CN109686976B - Fluorine-containing conjugated microporous sulfur copolymer, preparation method thereof and application of fluorine-containing conjugated microporous sulfur copolymer as positive electrode material of lithium-sulfur battery - Google Patents
Fluorine-containing conjugated microporous sulfur copolymer, preparation method thereof and application of fluorine-containing conjugated microporous sulfur copolymer as positive electrode material of lithium-sulfur battery Download PDFInfo
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Abstract
The invention discloses a fluorine-containing conjugated microporous sulfur copolymer, a preparation method thereof and application of the fluorine-containing conjugated microporous sulfur copolymer as a lithium-sulfur battery positive electrode material. Carrying out heat treatment on elemental sulfur and tetrafluorobenzoquinone or a fluorine-containing porous polymer at the temperature of 150-180 ℃, and carrying out cross-linking polymerization reaction at the temperature of 200-400 ℃ in a vacuum environment to obtain a fluorine-containing conjugated microporous sulfur copolymer; the polymer contains fluorine units, has a three-dimensional hierarchical pore structure, improves sulfur loading capacity and load stability, and is used for improving battery cycle stability and capacity of a lithium-sulfur battery.
Description
Technical Field
The invention relates to a lithium-sulfur battery positive electrode material, in particular to a fluorine-containing conjugated microporous sulfur copolymer and a preparation method thereof, and also relates to application of the fluorine-containing porous polymer as the lithium-sulfur battery positive electrode material, belonging to the technical field of novel battery materials.
Background
Porous Organic Polymers (POPs) are used as a highly crosslinked nano-pore polymer, have the characteristics of low skeleton density, high specific surface area, good thermal stability, functional modification and the like, and have wide application prospects in the fields of Organic catalysis, gas adsorption and storage, drug controlled release and the like. In the field of research on porous organic polymers, scientists at home and abroad have conducted extensive research and have achieved a series of important achievements. For example, the topic groups of Yaghi, Cooper, Bein, Thomas, Dichtel, Banerjee, Zhang Wei, Jiangdong forest and the like, which are abroad, have made outstanding efforts in the fields of molecular design, synthetic methods, functional development and the like. The national project group of Zhuguanshan reports a porous aromatic skeleton material with high specific surface area (Angew. chem. int. Ed.,2009,48, 9457-; the korean paohuang project group has developed intensive systematic studies on the preparation of porous polymers and the adsorption of various gases (j.am.chem.soc.,2012,134, 6084-; the treyoning topic group is fruitful in asymmetric catalysis of covalent organic frameworks (J.Am.chem.Soc.,2017,139, 8277-8285); tanbien adopts a new polycondensation method as a new strategy for constructing a covalent triazine ring framework, and can prepare a triazine ring framework material under low temperature and simple conditions (Angew. chem. int. Ed.,2017,56, 14149-14153); the Zhao new topic group successfully realizes the covalent organic framework of the heteroporous structure through theoretical simulation and molecular design (J.Am.chem.Soc.,2014,136, 15885-; wang has made a lot of systematic work in the catalytic application of covalent organic framework and the detection of heavy metal ions (J.Am.chem.Soc.,2016,138, 3031-3037). The subject groups of the fur-type nylon (J.Am.chem.Soc.,2017,139,17771-17774) and Wanchen-type nylon (J.Am.chem.Soc.,2017,139, 8705-8709) respectively have excellent work in the aspects of synthesis and function expansion of three-dimensional porous polymers. The Wangbo/Feng skipsis topic group discovers that a novel three-dimensional porous organic framework is successfully constructed by taking cyclodextrin as a structural unit (Angew. chem. int. Ed.,2017,56, 16313-. The bang topic group developed a pH-responsive covalent organic framework (chem. commun.2016,52, 11088-11091). Guojia topic group et al prepared highly catalytically active conjugated organic porous polymers (Angew. chem. int. Ed.,2016,55, 6013-. The Jianjiaxing topic group reports a thiophene-based conjugated porous polymer, which is successfully applied to a lithium battery positive electrode material (adv.funct.mater.,2018,28, adfm.201705432). These efforts have made progress in reducing the cost of porous organic polymers, optimizing structures, improving solubility, expanding functional applications (such as hydrogen storage, photovoltaics, catalysis, gas adsorption, energy materials), and the like.
Among the numerous lithium batteries, the lithium-sulfur battery has the advantages of high specific capacity, high energy density (theoretical energy density can reach 2600Wh/kg), rich sulfur resources, low price, environmental friendliness, high safety and the like. However, in the further development and application links, the problems of low sulfur content, sulfur dissolution, volume expansion effect and the like exist. Although many successful reports have been made on the application of porous polymer materials in lithium-sulfur batteries, the sulfur-supported materials also adopt two methods of physical adsorption and chemical bonding, so as to solve the problems of sulfur expansion effect, sulfur dissolution and the like in the charging and discharging processes. However, due to the lack of strong chemical bonds, most porous polymers have unsatisfactory sulfur fixing effects, and the stability and coulombic efficiency of the battery are obviously reduced after the battery is charged and discharged for many times.
Disclosure of Invention
Aiming at the defects of the porous polymer material applied to the lithium-sulfur battery in the prior art, the first object of the invention is to provide a fluorine-containing conjugated microporous sulfur copolymer which not only has a three-dimensional porous structure, but also introduces sulfur through a stable chemical bond, and dopes fluorine element in a microporous framework, so that the adsorption effect on polysulfide can be improved, the nucleophilic substitution reaction with sulfur can be carried out, and the problems of sulfur expansion effect, sulfur dissolution loss and the like in the charging and discharging processes of the existing lithium-sulfur battery material are well solved.
The second purpose of the invention is to provide a simple and low-cost method for preparing the fluorine-containing conjugated microporous sulfur copolymer.
The third purpose of the invention is to provide the application of the fluorine-containing conjugated microporous sulfur copolymer as a lithium sulfur positive electrode material, and the obtained lithium sulfur battery has high battery capacity and excellent battery stability.
In order to achieve the technical object, the invention provides a fluorine-containing conjugated microporous sulfur copolymer which has a formula I or a formula II
Repeating structural unit:
wherein in formula I or formula II, n is an integer of 1-100.
In a preferable scheme, the fluorine-containing conjugated microporous sulfur copolymer has a three-dimensional porous structure, and the average pore diameter is less than or equal to 100 nm.
The fluorine-containing conjugated microporous sulfur copolymer is in a powder or granular shape.
The fluorine-containing conjugated microporous sulfur copolymer has a three-dimensional porous structure, is favorable for the contact of a positive electrode material and an electrolyte and the improvement of chemical reaction activity on one hand, and can provide an expansion space for the reaction of sulfur on the other hand, thereby being favorable for improving the stability of the material.
The sulfur in the fluorine-containing conjugated microporous sulfur copolymer mainly plays a role in chemical crosslinking, and stable chemical bonds are formed at two ends of a simple substance sulfur molecule, so that the problems of dissolution loss and the like of sulfur can be well prevented.
The fluorine element is introduced into the fluorine-containing conjugated microporous sulfur copolymer, so that the adsorption effect on polysulfide is improved, the problems of sulfur dissolution loss and the like of the conventional lithium-sulfur battery material are well solved, and the fluorine element serving as a substituent group with high activity can perform nucleophilic substitution reaction with sulfur.
The invention also provides a preparation method of the fluorine-containing conjugated microporous sulfur copolymer, which comprises the steps of firstly carrying out heat treatment on monomer sulfur and tetrafluorobenzoquinone or a fluorine-containing porous polymer at the temperature of 150-180 ℃, and then carrying out cross-linking polymerization reaction at the temperature of 200-400 ℃ in a vacuum environment to obtain the fluorine-containing conjugated microporous sulfur copolymer;
the fluorine-containing porous polymer has a repeating structural unit of formula III:
in a preferable scheme, the mass ratio of the elemental sulfur to the tetrafluorobenzoquinone or the fluorine-containing porous polymer is 20-1: 1; more preferably 10 to 1: 1.
In a preferable scheme, the heat treatment time is 1-48 h. The preferable heat treatment time is 8-28 h, and the sulfur and the polymerization monomer are fully melted and mixed through the heat treatment.
In a preferable scheme, the time of the cross-linking polymerization reaction is 1-48 h. The preferable reaction time of the cross-linking polymerization is 8-28 h, and the complete cross-linking reaction is ensured.
The tetrafluorobenzoquinone of the present invention is a commercial tetrafluorobenzoquinone.
The fluorine-containing porous polymer is prepared by reacting tetrafluorobenzoquinone or blend of tetrafluorobenzoquinone and tetrafluorohydroquinone for 12 hours at 160 ℃ in a DMF solvent in the presence of inorganic salt potassium carbonate in a nitrogen atmosphere, and precipitating, filtering and drying the obtained solid to obtain the fluorine-containing porous polymer.
The invention also provides an application of the fluorine-containing conjugated microporous sulfur copolymer as a lithium-sulfur positive electrode material.
The fluorine-containing conjugated microporous sulfur copolymer is used for preparing a lithium-sulfur battery: mixing fluorine-containing conjugated microporous sulfur copolymer: acetylene black: PVDF was prepared in a 7:2:1 mass ratio by first dissolving PVDF in NMP (1 mL)0.4g), grinding the fluorine-containing conjugated microporous sulfur copolymer and acetylene black for 20min, stirring the mixture and a PVDF solution for 5h, coating the mixture on an aluminum foil by using a coating machine, wherein the coating thickness is 10-100um, carrying out vacuum drying at 60 ℃ for 12h, the weighed sulfur carrying amount is 0.8-2.5 mg, taking out the dried product and packaging the product in a glove box to form a button cell, the button cell takes the coated aluminum foil as a cathode and lithium metal as an anode, 1M lithium bistrifluoromethanesulfonylimide (LiTFSI) is dissolved in 1, 3-Dioxolane (DOL)/ethylene glycol dimethyl ether (DME) at a ratio of 1:1V, and 1% of LiNO is added3As an electrolyte.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the fluorine-containing conjugated microporous sulfur copolymer disclosed by the invention not only has a three-dimensional porous structure, but also introduces sulfur through a stable chemical bond, and dopes fluorine element in a microporous framework, so that the problems of sulfur expansion effect, sulfur dissolution and the like in the charging and discharging processes of the existing lithium-sulfur battery material are well solved, and the battery capacity is improved.
The fluorine-containing conjugated microporous sulfur copolymer is simple in preparation method, low in cost and beneficial to industrial production.
The fluorine-containing conjugated microporous sulfur copolymer is applied as a lithium-sulfur positive electrode material, and the obtained lithium-sulfur battery has high battery capacity and excellent battery stability.
Drawings
FIG. 1: (1) in the infrared spectrogram before and after the reaction of tetrafluorobenzoquinone with sulfur in example 1, the C-F bond strength is reduced, and a new C-S bond is formed; (2) in the infrared spectrogram before and after the reaction of the fluorine-containing organic porous polymer and the sulfur in the example 2, the strength of the C-F bond is reduced, and a new C-S bond is formed; (3) example 1 TBQ-S after reaction of Tetrafluorobenzoquinone with SulfurnA Raman spectrogram, wherein newly generated C-S and S-S peaks indicate that the sulfur-containing porous polymer is successfully generated; (4) example 2 TBP-S after reaction of fluorine-containing organic porous Polymer with SulfurnRaman spectrogram, newly generated C-S and S-S peaks show that the sulfur-containing porous polymer is successfully generated.
FIG. 2: (1) thermogravimetric curves before and after reaction of tetrafluorobenzoquinone with sulfur in example 1 illustrate polyThe thermal stability of the compound is greatly improved; (2) example 2 TBP-S before and after reaction of fluorine-containing organic porous Polymer with SulfurnAnd a TBP thermogravimetric curve shows that the thermal stability of the polymer is greatly improved.
FIG. 3: (1) TBQ scanning electron microscope; (2) TBQ-SnScanning an electron microscope; (3) TBP scanning electron microscope; (4) TBP-SnScanning an electron microscope; the appearance of the porous fluorine-containing organosulfur polymer produced by the reaction of tetrafluorobenzoquinone with sulfur in example 1 is greatly changed.
FIG. 4: (1) TBQ-SnThe cyclic voltammetry curve shows that the material has good electrochemical stability; (2) TBQ-SnThe alternating current impedance spectrum shows that the fluorine-containing organosulfur porous polymer prepared in the embodiment 1 has low resistance and is beneficial to being applied to the field of batteries; (3) TBQ-SnMultiplying power performance test shows that the material can be recycled; (4) TBQ-SnAnd the cycle stability curve shows that the battery material is very stable and can be used for a long time.
Detailed Description
The following examples are intended to illustrate the present disclosure in further detail, but are not intended to limit the scope of the present claims.
The polymer was confirmed by FT-IR on a Nicolet-6700 type infrared spectrometer and was tabletted with KBr to prepare a sample. Polymer thermal stability test: the decomposition temperature test of the Thermal Gravimetric Analysis (TGA) polymer is carried out on an SDT Q600V 8.0 synchronous thermal analyzer manufactured by American TA company, the heating rate is 10 ℃/min under the nitrogen atmosphere, the test temperature range is 30-400 ℃, and the 5 percent thermal gravimetric temperature is taken as the decomposition temperature of the polymer.
The button cell is prepared by the following steps: mixing fluorine-containing conjugated microporous sulfur copolymer: acetylene black: preparing PVDF (polyvinylidene fluoride) (7: 2: 1) in a mass ratio, dissolving the PVDF in NMP (1mL/0.4g), grinding the fluorine-containing conjugated microporous sulfur copolymer and acetylene black for 20min, stirring the mixture with the PVDF solution for 5h, coating the mixture on an aluminum foil by using a coating machine, wherein the thickness of the coating is 10-100um, drying the coating in vacuum at 60 ℃ for 12h, taking out the dried coating and packaging the dried coating in a glove box to form a button cell, wherein the button cell takes the coated aluminum foil as a cathode, lithium metal as an anode and 1M lithium bistrifluoromethanesulfonimide (LiTFSI)) Dissolved in 1, 3-Dioxolane (DOL)/ethylene glycol dimethyl ether (DME) at 1: 1V% and 1% LiNO added3As an electrolyte.
Example 1
Taking the mass ratio of the fluorine-containing monomer to the elemental sulfur as an example of 1:3, weighing and uniformly mixing tetrafluorobenzoquinone (100mg) and the elemental sulfur (300mg) in a glass bottle (10mL, 10mm of outer diameter and 8mm of inner diameter), and burning and sealing the glass bottle by a flame gun under the condition of exhausting air. The mixture was held at 160 ℃ for 16h and then heated to 200 ℃ for 16 h. The product was removed in the form of a cake and ground to a yellow powder. The sulfur content was tested to be 66%.
Example 2
Taking the mass ratio of the fluorine-containing porous polymer to the elemental sulfur as an example of 1:3, the polymer POP-TBP (100mg) and the elemental sulfur (300mg) are weighed and uniformly mixed in a glass bottle (10mL, the outer diameter is 10mm, and the inner diameter is 8mm), and the glass bottle is blown and sealed by a flame gun under the condition of air suction. The mixture was held at 160 ℃ for 16h and then heated to 200 ℃ for 16 h. The cake was removed and ground to a black powder. The sulfur content was tested to be 53%.
Example 3
Taking the mass ratio of the fluorine-containing monomer to the elemental sulfur as an example of 1:10, weighing and uniformly mixing tetrafluorobenzoquinone (100mg) and the elemental sulfur (1000mg) in a glass bottle (10mL, 10mm of outer diameter and 8mm of inner diameter), and burning and sealing the glass bottle by a flame gun under the condition of exhausting air. The mixture was held at 180 ℃ for 10h and then heated to 250 ℃ for 10 h. The product was removed in the form of a cake and ground to a yellow powder. The sulfur content was tested to be 70%.
Example 4
The reaction is carried out by taking the mass ratio of the fluorine-containing porous polymer to the elemental sulfur as an example of 1:5, weighing the polymer POP-TBP (100mg) and the elemental sulfur (500mg), uniformly mixing in a glass bottle (10mL, 10mm external diameter and 8mm internal diameter), and burning and sealing by a flame gun under the condition of exhausting air from the glass bottle. The mixture was held at 150 ℃ for 20h and then heated to 280 ℃ for 12 h. The cake was removed and ground to a black powder. The sulfur content was tested to be 63%.
Claims (7)
1. A fluorine-containing conjugated microporous sulfur copolymer characterized in that: having a repeating structural unit of formula I or formula II:
wherein in formula I or formula II, n is an integer of 1-100.
2. The fluorine-containing conjugated microporous sulfur copolymer according to claim 1, wherein: the fluorine-containing conjugated microporous sulfur copolymer has a three-dimensional porous structure, and the average pore diameter is less than or equal to 100 nm.
3. The process for producing a fluorine-containing conjugated microporous sulfur copolymer according to claim 1 or 2, wherein: carrying out heat treatment on elemental sulfur and tetrafluorobenzoquinone or fluorine-containing porous polymer at the temperature of 150-180 ℃, and carrying out cross-linking polymerization reaction at the temperature of 200-400 ℃ in a vacuum environment to obtain the sulfur-containing porous polymer;
the fluorine-containing porous polymer has a repeating structural unit of formula III:
4. the method for preparing a fluorine-containing conjugated microporous sulfur copolymer according to claim 3, wherein: the mass ratio of the elemental sulfur to the tetrafluorobenzoquinone or the fluorine-containing porous polymer is 20-1: 1.
5. The method for preparing a fluorine-containing conjugated microporous sulfur copolymer according to claim 3, wherein: the heat treatment time is 1-48 h.
6. The method for preparing a fluorine-containing conjugated microporous sulfur copolymer according to claim 3, wherein: the time of the cross-linking polymerization reaction is 1-48 h.
7. Use of a fluorine-containing conjugated microporous sulfur copolymer according to any one of claims 1 or 2, wherein: the lithium-sulfur anode material is applied as a lithium-sulfur anode material.
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| CN105885048A (en) * | 2014-12-12 | 2016-08-24 | 中国人民解放军63971部队 | Polythioquinone and preparation method thereof |
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| US9257699B2 (en) * | 2013-03-07 | 2016-02-09 | Uchicago Argonne, Llc | Sulfur cathode hosted in porous organic polymeric matrices |
| US20150056507A1 (en) * | 2013-08-21 | 2015-02-26 | GM Global Technology Operations LLC | Lithium-based battery electrodes |
| DE102014221731A1 (en) * | 2014-06-06 | 2016-01-21 | Robert Bosch Gmbh | Polymer electrolyte for lithium-sulfur cell |
| CN107293694A (en) * | 2017-05-22 | 2017-10-24 | 深圳大学 | Polysulphide polymer composite its preparation method and application |
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| EP0901180A1 (en) * | 1997-08-29 | 1999-03-10 | Alcatel | Rechargeable lithium battery with organic electrolyte and carbone anode |
| CN105885048A (en) * | 2014-12-12 | 2016-08-24 | 中国人民解放军63971部队 | Polythioquinone and preparation method thereof |
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| "Highly Fluoro-Substituted Covalent Organic Framework and Its Application in Lithium-Sulfur Batteries";De-Gao Wang et al.;《ACS APPLIED MATERIALS AND INTERFACES》;20181115;摘要，说明书第42234页，附图1 * |
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