CN117878528A - Preparation method and application of self-supporting diaphragm of covalent organic framework - Google Patents
Preparation method and application of self-supporting diaphragm of covalent organic framework Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000012528 membrane Substances 0.000 claims abstract description 22
- 229920002749 Bacterial cellulose Polymers 0.000 claims abstract description 13
- 239000005016 bacterial cellulose Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 150000001768 cations Chemical group 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000010257 thawing Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000000944 Soxhlet extraction Methods 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011701 zinc Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052725 zinc Inorganic materials 0.000 abstract description 6
- 150000002500 ions Chemical group 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 5
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 230000035699 permeability Effects 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 2
- 230000002411 adverse Effects 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 abstract description 2
- 102000004310 Ion Channels Human genes 0.000 abstract 1
- 239000011363 dried mixture Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 10
- 230000001351 cycling effect Effects 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 4
- CZLMUMZXIXSCFI-UHFFFAOYSA-N [Zn].[I] Chemical compound [Zn].[I] CZLMUMZXIXSCFI-UHFFFAOYSA-N 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- HEAHMJLHQCESBZ-UHFFFAOYSA-N 2,5-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(N)C(S(O)(=O)=O)=C1 HEAHMJLHQCESBZ-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 2
- 229960001553 phloroglucinol Drugs 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- -1 sodium hexafluorophosphate Chemical compound 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 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 description 1
- MKHDOBRSMHTMOK-UHFFFAOYSA-N 5-amino-2-(4-amino-2-carboxyphenyl)benzoic acid Chemical compound OC(=O)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(O)=O MKHDOBRSMHTMOK-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 1
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method and application of a self-supporting diaphragm of a covalent organic framework, which are applicable to the technical field of new energy battery materials. The covalent organic frame self-supporting membrane is obtained by mixing covalent organic frame materials and bacterial cellulose in aqueous solution, filtering the mixture to a microporous filter membrane, drying the mixture, and uncovering the dried mixture. The covalent organic framework material contains metal cation groups and regular pore canal structures, improves the selective permeability of metal ions, forms a single ion channel, and inhibits adverse side reactions of electrode interfaces. The preparation method of the diaphragm has the advantages of simple process, good universality, low cost, controllable thickness and strong practicability, and can be applied to lithium, sodium and zinc secondary ion batteries. The capacity retention rate of the assembled lithium sulfur battery after 100 circles of circulation under the current density of 0.2C is as high as 87.5%, and the assembled lithium sulfur battery has excellent circulation stability and potential application prospect.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a preparation method and application of a self-supporting diaphragm of a covalent organic framework.
Background
As the global population continues to grow and economy rapidly evolves, the demand for energy continues to increase. Conventional energy sources such as fossil fuels have problems of shortage of supply, environmental pollution, and the like, so searching for sustainable and clean energy substitutes is an urgent need. The secondary battery is used as a device capable of converting chemical energy into electric energy, has the characteristics of high energy density, portability, repeated charge and discharge and the like, and is an important technical means for energy storage and conversion.
Current research in the battery field is also challenged, with one of the most important problems being short service life and poor cycling stability. The life and cycling stability of the battery are critical to battery reliability and economy. During long-time use and cyclic charge and discharge processes of the battery, dendrites are formed on the metal anode, and the metal anode pierces through the diaphragm in the cyclic process to enable the anode and the cathode to be in contact with each other so as to cause internal short circuit of the battery; at the same time, repeated oxidation-reduction reactions of the cathode occur, so that the structure of the cathode is destroyed or discharge products which are easily dissolved in the electrolyte are generated, and capacity fading occurs. In view of the above challenges, scientists and engineers are developing various researches and innovations including development of new materials, optimization of electrode structures and designs, improvement of electrolytes, modification of separators, etc., to promote progress and breakthrough in energy density and cycle stability of secondary batteries.
Covalent organic framework materials (COFs) are currently being widely studied as an emerging class of materials. COFs generally have crystalline structures composed of repeating units with rich pore channels, large specific surface area, low density, and other characteristics. COFs also have higher chemical and thermal stability due to the presence of covalent bonds. Meanwhile, the COFs can be regulated and controlled by selecting different organic monomer molecules and synthetic methods, and various COFs with different structures and topology types can be constructed. The pore size, pore structure and intrinsic chemical property of the organic monomer molecule can be regulated by regulating the strategies such as the structure of the organic monomer molecule, the introduction of functional groups and the like, so that the regulation and control of the adsorptivity, selectivity and catalytic performance of the object are realized. The single ion conductive covalent organic frame membrane is prepared by doping metal cations into the COFs, so that the selective permeability of corresponding ions can be enhanced, the migration number of the metal ions can be increased, and adverse interface side reactions between electrolyte anions and metal electrodes can be reduced. However, COFs powder is difficult to form films effectively in the prior art, and COFs separators synthesized by phase interface reaction are dense but have insufficient mechanical strength, so that the COFs powder is difficult to be applied effectively in metal ion secondary batteries. How to construct a COFs self-supporting separator that is uniform, compact, good in mechanical properties, and easy to process is an important challenge for current COFs materials in secondary battery applications.
Disclosure of Invention
The invention aims to provide a preparation method of a self-supporting diaphragm of a covalent organic framework and application of the self-supporting diaphragm in a battery, so as to solve the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method of preparing a covalent organic framework self-supporting separator comprising the steps of:
step one: by incorporating organic monomers M 1 、M 2 Adding the mixed solution of mesitylene, dioxane and acetic acid into a heat-resistant glass tube, uniformly dispersing by ultrasonic, freezing in liquid nitrogen, vacuumizing, thawing to room temperature, repeating the freezing-vacuumizing-thawing process for 3-5 times, sealing by flame, placing in a drying oven at 120 ℃ for reaction and heating for 3 days, collecting precipitate, and carrying out Soxhlet extraction treatment for 6-24 hours by using the mixed solution of tetrahydrofuran and dichloromethane. And then vacuum drying is carried out for 6 to 12 hours at the temperature of 60 to 80 ℃ to obtain the COF material.
Step two: and (3) placing the COF material in acetate solution, stirring at room temperature for 72 hours, washing with water after the reaction is finished, collecting solids, and then drying in vacuum at 80-120 ℃ for 15-20 hours to obtain the metal cation substituted COF material.
Step three: and dispersing the metal cation substituted COF material and bacterial cellulose in water uniformly, mixing and stirring uniformly, performing vacuum filtration on the mixture to a microporous filter membrane, and removing the dried membrane to obtain the covalent organic framework self-supporting membrane.
Based on the technical scheme, the invention also provides the following optional technical schemes:
in one alternative: the organic monomer M 1 The structure is as follows:
wherein:
x is H, OH or OCH 3 Any one element or group of Cl, br and I.
In one alternative: the organic monomer M 2 The structure is as follows:
wherein:
y is COOH, SO 3 H and PO 4 H 2 Any one of the groups;
z is H, OH and OCH 3 Any one of the elements or groups;
q is H, COOH, SO 3 H and PO 4 H 2 Any one of the elements or groups.
In one alternative: in step one, the organic monomer M 1 And M is as follows 2 The ratio of the added substances is 1:1.2-1:1.8; the volume ratio of the added mesitylene to the dioxane is 0.3 to 3, and 3 to 6 mol.L is added -1 The volume amount of the acetic acid with the concentration is 0.2-1.0 mL.
In one alternative: acetate in the second step is any one of zinc salt, sodium salt and lithium salt, and the concentration of the acetate is 0.8-2.5 mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The mass ratio of the COF material to the acetate is 1:10-1:100.
In one alternative: in the third step, the mass ratio of the COF material doped with metal ions to bacterial cellulose to water is 1:4-1:10 and 1:20-1:100 respectively; the drying is carried out by adopting any one method of vacuum drying, normal pressure blast drying and vacuum freeze drying, and the drying is carried out for 6-24 hours at the temperature of minus 50-120 ℃.
Use of a covalent organic framework self-supporting separator in a battery, characterized in that the self-supporting separator is used for the assembly of a button cell or prismatic cell or a cylindrical cell or a pouch cell.
In one alternative: the assembled battery may be a lithium ion battery or a sodium ion battery or a zinc ion battery.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method of the diaphragm provided by the invention has scientific and reasonable design, simple process and strong applicability, and can be applied to lithium, sodium and zinc ion batteries. The prepared covalent organic framework self-supporting diaphragm can prevent the structure of the anode from being damaged in the multiple reaction processes, inhibit the side reaction of the metal anode interface, and effectively improve the cycle stability of the battery.
2. The covalent organic framework diaphragm has a regular pore canal structure, and the doped metal cations enhance the ion selective permeability, so that the effective migration number of ions can be improved, and the rapid charge and discharge performance of the battery under high current multiplying power is effectively improved.
3. The covalent organic framework diaphragm can maintain structural integrity under higher temperature and chemical environment due to the existence of covalent bonds, and can improve the cycling stability of the battery in a wide temperature range; meanwhile, the mixed bacterial cellulose has good mechanical properties after being made into a film, and the assembled battery can avoid metal dendrites from penetrating through a diaphragm, so that the service life of the battery is prolonged.
Drawings
FIG. 1 is a TpPa-SO prepared in example 1 3 Schematic of Li structure.
FIG. 2 is a TpPa-SO prepared in example 1 3 Powder X-ray diffraction pattern of Li.
Fig. 3 is a graph of the cycling performance of the lithium sulfur battery prepared in example 1 at a current density of 0.2C.
Fig. 4 is a schematic structural diagram of a lithium ion substituted COF material prepared in example 2.
Fig. 5 is a graph of the cycling performance of the lithium ion battery prepared in example 2 at a current density of 0.2C.
Fig. 6 is a schematic structural diagram of a sodium ion substituted COF material prepared in example 3.
Fig. 7 is a graph of the cycling performance of the sodium ion cell prepared in example 3 at a current density of 0.2C.
Fig. 8 is a schematic structural diagram of a zinc ion-substituted COF material prepared in example 4.
Fig. 9 is a graph of the cycling performance of the zinc-ion cell prepared in example 4 at a current density of 0.2C.
Fig. 10 is a schematic structural diagram of a zinc ion-substituted COF material prepared in example 5.
Fig. 11 is a graph of the cycling performance of the zinc-iodine battery prepared in example 5 at a current density of 10C.
Detailed Description
In order to make the technical scheme of the present invention more clear, the technical scheme of the embodiment of the present invention will be fully and specifically described below with reference to the accompanying drawings. It is emphasized that the following examples are given solely for the better understanding of the present invention and are not intended to limit the scope of the invention.
Example 1
The preparation and application of the sulfonic acid group covalent organic framework diaphragm in the lithium sulfur battery:
step one, 31.5mg of trialdehyde phloroglucinol is weighed as an organic monomer M 1 43mg of 2, 5-diaminobenzenesulfonic acid was weighed as the organic monomer M 2 By combining organic monomers M 1 And an organic monomer M 2 Placing the glass tube into a heat-resistant glass tube; into a glass tube, 0.75mL of mesitylene, 0.75mL of dioxane, 0.3mL of 3 mol.L were added -1 A mixed solution of acetic acid and uniformly dispersed by ultrasonic waves; freezing in liquid nitrogen, vacuumizing, thawing to room temperature, repeating for 3 times, sealing with flame, heating in a drying oven at 120deg.C for 3 days, collecting precipitate, and collecting precipitateThe mixed solution of tetrahydrofuran and methylene chloride was subjected to a soxhlet extraction treatment for 24 hours. Then vacuum drying at 80deg.C for 6 hr to obtain COF material (TpPa-SO 3 H)。
Step two: the TpPa-SO obtained above is subjected to 3 H material is put into 40mL with the concentration of 1 mol.L -1 Stirring at room temperature for 72 hours, washing with water after the reaction, collecting the solid, and vacuum drying at 80deg.C for 15 hours to obtain lithium ion substituted COF material (TpPa-SO 3 Li) whose molecular structure is shown in FIG. 1 and powder X-ray diffraction pattern is shown in FIG. 2.
Step three: referred to as TpPa-SO 3 And (3) uniformly dispersing 4mg of Li material and 0.3g of Bacterial Cellulose (BC) dispersion liquid (content of 0.8%) in 20mL of water respectively, mixing, uniformly stirring, performing vacuum filtration on the mixture to a microporous filter membrane, and performing normal pressure drying at 70 ℃ for 12 hours to obtain the self-supporting membrane.
Then, the obtained diaphragm is used for a lithium sulfur battery, a Ketjen black/sulfur composite positive electrode (70 wt.% sulfur load) is selected as a positive electrode material, a lithium sheet is used as a negative electrode, an electrolyte is a traditional ether electrolyte, and the lithium sulfur battery is assembled to obtain the lithium sulfur battery, wherein the initial ring discharge specific capacity can reach 1076mAh g under the current density of 0.2C -1 After 100 circles of circulation, 941mAh g can be obtained -1 The performance is shown in figure 3. The self-supporting diaphragm effectively inhibits dissolution shuttling of polysulfide in the charge-discharge cycle process, and improves the cycle stability of the lithium-sulfur battery.
Example 2
The preparation and application of the sulfonic acid group covalent organic framework diaphragm in the lithium ion battery:
step one, weighing 14mg of trimesic aldehyde as an organic monomer M 1 43mg of 2, 5-diaminobenzenesulfonic acid was weighed as the organic monomer M 2 By combining organic monomers M 1 And an organic monomer M 2 Placing the glass tube into a heat-resistant glass tube; 1mL of mesitylene, 1mL of dioxane, and 0.3mL of a concentration of 6 mol.L were added to a glass tube -1 The procedure used subsequently for the preparation of the acetic acid mixture was identical to that used in step one of example 1.
Step two, 300mg of the COF material obtained in the step one is put into 40mL of a material with the concentration of 1 mol.L -1 The method adopted in the subsequent step is consistent with the preparation method of the step two in the example 1, and after the reaction, the lithium ion substituted COF material can be obtained, and the molecular structure of the material is shown in figure 4.
And thirdly, weighing 5mg of the lithium ion substituted COF material and 0.5g of BC dispersion liquid (the content is 0.8%) to be uniformly dispersed in 30mL of water respectively, then mixing, stirring uniformly, carrying out vacuum filtration on the mixture to a microporous filter membrane, and carrying out vacuum drying at-50 ℃ for 12 hours to obtain the self-supporting membrane of the covalent organic framework.
Subsequently, the separator obtained as described above was used in a lithium ion battery, commercial graphite was selected for the negative electrode, and commercial lithium iron phosphate (average active material loading of 10mg·cm was used for the positive electrode -2 ) The electrolyte is a traditional ester electrolyte, and the initial ring discharge is 156mAh g under the current density of 0.2C -1 After 50 cycles, the alloy still has 155mAh g -1 The discharge specific capacity of (2) is almost the same as that of (5), and the cycle performance is shown in FIG. 5.
Example 3
Preparation application of sodium ion substituted covalent organic framework membrane in sodium ion battery:
step one, trimesic aldehyde is taken as an organic monomer M 1 4,4 '-diaminobiphenyl-2, 2' -dicarboxylic acid as organic monomer M 2 The COF material is constructed by a schiff base system. The synthesis procedure was identical to that of step one of example 1.
Step two, the COF material synthesized in the step one is put into 40mL with the concentration of 2 mol.L -1 The method adopted in the subsequent step is consistent with the preparation method of the step two in the example 1, and a sodium ion substituted COF material can be obtained after the reaction, and the molecular structure of the material is shown in figure 6.
And step three, preparing a self-supporting diaphragm by using the synthesized sodium ion substituted COF material, wherein the adopted method is identical to the preparation method of the step three in the example 1.
Subsequently, the separator obtained above was used for a sodium ion battery, negative electrodeSodium metal is selected, a pyrene tetraketone/active carbon composite positive electrode (70 wt.% pyrene tetraketone content) is adopted as a positive electrode, an ester electrolyte containing sodium hexafluorophosphate is adopted, and a button cell is assembled at 0.2Ag -1 The cycle performance test is carried out under the current density of (1), and the first-circle contribution capacity is 324mAh g -1 After 100 cycles, the capacity is kept at 280mAh g -1 The capacity retention was 86.4% and the cycle performance was as shown in fig. 7.
Example 4
The preparation and application of the sulfonic acid group covalent organic framework diaphragm in the zinc ion battery:
step one: taking the TpPa-SO obtained in example 3 H material is put into 40mL with the concentration of 1 mol.L -1 Stirring at room temperature for 72 hours, washing with water after the reaction, collecting the solid, and vacuum drying at 80deg.C for 15 hours to obtain zinc ion substituted COF material (TpPa-SO 3 Zn 0.5 ) The molecular structure is shown in FIG. 8.
Step two: referred to as TpPa-SO 3 Zn 0.5 And (3) uniformly dispersing 10mg of the material and 0.5g of Bacterial Cellulose (BC) dispersion liquid (the content is 0.8%) in 50mL of water respectively, then uniformly mixing and stirring, performing vacuum filtration on the mixture to a microporous filter membrane, and removing the membrane after vacuum drying for 12 hours at 50 ℃ to obtain the self-supporting membrane.
Then, the obtained diaphragm is used for a water-based zinc ion battery, vanadium pentoxide is selected as a positive electrode material, a zinc sheet is selected as a negative electrode, and the electrolyte is 1mol L -1 And (3) assembling the zinc trifluoromethane sulfonate aqueous solution to obtain the zinc ion battery. At 0.2Ag -1 The cycle performance test is carried out under the current density, and the specific capacity of the first-cycle discharge is 422mAh g -1 After 200 circles of circulation, the specific discharge capacity is kept at 354mAh g -1 Shows a capacity retention of 84% and cycle performance as shown in fig. 9. The zinc ion battery assembled by the diaphragm has coulombic efficiency approaching 100% in the whole cycle test process, and shows excellent electrochemical reversibility.
Example 5
The preparation and application of the sulfonic acid group covalent organic framework diaphragm in the water-based zinc-iodine battery:
step one, weighing 14mg of trialdehyde phloroglucinol as an organic monomer M 1 Weighing 4,4' -diamino-5 ' - (4-amino-2-sulfophenyl) - [1,1':3', 1' -terphenyl ]]59mg of 2,2' -disulfonic acid as organic monomer M 2 The remaining procedure was as in step one of example 1. Covalent organic framework materials rich in sulfonic acid groups are obtained.
Step two: weighing the COF material obtained in the first step, and placing 40mL of the COF material with the concentration of 1 mol.L -1 After the completion of the reaction, the mixture was washed with water and the solid was collected, and then dried in vacuo at 80℃for 15 hours to give a zinc ion-substituted COF material having a molecular structure shown in FIG. 10.
And step three, taking 10mg of the COF material and 0.5g of Bacterial Cellulose (BC) dispersion liquid (the content is 0.8%) in the step two, dispersing uniformly in 50mL of water respectively, mixing, stirring uniformly, carrying out vacuum filtration on the mixture to a microporous filter membrane, and carrying out vacuum drying at 50 ℃ for 12 hours to obtain the self-supporting membrane.
Subsequently, the separator obtained above was used in a water-based zinc-iodine battery, activated carbon/iodine (iodine content 60 wt.%) was selected as the positive electrode, a zinc sheet was used as the negative electrode, and the electrolyte was 1mol L -1 And (3) assembling to obtain the zinc ion battery. At a current density of 10C (1c=211 mAg -1 ) The initial capacity of the sample is 181mAh g -1 The capacity of the material still keeps 163mAh g after 980 circles -1 The capacity retention was 90%, and very good electrochemical stability was exhibited, and the cycle performance was shown in fig. 11.
The foregoing is merely illustrative of specific embodiments of the present disclosure, and the detailed description of the embodiments above is intended to be illustrative, rather than limiting. The specific embodiments of the present invention are not limited to the above examples, and modifications and equivalents of the technical solutions without departing from the spirit of the present invention should be considered as belonging to the scope of protection defined in the claims filed herewith.
Claims (8)
1. A method for preparing a self-supporting membrane of a covalent organic framework, comprising the steps of:
step one: by incorporating organic monomers M 1 、M 2 Adding a mixed solution of mesitylene, dioxane and acetic acid into a heat-resistant glass tube, performing ultrasonic dispersion uniformly, freezing in liquid nitrogen, vacuumizing, thawing to room temperature, repeating the steps for 3-5 times, sealing by flame, placing in a drying box at 120 ℃ for heating reaction for 3 days, collecting a precipitate, performing Soxhlet extraction treatment for 6-24 hours by using a mixed solvent of tetrahydrofuran and dichloromethane, and then performing vacuum drying at 60-80 ℃ for 6-12 hours to obtain the covalent organic framework material;
step two: placing the covalent organic frame material into acetate solution, stirring for 72 hours at room temperature, washing with water after the reaction is finished, collecting solids, and then drying in vacuum at 80-120 ℃ for 15-20 hours to obtain the covalent organic frame material substituted by metal cations;
step three: and (3) dispersing the covalent organic framework material substituted by the metal cations and the bacterial cellulose in water uniformly, mixing, stirring uniformly, carrying out vacuum filtration on the mixture to a microporous filter membrane, and removing the dried membrane to obtain the covalent organic framework self-supporting membrane.
2. The method for preparing a self-supporting separator for covalent organic frameworks according to claim 1, wherein said organic monomer M 1 The structure is as follows:
wherein:
x is H, OH or OCH 3 Any one element or group of Cl, br and I.
3. The method for preparing a self-supporting separator for covalent organic frameworks according to claim 1, wherein said organic monomer M 2 The structure is as follows:
wherein:
y is COOH, SO 3 H and PO 4 H 2 Any one of the groups;
z is H, OH and OCH 3 Any one of the elements or groups;
q is H, COOH, SO 3 H and PO 4 H 2 Any one of the elements or groups.
4. The method for preparing a self-supporting separator for covalent organic frameworks according to claim 1, wherein the organic monomer M in step one 1 And M is as follows 2 Adding the water into the mixture in a molar ratio of 1:1.2-1:1.8, wherein the volume ratio of the added mesitylene to the dioxane is 0.3-3, and the concentration of the added acetic acid is 3-6mol.L -1 。
5. The method for preparing a self-supporting membrane of a covalent organic framework according to claim 1, wherein acetate in the second step is any one of zinc salt, sodium salt and lithium salt, and the concentration of the acetate is 0.8-2.5 mol.L -1 The mass ratio of the covalent organic framework material to the acetate is 1:10-1:100.
6. The method for preparing a self-supporting membrane of a covalent organic framework according to claim 1, wherein the mass ratio of the covalent organic framework material substituted by metal ions to bacterial cellulose and water in the step three is 1:4-1:10 and 1:20-1:100 respectively; the drying is carried out by adopting any one method of vacuum drying, normal pressure blast drying and vacuum freeze drying, and the drying is carried out for 6-24 hours at the temperature of minus 50-120 ℃.
7. Use of a covalent organic framework self-supporting separator according to any of claims 1-6 in a battery, characterized in that the covalent organic framework self-supporting separator is used for the assembly of a button cell or prismatic cell or a cylindrical cell or a pouch cell.
8. The battery application according to claim 7, wherein the battery type is a lithium ion battery or a sodium ion battery or a zinc ion battery.
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