CN108503834A - A kind of the 4- methyl -5- vinylthiazoles-sulphur copolymer and preparation method of the auto-dope of sulphur nitrogen - Google Patents
A kind of the 4- methyl -5- vinylthiazoles-sulphur copolymer and preparation method of the auto-dope of sulphur nitrogen Download PDFInfo
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- CN108503834A CN108503834A CN201710102754.1A CN201710102754A CN108503834A CN 108503834 A CN108503834 A CN 108503834A CN 201710102754 A CN201710102754 A CN 201710102754A CN 108503834 A CN108503834 A CN 108503834A
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- methyl
- sulphur
- vinylthiazoles
- copolymer
- elemental sulfur
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- 239000005864 Sulphur Substances 0.000 title claims abstract description 52
- 229920001577 copolymer Polymers 0.000 title claims abstract description 35
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 23
- 239000011593 sulfur Substances 0.000 claims abstract description 19
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000003254 radicals Chemical class 0.000 claims abstract description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 7
- SZMYFESRCUFULU-UHFFFAOYSA-N 5-ethenyl-1,3-thiazole Chemical compound C=CC1=CN=CS1 SZMYFESRCUFULU-UHFFFAOYSA-N 0.000 claims abstract description 6
- QUAMMXIRDIIGDJ-UHFFFAOYSA-N 5-ethenyl-4-methyl-1,3-thiazole Chemical class CC=1N=CSC=1C=C QUAMMXIRDIIGDJ-UHFFFAOYSA-N 0.000 claims description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 12
- 230000006399 behavior Effects 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- -1 alkenyl thiazole Chemical compound 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 230000000007 visual effect Effects 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 3
- 239000011149 active material Substances 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 4
- 235000001508 sulfur Nutrition 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000005077 polysulfide Substances 0.000 description 8
- 229920001021 polysulfide Polymers 0.000 description 8
- 150000008117 polysulfides Polymers 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000003487 electrochemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 244000288157 Passiflora edulis Species 0.000 description 2
- 235000000370 Passiflora edulis Nutrition 0.000 description 2
- 235000009470 Theobroma cacao Nutrition 0.000 description 2
- 244000299461 Theobroma cacao Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000008116 organic polysulfides Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/025—Preparatory processes
- C08G75/0263—Preparatory processes using elemental sulfur
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The present invention discloses a kind of 4 methyl, the 5 vinylthiazole sulphur copolymer and preparation method of the auto-dope of sulphur nitrogen, elemental sulfur is heated to molten condition, so as to be broken by the sulphur ring that 8 sulphur atoms form, form the sulphur chain with diradical end group, after 4 methyl, 5 vinylthiazole is added, the carbon-carbon double bond that the chain free radical in molten sulfur causes in 4 methyl, 5 vinylthiazole is free-radical polymerized to carry out.Elemental sulfur is reacted with 4 methyl, 5 vinylthiazole in the present invention, and high sulfur content copolymer can be made, and is used as lithium sulfur battery anode material, is greatly improved the content of active material in anode.
Description
Technical field
The present invention relates to the synthesis of high sulfur-containing polymer, belong to synthetic technology and lithium-sulfur cell preparing technical field, specifically
It is related to a kind of lithium-sulphur cell positive electrode active material 4- methyl -5- vinylthiazoles-sulphur copolymer and preparation method.
Background technology
Using sulphur be the lithium-sulfur cell of positive electrode active materials due to sulphur anode have high theoretical specific capacity (1675mAhg-1)
Favored by researcher with the advantages such as the natural abundance of sulfur feedstock.However due to the limitation of the present art, lithium sulphur
Battery also faces some problems on the road for moving towards commercial, if elemental sulfur itself is non-conductive, sulphur anode electrochemical reaction
Intermediate lithium polysulfide can be dissolved in electrolyte；The volume expansion etc. of positive electrode, seriously affects battery in reaction process
Whole service life and safe to use.For these problems, it is developed organic polysulfide in recent years.By by sulphur with covalent
It is keyed on organic molecule, forms polymer chain, effectively inhibit the dissolving of the polysulfide in electrochemical reaction process, improve
Cyclical stability.Research finds that the heteroatomic doping such as sulphur, nitrogen, boron helps to improve leading for positive electrode in positive carbon material
Electrically, enhance the effect between positive electrode active materials and polysulfide, and then carbon material is assisted preferably to inhibit shuttle phenomenon.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of 4- methyl -5- ethylene of sulphur nitrogen auto-dope
Base thiazole-sulphur copolymer and preparation method select one kind to be widely present in cocoa, passion fruit etc., sulfur-bearing, nitrogen heteroatom (- C-
S-C keys and-C=N- keys) natural olefin hydrocarbon molecules 4- methyl -5- vinylthiazoles (MVT) be raw material, it is anti-with the inverse vulcanization of elemental sulfur
Answer, be made sulphur, nitrogen auto-dope novel high sulfur-containing polymer.Can be prepared using this polymer as positive electrode can with height
The lithium-sulfur cell of inverse capacity and cyclical stability.
The technical purpose of the present invention is achieved by following technical proposals：
A kind of the 4- methyl -5- vinylthiazoles-sulphur copolymer and preparation method of the auto-dope of sulphur nitrogen, with elemental sulfur and 4- first
Base -5- vinylthiazoles carry out melting copolymerization, i.e., elemental sulfur are heated to molten condition, so that by 8 sulphur atom groups under room temperature
At sulphur ringFracture forms the sulphur chain with diradical end group, and 4- methyl -5- vinylthiazoles are addedAfterwards, the chain free radical in molten sulfur causes the carbon-carbon double bond in 4- methyl -5- vinylthiazoles to carry out certainly
It is copolymerized by base.
By above-mentioned free-radical polymerized obtained 4- methyl -5- vinylthiazoles-sulphur copolymer, there is following chemical formula
Structure
Wherein n is the degree of polymerization of sulphur, and the sulphur chain of diradical end group is broken to form in view of 8 yuan of sulphur rings, is more than or equal to 6；M is
The degree of polymerization of 4- methyl -5- vinylthiazoles is more than or equal to 1.The ratio of the specific visual response object of m, n is different and changes, and m is preferred
6-18, n preferably 10-50.
4- methyl -5- vinylthiazoles-sulphur copolymer of preparation, sulfur content are：50-99wt%, preferably 80-
90wt%.
According to quality percentage meter (i.e. elemental sulfur and 4- methyl -5- vinylthiazole quality sums are 100%), elemental sulfur
Mass percent is 50-99wt%, and the mass percent of 4- methyl -5- vinylthiazoles is 1-50wt%；It is preferred that elemental sulfur
Mass percent is 80-90wt%, and the mass percent of 4- methyl -5- vinylthiazoles is 10-20wt%.
When being prepared, elemental sulfur is heated to molten condition, is added 4- methyl -5- vinylthiazoles, in molten sulfur
Chain free radical cause 4- methyl -5- vinylthiazoles in carbon-carbon double bond it is free-radical polymerized to carry out, whole process is in anaerobic
Under the conditions of carry out.
Using oil bath heating so that elemental sulfur is heated to 120-160 DEG C, preferably 140-160 DEG C, formed limpid orange molten
Melt phase.4- methyl -5- vinylthiazoles are added dropwise into the elemental sulfur of melting behaviors under agitation, and heat the mixture to
It carries out free-radical polymerized at 160-200 DEG C, whole system is cooled to room temperature 20-25 DEG C after reaction, product metal slice is direct
It is scraped from reaction vessel.Mixing speed is that 100-200 turns/min, and the speed that 4- methyl -5- vinylthiazoles are added dropwise is every point
Clock 1-10ml, preferably heat the mixture at 160-190 DEG C carry out it is 30-120 minutes free-radical polymerized.In whole preparation process
In, using inert atmosphere is passed through, if nitrogen, helium or argon gas are protected, avoid the influence of oxygen.
Using 4- methyl -5- vinylthiazoles as monomer, using elemental sulfur heating open loop can occur for technical scheme of the present invention
The characteristics of polymerisation, makes it polymerize with the carbon-carbon double bond in 4- methyl -5- vinylthiazoles, forms sulphur, nitrogen auto-dope
Stable structure and with electro-chemical activity high sulfur-containing polymer.In the inventive solutions, under room temperature, thermodynamics is steady
Fixed simple substance sulfur molecule is the sulphur ring of 8 sulphur atoms composition.When being heated to temperature T>At 119 DEG C, elemental sulfur starts to melt, molecule
Structure is still sulphur ring.As temperature T>At 159 DEG C, sulphur chain starts to be broken, and forms the sulphur chain with diradical end group.Chain simultaneously
Reversible polymerization is carried out between free radical (i.e. the sulphur chain with diradical end group), forms the chain free radical of more long-chain.To 159 DEG C
4- methyl -5- vinylthiazole monomers are added in the sulphur of temperatures above melting, the chain free radical in molten sulfur causes 4- methyl -
Carbon-carbon double bond in 5- vinylthiazoles carries out free radical polymerization therewith, i.e., elemental sulfur and 4- methyl -5- vinylthiazoles from
It is copolymerized by base.Comonomer can be added, can also heat molten first by after elemental sulfur heating melting and after generating free radicals in practice
It is uniformly mixed, then heats up to cause free radical polymerization with comonomer after melting.
The present invention has the advantages that：(1) elemental sulfur can be anti-with arbitrary proportion and 4- methyl -5- vinylthiazoles
It answers, high sulfur content copolymer can be made, be used as lithium sulfur battery anode material, greatly improve the content of active material in anode.(2)
C and S is with Covalent bonding together in 4- methyl -5- vinylthiazoles-sulphur copolymer so that is generated during electrochemical reaction
Polysulfide is copolymerized object molecule and is fettered in the form of covalent bond, and the dissolving of polysulfide and alleviation volume can be inhibited swollen
It is swollen, while S, N (- C-S-C- keys and-C=N- keys) for containing in 4- methyl -5- vinylthiazole molecular structures can be with more sulphur
Interaction is generated between compound, and then assists preferably shuttle phenomenon being inhibited to improve its chemical property.(3) present invention provides
High sulfur-containing polymer polymerisation without additional addition solvent, it is only necessary to heating can be carried out, simple for process.(4) of the invention
Selected raw material 4- methyl -5- vinylthiazoles, are naturally occurring in cocoa, passion fruit etc., derive from a wealth of sources, and is nontoxic, right
Environmental nonpollution.
Description of the drawings
Fig. 1 is the infrared of 4- methyl -5- vinylthiazoles-sulphur copolymer and 4- methyl -5- vinylthiazoles of the invention
Spectrogram.
Fig. 2 is the XRD spectrum of 4- methyl -5- vinylthiazoles-sulphur copolymer of 60wt%S prepared by the present invention.
Fig. 3 is the XRD spectrum of 4- methyl -5- vinylthiazoles-sulphur copolymer of 80%S prepared by the present invention.
Fig. 4 is the XRD spectrum of elemental sulfur.
Fig. 5 is that the battery that 4- methyl -5- vinylthiazoles-sulphur copolymer of the present invention is assembled as positive electrode active materials exists
Charge and discharge cycles curve under 0.1C.
Charge and discharge cycles curve of the battery that Fig. 6, which is pure simple substance sulphur, to be assembled as positive electrode active materials at 0.1C.
Specific implementation mode
The technical solution further illustrated the present invention with reference to specific embodiment.
Example 1
0.95g elemental sulfurs are weighed, are put into togerther in the three-necked flask of 25ml with rotor, argon gas protection is led to.Then in constant temperature
130 DEG C are heated with stirring on oil bath pan until forming limpid orange melting behaviors.0.05gMVT is pipetted with syringe, is injected into molten
Melt in sulphur, stirs 10min.Then mixture is stirred to react 120min at 160 DEG C.It waits for that reaction mixture is cooled to room temperature, produces
Object is directly scraped from bottle with metal slice.
Example 2
0.9g elemental sulfurs are weighed, are put into togerther in the three-necked flask of 25ml with rotor, argon gas protection is led to.Then in thermostatical oil
130 DEG C are heated with stirring on bath until forming limpid orange melting behaviors.0.1gMVT is pipetted with syringe, is injected into melting
In sulphur, 10min is stirred.Then mixture is stirred to react 90min at 170 DEG C.Wait for that reaction mixture is cooled to room temperature, product is used
Metal slice is directly scraped from bottle.
Example 3
0.8g elemental sulfurs are weighed, are put into togerther in the three-necked flask of 25ml with rotor, argon gas protection is led to.Then in thermostatical oil
140 DEG C are heated with stirring on bath until forming limpid orange melting behaviors.0.2gMVT is pipetted with syringe, is injected into melting
In sulphur, 10min is stirred.Then mixture is stirred to react 60min at 180 DEG C.Wait for that reaction mixture is cooled to room temperature, product is used
Metal slice is directly scraped from bottle.
Example 4
0.7g elemental sulfurs are weighed, are put into togerther in the three-necked flask of 25ml with rotor, argon gas protection is led to.Then in thermostatical oil
150 DEG C are heated with stirring on bath until forming limpid orange melting behaviors.0.3gMVT is pipetted with syringe, is injected into melting
In sulphur, 10min is stirred.Then mixture is stirred to react 30min at 190 DEG C.Wait for that reaction mixture is cooled to room temperature, product is used
Metal slice is directly scraped from bottle.
Example 5
0.6g elemental sulfurs are weighed, are put into togerther in the three-necked flask of 25ml with rotor, argon gas protection is led to.Then in thermostatical oil
160 DEG C are heated with stirring on bath until forming limpid orange melting behaviors.0.4gMVT is pipetted with syringe, is injected into melting
In sulphur, 10min is stirred.Then mixture is stirred to react 30min at 200 DEG C.Wait for that reaction mixture is cooled to room temperature, product is used
Metal slice is directly scraped from bottle.
Example 6
0.5g elemental sulfurs are weighed, are put into togerther in the three-necked flask of 25ml with rotor, argon gas protection is led to.Then in thermostatical oil
160 DEG C are heated with stirring on bath until forming limpid orange melting behaviors.0.5gMVT is pipetted with syringe, is injected into melting
In sulphur, 10min is stirred.Then mixture is stirred to react 30min at 200 DEG C.Wait for that reaction mixture is cooled to room temperature, product is used
Metal slice is directly scraped from bottle.
Example 7
0.99g elemental sulfurs are weighed, are put into togerther in the three-necked flask of 25ml with rotor, argon gas protection is led to.Then in constant temperature
160 DEG C are heated with stirring on oil bath pan until forming limpid orange melting behaviors.0.01gMVT is pipetted with syringe, is injected into molten
Melt in sulphur, stirs 10min.Then mixture is stirred to react 30min at 200 DEG C.Wait for that reaction mixture is cooled to room temperature, product
It is directly scraped from bottle with metal slice.
Use 27 type infrared spectrometers of German Brooker Tensor and German Brooker D8Advanced type X-ray diffractions
Instrument carries out property representation：There is S -- S from can be seen that in product in infrared spectrogram, and new C-S keys, explanation occurs
Sulphur is intermolecular after being reacted with 4- methyl -5- vinylthiazoles to be bonded conjunction with C-S so that is generated during electrochemical reaction
Polysulfide is copolymerized object molecule and is fettered in the form of covalent bond.And contained in 4- methyl -5- vinylthiazoles-sulphur copolymer
- C-S-C- keys and-C=N- keys there is certain effect of contraction to polysulfide, thus the polymer prepared by the present invention is made
It can effectively slow down the dissolving of polysulfide in the electrolytic solution for lithium sulfur battery anode material, be conducive to the electrochemistry for improving material
Energy.From XRD spectra, compare the reduction that can be seen that with sulfur content in 4- methyl -5- vinylthiazoles-sulphur copolymer,
The property of copolymer becomes closer to the amorphous state in high molecular polymer；Otherwise with the increase of sulfur content, the knot of copolymer
Crystalline substance becomes closer to elemental sulfur.Illustrate to be random copolymerization between elemental sulfur and 4- methyl -5- vinylthiazoles, further proves
Sulphur is connect in the form of covalent bond with organic molecule in copolymer, and structure is more stable.
Using 4- methyl -5- vinylthiazoles-sulphur copolymer produced by the present invention as positive electrode active materials and conductive black
(Super P), sodium cellulose glycolate (CMC), in mass ratio 8:1:1 mixing, water is dispersant, is uniformly mixing to obtain mixing slurry
Material.Then it is equably coated on aluminium foil, it is spare that 55 DEG C of vacuum drying obtain pole piece in 12 hours.It is just with the above-mentioned pole piece for preparing
Pole, metal lithium sheet are cathode, diaphragm Celgrad3500 (diaphragm model Celgrad3500), the LiTFSI/DOL- of 0.38mol/L
DME (volume ratios 1:1) it is that (solute is double trifluoromethanesulfonimide lithiums to electrolyte, and solvent is isometric 1,3-dioxolane
With the mixed solvent of glycol dimethyl ether), 0.32mol/L LiNO3 are additive, are assembled into the glove box full of argon gas
Button cell.Constant current charge-discharge test is carried out using Land battery test systems.Charging/discharging voltage ranging from 1-3V, current density
It for 0.1C, recycles 100 times, measures capacity retention ratio and specific capacity.
As a result as shown, under the current density of 0.1C, gram based on 4- methyl -5- vinylthiazoles-sulphur copolymer
Capacity, initial discharge capacity are 872mAh g-1, discharge capacity is 514mAh g after recycling 100 times-1, the positive electrode with bright sulfur
It compares, recycles the residual capacity after same number and capacity retention ratio will be much higher, i.e., chemical property is significantly improved.
In addition, according to the requirement of practical application, 4- methyl -5- vinylthiazoles-sulphur copolymer of the present invention is used as positive electrode institute
The specific capacity of test is the gram volume based on polymer, still greater than 500mAh g after recycling 100 times-1, it is relatively beneficial to actually answer
With.Technological parameter is recorded according to the content of present invention to be adjusted, can prepare 4- methyl -5- vinylthiazoles-sulphur copolymer, is made
For the performance for showing almost the same with embodiment when positive electrode active materials：The copolymer of preferred sulfur content 80-90wt%,
Under the current density of 0.1C, based on the gram volume of 4- methyl -5- vinylthiazoles-sulphur copolymer, initial discharge capacity 870-
920mAh g-1, discharge capacity is 510-560mAh g after recycling 100 times-1。
The process conditions that content is recorded according to the present invention are adjusted, and it is total can to prepare 4- methyl -5- vinylthiazoles-sulphur
Polymers, and show the performance almost the same with above-described embodiment.Illustrative description is done to the present invention above, it should illustrate
, in the case where not departing from core of the invention, any simple deformation, modification or other skilled in the art's energy
It is enough that the equivalent replacement of creative work is not spent to each fall within protection scope of the present invention.
Claims (9)
1. a kind of 4- methyl -5- vinylthiazoles-sulphur copolymer of sulphur nitrogen auto-dope, which is characterized in that elemental sulfur to be heated to
Molten condition forms the sulphur chain with diradical end group so as to be broken by the sulphur ring that 8 sulphur atoms form, and 4- methyl-is added
After 5- vinylthiazoles, the chain free radical in molten sulfur causes the carbon-carbon double bond in 4- methyl -5- vinylthiazoles to carry out certainly
It is copolymerized by base.
2. a kind of 4- methyl -5- vinylthiazoles-sulphur copolymer of sulphur nitrogen auto-dope according to claim 1, feature
It is, according to quality percentage meter (i.e. elemental sulfur and 4- methyl -5- vinylthiazole quality sums are 100%), the matter of elemental sulfur
Amount percentage is 50-99wt%, and the mass percent of 4- methyl -5- vinylthiazoles is 1-50wt%；It is preferred that the matter of elemental sulfur
Amount percentage is 80-90wt%, and the mass percent of 4- methyl -5- vinylthiazoles is 10-20wt%.
3. a kind of 4- methyl -5- vinylthiazoles-sulphur copolymer of sulphur nitrogen auto-dope according to claim 1, feature
It is, n is the degree of polymerization of sulphur, is more than or equal to 6；M is the degree of polymerization of 4- methyl -5- vinylthiazoles, is more than or equal to 1；M, n are specific
The ratio of visual response object is different and changes, m preferably 6-18, n preferably 10-50.
4. a kind of preparation method of 4- methyl -5- vinylthiazoles-sulphur copolymer of sulphur nitrogen auto-dope, which is characterized in that will be single
Matter sulphur is heated to molten condition, and 4- methyl -5- vinylthiazoles are added, and the chain free radical in molten sulfur causes 4- methyl -5- second
Carbon-carbon double bond in alkenyl thiazole is free-radical polymerized to carry out, and whole process carries out under anaerobic, wherein：
According to quality percentage meter (i.e. elemental sulfur and 4- methyl -5- vinylthiazole quality sums are 100%), the quality of elemental sulfur
Percentage is 50-99wt%, and the mass percent of 4- methyl -5- vinylthiazoles is 1-50wt%；Using oil bath heating so that
Elemental sulfur is heated to 120-160 DEG C, forms limpid orange melting behaviors；It is added dropwise under agitation into the elemental sulfur of melting behaviors
4- methyl -5- vinylthiazoles, and heat the mixture at 160-200 DEG C carry out it is free-radical polymerized, by entire body after reaction
System is cooled to room temperature 20-25 DEG C.
5. a kind of preparation side of 4- methyl -5- vinylthiazoles-sulphur copolymer of sulphur nitrogen auto-dope according to claim 4
Method, which is characterized in that excellent according to quality percentage meter (i.e. elemental sulfur and 4- methyl -5- vinylthiazole quality sums are 100%)
It is 80-90wt% to select the mass percent of elemental sulfur, and the mass percent of 4- methyl -5- vinylthiazoles is 10-20wt%.
6. a kind of preparation side of 4- methyl -5- vinylthiazoles-sulphur copolymer of sulphur nitrogen auto-dope according to claim 4
Method, which is characterized in that in whole preparation process, using inert atmosphere is passed through, if nitrogen, helium or argon gas are protected,
Avoid the influence of oxygen.
7. a kind of preparation side of 4- methyl -5- vinylthiazoles-sulphur copolymer of sulphur nitrogen auto-dope according to claim 4
Method, which is characterized in that using oil bath heating so that elemental sulfur is heated to 140-160 DEG C, form limpid orange melting behaviors.
8. a kind of preparation side of 4- methyl -5- vinylthiazoles-sulphur copolymer of sulphur nitrogen auto-dope according to claim 4
Method, which is characterized in that mixing speed is that 100-200 turns/min, and the speed that 4- methyl -5- vinylthiazoles are added dropwise is 1- per minute
10ml, preferably heat the mixture at 160-190 DEG C carry out it is 30-120 minutes free-radical polymerized.
9. 4- methyl -5- vinylthiazoles-sulphur copolymer of sulphur nitrogen auto-dope as described in claim 1 as lithium-sulfur cell just
Application in the material of pole.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111599997A (en) * | 2020-05-11 | 2020-08-28 | 浙江大学 | All-solid-state battery polymeric sulfur positive electrode material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020182495A1 (en) * | 1998-03-31 | 2002-12-05 | Shizuo Ogura | Lithium battery and electrode |
| CN1464576A (en) * | 2002-06-05 | 2003-12-31 | 中国人民解放军63971部队 | Multiple sulpho conjugated polymer for lithium battery anode material |
| CN106432726A (en) * | 2016-09-08 | 2017-02-22 | 天津大学 | High-sulfur-content polymers for positive electrode of lithium-sulfur battery and preparation method of high-sulfur-content polymers |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020182495A1 (en) * | 1998-03-31 | 2002-12-05 | Shizuo Ogura | Lithium battery and electrode |
| CN1464576A (en) * | 2002-06-05 | 2003-12-31 | 中国人民解放军63971部队 | Multiple sulpho conjugated polymer for lithium battery anode material |
| CN106432726A (en) * | 2016-09-08 | 2017-02-22 | 天津大学 | High-sulfur-content polymers for positive electrode of lithium-sulfur battery and preparation method of high-sulfur-content polymers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111599997A (en) * | 2020-05-11 | 2020-08-28 | 浙江大学 | All-solid-state battery polymeric sulfur positive electrode material and preparation method and application thereof |
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