluoropropylene copolymer on two sides of the membrane by adopting a coating process. The covalent organic framework-based semi-solid electrolyte composite membrane has excellent lithium ion conduction effect and lithium dendrite inhibition effect, and the assembled lithium ion battery has good battery cycle stability and excellent charge-discharge specific capacity.
Description
Technical Field
The invention belongs to the field of covalent organic framework materials, and relates to a covalent organic framework-based semi-solid electrolyte composite membrane, a preparation method and application thereof in lithium ion batteries.
Background
The lower energy density and safety issues of liquid lithium ion batteries have not met the increasing demands of large-scale energy storage systems. As a low cost alternative, solid state lithium metal batteries show great competitive advantages and broad application prospects due to their high energy density and good safety. However, solid-state electrolytes tend to have low ionic conductivity, and poor interfacial compatibility and poor stability between the solid-state electrolyte and the electrode can lead to continuous deterioration of electrochemical performance. At present, solid electrolytes prepared from inorganic ceramic materials and organic polymers are generally used, and lithium ion conduction and lithium dendrite inhibition cannot be realized efficiently. How to design the electrolyte separator of ultra-thin composite semi-solid lithium ion batteries remains a challenge.
Covalent Organic Framework (COFs) materials are porous organic framework materials composed of light elements (C, N, O, etc.), but COFs are generally solid powders and difficult to process into thin films. The literature uses composite membranes containing PVDF-HFP layers whose assembled liquid lithium iron phosphate cells have reduced specific capacities below 100mAh/g after 50 cycles, with poor cycling stability (int.j. Hydrogen Energy,2017, 42, 10, 6862-6875).
Disclosure of Invention
The invention aims to provide a covalent organic framework-based semi-solid electrolyte composite membrane, a preparation method and application thereof in a lithium ion battery, so as to solve the problem of lithium dendrite inhibition and realize efficient circulation and high specific capacity.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the covalent organic framework-based semi-solid electrolyte composite membrane comprises the following steps:
Step1, adding an organic solvent serving as an auxiliary agent into a covalent organic framework material modified by a long alkyl chain, ball-milling for 12-48 hours, standing the ball-milled mixed solution, and taking supernatant to obtain a covalent organic framework nano-sheet dispersion liquid modified by the long alkyl chain;
step2, vacuum-filtering the long alkyl chain modified covalent organic framework nano-sheet dispersion liquid by taking a polyethylene film as a base film, adding ethanol after the suction filtration, performing suction filtration and washing, and finally vacuum-drying to obtain the long alkyl chain modified covalent organic framework composite membrane;
and 3, uniformly coating acetone/water solution of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) on two sides of the covalent organic framework composite membrane modified by long alkyl chains in sequence, wherein the coating thickness is 2-50 mu m, and drying after the organic solvent volatilizes, so as to obtain the covalent organic framework-based semi-solid electrolyte composite membrane.
Preferably, in step 1, the organic solvent is N-methylpyrrolidone, dimethylformamide or acetonitrile, more preferably N-methylpyrrolidone.
Preferably, in step 1, the ball milling speed is 300 to 600rpm, more preferably 400rpm; the ball milling time is 6 to 48 hours, more preferably 24 hours.
Preferably, in step 2, the pore size of the polyethylene film is 50 to 200nm, more preferably 100nm.
Preferably, in the step 2, the thickness of the covalent organic framework nano-sheet layer in the composite membrane formed after vacuum filtration is 2-15 μm, more preferably 5 μm.
Preferably, in the step 2, the vacuum degree adopted in the vacuum filtration process is 0.1MPa.
Preferably, in the step 2, the vacuum drying temperature is 60-80 ℃ and the drying time is more than 10 hours.
Preferably, in step 3, the concentration of the polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) in the acetone/water solution is 5-15%, and the mass ratio of the acetone to the water is 9:1 to 6:1.
Preferably, in the step 3, the drying temperature is 80-90 ℃ and the drying time is 4-12 h.
The long alkyl chain modified covalent organic framework material is a hexagonal topological structure synthesized by connecting three aldehydes in trihydroxybenzene trioxymethylene and two amide groups of a long alkyl chain modified amino compound (NH 2 NH-C16) to form a-C=C-NH-NH-covalent bond, and has the following structural formula:
The preparation method of the covalent organic framework material modified by the long alkyl chain comprises the following steps:
Adding trihydroxybenzene trioxymethylene and an amino compound modified by a long alkyl chain into a mesitylene/1, 4-dioxane solution, adding acetic acid after ultrasonic dissolution, performing ultrasonic dissolution again to disperse into a suspension, performing liquid nitrogen freezing, vacuumizing and degassing treatment on the suspension, sealing a tube by using a flame gun in a vacuum state, then reacting for 48-168 hours at 120+/-20 ℃ to obtain a crude product, washing the crude product, performing suction filtration, performing Soxhlet extraction by tetrahydrofuran and chloroform, and finally performing vacuum drying to obtain a covalent organic framework material modified by the long alkyl chain, wherein the volume ratio of the mesitylene to the 1, 4-dioxane solution is 1: 7-7: 1.
The structural formula of the amino compound modified by the long alkyl chain is as follows:
the structural formula of the trihydroxy benzene tricarboxaldehyde is as follows:
preferably, the molar ratio of the trihydroxybenzene trioxaldehyde to the long alkyl chain modified amine compound is 2:3.
Preferably, the number of freezing, vacuuming and degassing treatments of liquid nitrogen is 3 or more.
Preferably, the concentration of the trihydroxybenzene trioxymethylene is 0.3-3 mol/L, and the concentration of the long alkyl chain modified amino compound is 0.2-2 mol/L.
Preferably, the acetic acid concentration is 3 to 12mol/L, more preferably 6mol/L.
Preferably, the reaction temperature is 120℃and the reaction time is 72 hours.
Preferably, the crude product is washed clean with dichloromethane, ethyl acetate, methanol, acetone in sequence.
Further, the invention provides application of the covalent organic framework-based semi-solid electrolyte composite membrane in semi-solid lithium ion batteries.
The semisolid lithium ion battery provided by the invention is a semisolid lithium ion battery common in the field, such as a lithium iron phosphate battery, a nickel-cobalt-manganese ternary lithium battery and the like.
Compared with the prior art, the invention has the following advantages:
(1) The covalent organic framework-based semi-solid electrolyte composite membrane provided by the invention has the advantages that the thickness of the membrane can be greatly reduced to 15 mu m by adopting a nano-sheet composite structure, the membrane is an ultrathin composite membrane, and meanwhile, the outermost uniform PVDF-HFP layer is rich in fluorine elements, so that lithium ions can uniformly shuttle and the formation of lithium dendrites can be inhibited. Can stably circulate for 900 hours under the current density of 1mA/cm 2, and the voltage trend is gradually reduced, which shows that the internal resistance is gradually reduced, and the lithium dendrite inhibition effect is excellent.
(2) The covalent organic framework-based semi-solid electrolyte composite membrane has a rich artificial pore structure, and ordered nanoscale pore channels of the membrane can realize lithium ion conduction, so that electrolyte is stored to realize the cycle stability of a semi-solid lithium ion battery and inhibit capacity attenuation to keep high specific capacity. The assembled lithium iron phosphate battery is stably circulated for 65 circles, and the specific capacity is 130mAh/g; the assembled nickel-cobalt-manganese ternary lithium battery is stably circulated for 50 circles, and the specific capacity is 125mAh/g.
Drawings
FIG. 1 is an XRD pattern of a long alkyl chain modified covalent organic framework material;
FIG. 2 is an infrared spectrogram of a covalent organic framework-based semi-solid electrolyte composite membrane;
FIG. 3 is a surface SEM image of a covalent organic framework-based semi-solid electrolyte composite separator;
FIG. 4 is a graph of cycling performance of a lithium-lithium symmetric battery assembled from a covalent organic framework-based semi-solid electrolyte composite separator;
FIG. 5 is a cycle chart of a lithium iron phosphate battery assembled from a covalent organic framework-based semi-solid electrolyte composite separator;
Fig. 6 is a cycle chart of a nickel-cobalt-manganese ternary lithium battery assembled by a covalent organic framework-based semi-solid electrolyte composite membrane.
Detailed Description
The present invention will be further described in detail below with reference to examples, which are provided to illustrate the objects, technical solutions and advantages of the present invention. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. To make several variants and improvements, all falling within the scope of protection of the present invention.
In the following examples, an acetone/water solution of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) was used, and the preparation method was as follows: PVDF-HFP in mass ratio: acetone: water = 1:8:1, mixing and stirring PVDF-HFP, acetone and water for 12 hours until a bubble-free mixed solution is formed, and obtaining an acetone/water solution of polyvinylidene fluoride-hexafluoropropylene copolymer.
The NH 2 NH-C16 can be purchased commercially or prepared by self, and the specific synthetic route is as follows:
The method comprises the following specific steps:
(1) Compound 1c: adding 1mmol of compound 1a,3mmol of compound 1b and 1mmol of K 2CO3 into 30ml of DMF, reacting for 48 hours at 65 ℃ under the protection atmosphere of N 2, extracting with dichloromethane after the reaction, washing with saturated saline, drying with anhydrous sodium sulfate, removing the solvent by vacuum spin-drying, and separating and purifying by using column chromatography to obtain a compound 1c;
(2) NH 2 NH-C16: adding the compound 1C and hydrazine hydrate into 15ml of ethanol solution for reaction for 12 hours, directly filtering after low-temperature freezing, and washing white solid with petroleum ether solvent for multiple times to obtain the target monomer NH 2 NH-C16.
Example 1
(1) The covalent organic framework material (COF-C16) modified by long alkyl chain is an organic framework structure formed by reacting trihydroxy trimellitic aldehyde and NH 2 NH-C16 through Schiff base, and the structure is shown as follows:
The structure of NH 2 NH-C16 is shown below:
the preparation method of the COF-C16 comprises the following specific steps:
A glass ampoule (volume about 20mL, length 18cm, neck length 9 cm) was charged with trihydroxybenzene trimethaldehyde (21.0 mg,0.1 mmol), NH 2 NH-C16 (101.3 mg,0.15 mmol) and mesitylene/1, 4-dioxane (3:1, v/v,4 mL). Then, the ampoule is immersed in an ultrasonic bath for 5 minutes; subsequently, 0.4mL of 6.0mol L-1 acetic acid aqueous solution was added, and the ampoule was immersed in the ultrasonic bath for 2 minutes. The mixture was sonicated for 2 minutes to obtain a uniform dispersion. The tube was then flash frozen at 77K with a liquid nitrogen bath and degassed by three freeze pump-thaw cycles, sealed under vacuum, and heated at 120 ℃ for 3 days. Breaking ampoule bottle neck, centrifuging to separate yellow gel product, washing with acetone (3×10mL), soaking in anhydrous acetone for 12h, and vacuum drying at 80deg.C for 12h to obtain COF-C16 as yellow colloid powder. The reaction formula is as follows:
(2) 100mg of COF-C16 colloid powder is added into a ball milling tank of polytetrafluoroethylene, 15 agate ball milling beads with the diameter of 5mm are added, 20mL of N-methyl pyrrolidone is added, ball milling is carried out for 24 hours at the rotating speed of 300rpm, standing is carried out after ball milling is finished, and the supernatant is taken as a well-dispersed COF-C16 nanosheet solution.
(3) Selecting a polyethylene film with the aperture of 100nm as a bottom film of a vacuum suction filtration device, then dripping 20mL of a well-dispersed COF-C16 nanosheet solution on the bottom film, performing suction filtration under the condition of 0.1MPa vacuum degree, waiting for the completion of the suction filtration of the solvent, adding 10mL of ethanol solvent for suction filtration and washing, and then drying the solvent in a vacuum oven at 50 ℃ to obtain the COF-C16 composite membrane.
(4) Spreading the COF-C16 composite diaphragm subjected to vacuum filtration on a platform, dripping the prepared polyvinylidene fluoride-hexafluoropropylene copolymer solution on the diaphragm, scraping once at a constant speed by a scraper with the height adjusted to be 5 mu m, carrying out the same coating operation on the other side after the solvent volatilizes, and putting the film into a 90 ℃ oven for drying for 8 hours after the organic solvent volatilizes, thus obtaining the covalent organic frame-based semi-solid electrolyte composite diaphragm.
Example 2
And adding the covalent organic framework-based semi-solid electrolyte composite membrane into a lithium-lithium balance battery in the form of a battery membrane, and completing the battery assembly in a glove box. The battery is tested for cycle stability, and the specific implementation method is as follows: the battery was placed in an incubator and tested for cycling stability of a lithium battery using a blue electric system at a current density of 0.1mA/cm 2.
Example 3
And taking the covalent organic framework-based semi-solid electrolyte composite membrane as a membrane of the lithium iron phosphate battery, and completing the assembly of the semi-solid lithium battery in a glove box. The battery charge-discharge curve is tested, and the specific implementation method is as follows: and (3) placing the battery in a clean incubator, and measuring the charge-discharge curve of the battery by using a blue electric system under the charge-discharge multiplying power condition of 0.1C within the voltage range of 2.7-3.8V. The charge-discharge curve shows that the battery has good cycling stability and high specific capacity retention.
Example 4
And taking the covalent organic framework-based semi-solid electrolyte composite diaphragm as a diaphragm of the nickel-cobalt-manganese ternary lithium battery, and completing the assembly of the semi-solid lithium battery in a glove box. The battery charge-discharge curve is tested, and the specific implementation method is as follows: and (3) placing the battery in a clean incubator, and measuring the charge-discharge curve of the battery by using a blue electric system under the charge-discharge multiplying power condition of 0.1C within the voltage range of 3.0-4.2V. The charge-discharge curve of the battery was tested, which showed that the battery had good cycling stability and high specific capacity retention.
Fig. 1 is an XRD pattern of a long alkyl chain modified covalent organic framework material, which can demonstrate the crystallinity of the covalent organic framework material.
Fig. 2 is an infrared spectrum of a covalent organic framework-based semi-solid electrolyte composite membrane, which can demonstrate the presence of effective functional groups (the presence of C-F bonds) in the outermost layer of the composite membrane.
Fig. 3 is a surface SEM image of a covalent organic framework-based semi-solid electrolyte composite membrane, which can demonstrate the uniform artificial pore size of the composite membrane surface, facilitating adsorption and storage of electrolyte.
Fig. 4 is a cycle performance graph of a lithium-lithium symmetric battery assembled by a covalent organic framework-based semi-solid electrolyte composite membrane, wherein the composite membrane has an excellent lithium dendrite inhibition effect, can stably circulate for 900 hours at a current density of 1mA/cm 2, and has an excellent lithium dendrite inhibition effect when the voltage trend is gradually reduced to show that the internal resistance is gradually reduced.
Fig. 5 is a cycle chart of a lithium iron phosphate battery assembled from a covalent organic framework-based semi-solid electrolyte composite separator, which can demonstrate that the semi-solid battery assembled from the covalent organic framework-based semi-solid electrolyte composite separator has good cycle stability (65 turns) and high specific capacity (130 mAh/g).
Fig. 6 is a cycle chart of a nickel-cobalt-manganese ternary lithium battery assembled by the covalent organic framework-based semi-solid electrolyte composite membrane, which can prove that the semi-solid battery assembled by the covalent organic framework-based semi-solid electrolyte composite membrane has good cycle stability (50 circles) and high specific capacity (125 mAh/g).
Claims (10)
1. The preparation method of the covalent organic framework-based semi-solid electrolyte composite membrane is characterized by comprising the following steps of:
Step 1, adding an organic solvent as an auxiliary agent into a covalent organic framework material modified by a long alkyl chain, ball-milling for 12-48 hours, standing the ball-milled mixed solution, and taking supernatant to obtain a covalent organic framework nano-sheet dispersion liquid modified by the long alkyl chain, wherein the structural formula of the covalent organic framework material modified by the long alkyl chain is as follows:
，
The preparation method comprises the following steps:
Adding trihydroxybenzene trioxymethylene and an amino compound modified by a long alkyl chain into a mesitylene/1, 4-dioxane solution, adding acetic acid after ultrasonic dissolution, performing ultrasonic dissolution again to disperse into a suspension, performing liquid nitrogen freezing, vacuumizing and degassing treatment on the suspension, sealing a tube by using a flame gun in a vacuum state, then reacting for 48-168 hours at 120+/-20 ℃ to obtain a crude product, washing the crude product, performing suction filtration, performing Soxhlet extraction by tetrahydrofuran and chloroform, and finally performing vacuum drying to obtain a covalent organic framework material modified by the long alkyl chain, wherein the volume ratio of the mesitylene to the 1, 4-dioxane solution is 1:7~7:1,
The structural formula of the long alkyl chain modified amino compound is as follows:
，
the structural formula of the trihydroxy benzene tricarboxaldehyde is as follows:
；
Step 2, vacuum-filtering the long alkyl chain modified covalent organic framework nano-sheet dispersion liquid by taking a polyethylene film as a bottom film of a vacuum-filtering device, adding ethanol after the vacuum-filtering is finished, performing suction-filtering washing, and finally vacuum-drying to obtain the long alkyl chain modified covalent organic framework composite membrane;
And step3, uniformly coating acetone/water solution of polyvinylidene fluoride-hexafluoropropylene copolymer on two sides of the covalent organic framework composite membrane modified by long alkyl chains in sequence, wherein the coating thickness is 2-50 mu m, and drying after volatilizing the organic solvent to obtain the covalent organic framework-based semi-solid electrolyte composite membrane.
2. The preparation method according to claim 1, wherein in step1, the organic solvent is N-methylpyrrolidone, dimethylformamide or acetonitrile; the ball milling rotating speed is 300-600 rpm; the ball milling time is 6-48 h.
3. The method according to claim 1, wherein in the step 2, the pore diameter of the polyethylene film is 50-200 nm; in the composite membrane formed after vacuum filtration, the thickness of the covalent organic framework nano sheet layer is 2-15 mu m; in the vacuum filtration process, the vacuum degree is 0.1MPa; the vacuum drying temperature is 60-80 ℃, and the drying time is more than 10 hours.
4. The preparation method according to claim 1, wherein in the step 3, in the acetone/water solution of the polyvinylidene fluoride-hexafluoropropylene copolymer, the concentration of the polyvinylidene fluoride-hexafluoropropylene copolymer is 5-15%, and the mass ratio of acetone to water is 9: 1-6: 1, a step of; the drying temperature is 80-90 ℃, and the drying time is 4-12 hours.
5. The method according to claim 1, wherein in the step1 of preparing the covalent organic framework material modified by long alkyl chain, the molar ratio of the trihydroxybenzene trioxymethylene to the amino compound modified by long alkyl chain is 2:3, and the times of freezing in liquid nitrogen, vacuumizing and degassing are 3 or more.
6. The preparation method of the long alkyl chain modified covalent organic framework material according to claim 1, wherein in the preparation step of the long alkyl chain modified covalent organic framework material in step 1, the concentration of the trihydroxybenzene trioxymethylene is 0.3-3 mol/L, the concentration of the long alkyl chain modified amino compound is 0.2-2 mol/L, and the concentration of the acetic acid is 3-12 mol/L.
7. The method of claim 1, wherein in the step of preparing the covalent organic framework material modified by long alkyl chain in step 1, the reaction temperature is 120 ℃ and the reaction time is 72 h; the crude product was washed successively with dichloromethane, ethyl acetate, methanol and acetone.
8. The covalent organic framework-based semi-solid electrolyte composite membrane prepared by the preparation method according to any one of claims 1 to 7.
9. The use of a covalent organic framework-based semi-solid electrolyte composite separator according to claim 8 in a semi-solid lithium ion battery.
10. The use of claim 9, wherein the semi-solid lithium ion battery is a lithium iron phosphate battery or a nickel cobalt manganese ternary lithium battery.
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