CN109755503B - Preparation method of manganese compound/carbon tube sulfur-supported composite material and its application in lithium-sulfur battery - Google Patents
Preparation method of manganese compound/carbon tube sulfur-supported composite material and its application in lithium-sulfur battery Download PDFInfo
- Publication number
- CN109755503B CN109755503B CN201811521713.7A CN201811521713A CN109755503B CN 109755503 B CN109755503 B CN 109755503B CN 201811521713 A CN201811521713 A CN 201811521713A CN 109755503 B CN109755503 B CN 109755503B
- Authority
- CN
- China
- Prior art keywords
- sulfur
- carbon tube
- manganese
- lithium
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 86
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 82
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 150000002697 manganese compounds Chemical class 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011572 manganese Substances 0.000 claims abstract description 29
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 29
- 239000011593 sulfur Substances 0.000 claims abstract description 29
- 239000011888 foil Substances 0.000 claims abstract description 25
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 24
- 239000007774 positive electrode material Substances 0.000 claims abstract description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010406 cathode material Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000002033 PVDF binder Substances 0.000 claims abstract description 9
- 239000006229 carbon black Substances 0.000 claims abstract description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract 10
- 239000000463 material Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000007983 Tris buffer Substances 0.000 claims description 8
- KPSZWAJWFMFMFF-UHFFFAOYSA-N delta-Hexylen-alpha-carbonsaeure Natural products CC=CCCCC(O)=O KPSZWAJWFMFMFF-UHFFFAOYSA-N 0.000 claims description 8
- KPSZWAJWFMFMFF-NSCUHMNNSA-N delta-heptenoic acid Chemical compound C\C=C\CCCC(O)=O KPSZWAJWFMFMFF-NSCUHMNNSA-N 0.000 claims description 8
- -1 3,5-di-tert-butylsalicylidene Chemical group 0.000 claims description 7
- UDBAOKKMUMKEGZ-UHFFFAOYSA-K trichloromanganese Chemical compound [Cl-].[Cl-].[Cl-].[Mn+3] UDBAOKKMUMKEGZ-UHFFFAOYSA-K 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002482 conductive additive Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000006479 redox reaction Methods 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 8
- 239000011244 liquid electrolyte Substances 0.000 abstract description 7
- 239000005077 polysulfide Substances 0.000 abstract description 6
- 229920001021 polysulfide Polymers 0.000 abstract description 6
- 150000008117 polysulfides Polymers 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 4
- 238000000227 grinding Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000010405 anode material Substances 0.000 description 25
- 238000012360 testing method Methods 0.000 description 20
- IPFASKMZBDWRNG-UHFFFAOYSA-N manganese 5,10,15,20-tetraphenyl-21,23-dihydroporphyrin Chemical compound [Mn].c1cc2nc1c(-c1ccccc1)c1ccc([nH]1)c(-c1ccccc1)c1ccc(n1)c(-c1ccccc1)c1ccc([nH]1)c2-c1ccccc1 IPFASKMZBDWRNG-UHFFFAOYSA-N 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000005303 weighing Methods 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 7
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 6
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 6
- RDMHXWZYVFGYSF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese Chemical compound [Mn].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RDMHXWZYVFGYSF-LNTINUHCSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 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 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- 229910013553 LiNO Inorganic materials 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- SSJXIUAHEKJCMH-WDSKDSINSA-N (1s,2s)-cyclohexane-1,2-diamine Chemical compound N[C@H]1CCCC[C@@H]1N SSJXIUAHEKJCMH-WDSKDSINSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
- AMIQXMHDLJIUBQ-UHFFFAOYSA-N manganese(3+) pentane-2,4-dione Chemical compound C(C)(=O)CC(C)=O.[Mn+3] AMIQXMHDLJIUBQ-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
本发明提供了锰系化合物/碳管载硫复合材料的制备方法及其在锂硫电池中的应用，其过程为：将碳管与硫单质混合研磨，加入CS2充分搅拌之后烘干制得碳管载硫复合材料；将碳管载硫复合材料与炭黑、聚偏氟乙烯按一定质量比混合，然后加入N‑甲基吡咯烷酮，以及锰系化合物搅拌并超声分散均匀，将所得浆料均匀涂覆在集流体铝箔上，然后将铝箔转移至烘箱内烘干，即得锰系化合物与碳管载硫复合正极材料；本发明提供的制备方法，操作简单，条件温和，易于大规模生产；制得的锰系化合物与碳管载硫复合正极材料用于锂硫电池中，可以解决锂硫电池充放电过程中多硫离子在液态电解液中的溶解，有效抑制穿梭效应，提高锂硫电池的库伦效率和循环稳定性。
The invention provides a preparation method of a manganese-based compound/carbon tube sulfur-loaded composite material and its application in a lithium-sulfur battery. The process is as follows: mixing and grinding a carbon tube and a simple substance of sulfur, adding CS 2 and fully stirring, and then drying to obtain the preparation. Carbon tube sulfur-loaded composite material; the carbon tube sulfur-loaded composite material is mixed with carbon black and polyvinylidene fluoride according to a certain mass ratio, then N-methylpyrrolidone and manganese compounds are added and stirred and ultrasonically dispersed uniformly, and the obtained slurry is It is evenly coated on the current collector aluminum foil, and then the aluminum foil is transferred to an oven for drying to obtain a manganese-based compound and a carbon tube sulfur-carrying composite positive electrode material; the preparation method provided by the present invention has simple operation, mild conditions and easy mass production. The prepared manganese-based compound and carbon tube sulfur-loaded composite cathode material are used in lithium-sulfur batteries, which can solve the dissolution of polysulfide ions in liquid electrolyte during the charging and discharging process of lithium-sulfur batteries, effectively inhibit the shuttle effect, and improve lithium-sulfur batteries. Coulombic efficiency and cycling stability of batteries.
Description
Technical Field
The invention belongs to the field of nano composite material research, and particularly relates to a preparation method of a manganese compound/carbon tube composite positive electrode material for a lithium-sulfur battery in the aspects of improving the electrochemical performance of the lithium-sulfur battery, inhibiting polysulfide shuttling effect and the like.
Background
With the rapid development of economy and the improvement of life style of people, the demand of people on energy is increasing day by day, however, the environmental pollution and the exhaustion of reserves thereof caused by fossil fuel make the demand of people on novel alternative energy more and more urgent. The new energy, especially the chemical energy, has the characteristics of cleanness, environmental protection, safety, high efficiency and the like, and is favored by meeting the requirements of the strategy of sustainable development of human beings. Solar panels and wind farms are currently being installed worldwide, but to take full advantage of these intermittent energy sources, rechargeable battery systems are a vital part. Since the commercialization of lithium ion batteries in 1991, through the development of more than 20 years, the performances of the anode and cathode materials of the traditional lithium ion batteries are close to the theoretical limit, but the lithium ion batteries still have unsatisfactory effects in terms of increasingly large energy storage systems. The theoretical specific capacity of the lithium-sulfur battery is 1675 mAh.g-1The lithium ion battery is 10 times of the traditional lithium ion battery, and has the advantages of rich sulfur storage, low price, low toxicity, no public nuisance and the like, thereby bringing wide attention to people. However, the shuttling effect of the lithium-sulfur battery is easy to generate during the charging and discharging process, and the problems of volume expansion, lithium corrosion and the like during the charging and discharging process cause the problems of low utilization rate of active materials, low coulombic efficiency, poor cycle performance and the like of the lithium-sulfur battery, so that the shuttling effect becomes an obstacle in the commercial application process of the lithium-sulfur battery.
In order to solve the problems and realize large-scale use of the lithium sulfur battery, a novel electrode structure needs to be designed and developed, and a simple and convenient preparation method with low cost is developed to improve the electrochemical performance of the lithium sulfur battery, so that the practical application prospect of the lithium sulfur battery is improved.
Disclosure of Invention
The technical problem to be solved by the embodiments of the present invention is to provide a preparation method of a manganese compound/carbon tube sulfur-loaded composite material and an application thereof in a lithium-sulfur battery. The manganese compound/carbon tube sulfur-carrying composite material provided by the invention improves the problems of conductivity of the positive electrode of the lithium sulfur battery, shuttle effect of polysulfide and the like, shows excellent cycle stability and has the advantage of large-scale production.
To achieve the above object, a first object of the present invention is to provide a method comprising the steps of:
(1) preparing a carbon tube sulfur-carrying composite material: mixing a carbon tube and elemental sulfur according to a mass ratio of 1: 1-2, uniformly grinding, and mixing the materials in a feed liquid mass ratio of 1: 10-15 addition of CS2Stirring, and standing at room temperature to CS2After complete volatilization, preserving the heat of the residual substances in an oven at 120-160 ℃ for 8-12 h, and then cooling to room temperature to obtain the carbon tube sulfur-carrying composite material;
(2) preparation of manganese compound/carbon tube sulfur-carrying composite material: mixing the carbon tube sulfur-carrying composite material obtained in the step (1) with conductive additive carbon black and binder polyvinylidene fluoride, adding solvent N-methyl pyrrolidone and manganese compound, stirring and ultrasonically dispersing uniformly, controlling the viscosity to be 1000-10000 cps, obtaining composite material slurry, drying the obtained composite material slurry, and obtaining the manganese compound/carbon tube sulfur-carrying composite material, wherein the manganese compound has catalytic conversion capability on redox reaction in a lithium sulfur battery, and the mass ratio of the carbon tube sulfur-carrying composite material, the carbon black, the polyvinylidene fluoride and the manganese compound is (300-400): (15-50): (15-50): (3-5).
Further setting, uniformly coating the composite material slurry on a current collector aluminum foil with the thickness of 150-400 microns by using a scraper, and then transferring the current collector aluminum foil into an oven at 40-60 ℃ for drying to obtain the manganese compound and carbon tube negative sulfur composite cathode material in a sheet shape.
The current collector aluminum foil is 30um in thickness, and is cleaned by N-methyl pyrrolidone and alcohol before use to remove a surface oxide layer and impurities, and the current collector aluminum foil is naturally dried for later use.
The manganese compound is manganese tetraphenylporphyrin, manganese (III) acetylacetonate, (1S,2S) - (+) - [1, 2-cyclohexanediaminazon-N, N' -bis (3, 5-di-tert-butylsalicylidene) ] manganese (III) chloride or manganese tris (2,2,6, 6-tetramethyl-3, 5-heptenoic acid).
The second purpose of the invention is to provide a manganese compound/carbon tube sulfur-carrying composite material prepared by the preparation method.
The invention also provides an application of the composite material in a positive electrode material of a lithium-sulfur battery.
The influence of the manganese compound/carbon tube composite positive material on the performance of the lithium-sulfur battery is tested as follows:
(1) assembling the battery: cutting the manganese compound and the carbon tube sulfur-loaded composite anode material into round pieces with the diameter of 14mm, weighing in a dry environment, and deducting the mass of blank aluminum sheets to prepare an anode piece for later use; as a contrast experiment, the carbon tube sulfur-carrying composite positive electrode material without the manganese compound is also prepared into a contrast positive electrode piece for standby by the same method;
the cell assembly was carried out in a glove box filled with argon, water and oxygen, each less than lpm: using commercial lithium metal sheets as reference electrode and counter electrode, adopting lithium bistrifluoromethanesulfonylimide/1, 3-Dioxolane (DOL), ethylene glycol dimethyl ether (DME) LiTFSI/DOL. DMC (1: 1) and dissolving 1% LiNO3After a diaphragm of the liquid electrolyte is assembled into a CR2025 button cell by adopting Celgard2400, standing for 24 hours, and then carrying out charge and discharge tests;
(2) carrying out battery charge and discharge tests under different multiplying powers by adopting a blue/Xinwei battery test system under the test conditions of room temperature environment and 1.5-3.0V of window voltage;
the room temperature in the invention is 10-30 ℃.
The invention has the beneficial effects that:
(1) manganese compounds can catalyze the oxidation-reduction reaction in the battery;
(2) the prepared manganese compound and carbon tube sulfur-loaded composite anode material can additionally provide an electron/ion conduction path, reduce the internal resistance of the battery and greatly improve the discharge capacity and the cycle stability of the battery;
(3) the composite positive electrode material containing the manganese compound can enhance the reactivity with polysulfide and accelerate the chemical reaction kinetics, thereby inhibiting the shuttle effect and improving the performance of the lithium-sulfur battery;
(4) the carrier porous carbon provides a sulfur storage space and can limit the diffusion and transportation of polysulfide and lithium sulfide;
in summary, on the one hand, the invention provides a preparation method of a manganese compound/carbon tube sulfur-carrying composite anode material, which is simple to operate, does not involve high temperature and high pressure, can be completed at room temperature, and is easy for large-scale production; on the other hand, when the prepared composite cathode material is used in a lithium-sulfur battery, the problem that polysulfide ions are dissolved in liquid electrolyte in the charging and discharging processes of the lithium-sulfur battery can be solved, the shuttle effect is effectively inhibited, and the coulomb efficiency and the cycling stability of the lithium-sulfur battery are improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1: manganese tetraphenylporphyrin C prepared in example 1 of the present invention44H30ClMnN4The multiplying power performance of the carbon tube sulfur-carried composite anode material used for the lithium sulfur battery and the lithium sulfur battery without the manganese compound material is compared;
FIG. 2: manganese tetraphenylporphyrin C prepared in example 1 of the present invention44H30ClMnN4Carbon tube-carried sulfur composite positive electrode material for lithium-sulfur battery and manganese C without tetraphenylporphyrin44H30ClMnN4A charge-discharge platform contrast diagram of a lithium-sulfur battery of the material at 1C;
FIG. 3: manganese tetraphenylporphyrin C prepared in example 1 of the present invention44H30ClMnN4Use of carbon tube graphite composite anode material in lithium sulfur electricityCycling performance plot for the pool.
FIG. 4: four manganese compounds (manganese tetraphenylporphyrin C) prepared in examples 1,2, 3 and 4 of the present invention44H30ClMnN4(1S,2S) - (+) - [1, 2-cyclohexanediaminazine-N, N' -bis (3, 5-di-tert-butylsalicylidene)]Manganese (III) chloride C36H52ClMnN2O2Manganese (C) tris (2,2,6, 6-tetramethyl-3, 5-heptenoic acid)11H19O2)3Manganese (III) acetylacetonate C15H21MnO6) The multiplying power performance of the carbon tube sulfur-carried composite anode material used for the lithium sulfur battery and the lithium sulfur battery without the manganese compound material is compared.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1: manganese tetraphenylporphyrin C44H30ClMnN4Preparation of carbon tube-carried sulfur composite anode material and application of anode material in lithium-sulfur battery
(1) Preparing a carbon tube sulfur-carrying composite material: putting 200mg of carbon tube and 200mg of elemental sulfur into a mortar, fully and uniformly grinding porous carbon and sulfur, transferring the obtained mixture into a 25mL weighing bottle, and adding 3.2mL of CS2Stirring thoroughly until CS is obtained2Completely volatilizing, transferring the mixture to a 120 ℃ oven, preserving the temperature for 12h, then cooling to room temperature, and collecting the obtained product to obtain the carbon tube sulfur-carrying composite material;
(2) manganese tetraphenylporphyrin C44H30ClMnN4Preparing a carbon tube sulfur-carrying composite anode material: 300mg of carbon tube sulfur-carrying composite material, 15mg of conductive additive carbon black, 15mg of adhesive polyvinylidene fluoride and 3-4 mg of tetraphenylporphyrinmanganese C44H30ClMnN4Mixing, adding 2.5mL NMP, ultrasonic dispersing, stirring thoroughly, controlling the viscosity of the slurry to 10000cps, and coating on a current collector aluminum foil with a scraper at a thickness of 150 μm (the aluminum foil is washed twice with NMP and alcohol to remove surface oxide layer and impurities, and air-dried naturally, the aluminum foil thickness is 30 μm). Then the aluminum foil is rotatedMoving the anode material into a drying oven at 40 ℃ and drying to obtain the required anode material;
(3) assembling the battery: and (3) cutting the composite electrode material prepared in the step (2) into round pieces with the diameter of 14mm, weighing in a dry environment, and deducting the mass of blank aluminum pieces to prepare a positive electrode piece for later use. As a control experiment, manganese C tetraphenylporphyrin was absent44H30ClMnN4The carbon tube sulfur-carrying composite anode material is also prepared into a comparison anode pole piece for standby by the same method; the cell assembly was carried out in a glove box filled with argon, water and oxygen, each less than lpm. Commercial lithium metal sheets were used as reference and counter electrodes, and LiTFSI/DOL.DMC (1: 1) was used with 1% LiNO dissolved3After a diaphragm of the liquid electrolyte is assembled into a CR2025 button cell by adopting Celgard2400, standing for 24 hours, and then carrying out charge and discharge tests;
(4) the Xinwei battery testing system performs battery charge and discharge tests under different multiplying powers, the testing conditions are room temperature environment, the window initial voltage is 1.5V, and the termination voltage is 3.0V;
FIG. 1 shows manganese tetraphenylporphyrin C prepared in this example44H30ClMnN4Carbon tube sulfur-carried composite positive electrode material for lithium sulfur battery and manganese C without adding tetraphenylporphyrin44H30ClMnN4The rate performance of the lithium-sulfur battery is compared, and the manganese C tetraphenylporphyrin is shown in the figure44H30ClMnN4The capacity of the lithium-sulfur battery of the carbon tube-carried sulfur composite material is obviously better than that of the lithium-sulfur battery without adding tetraphenylporphyrin manganese C44H30ClMnN4The battery of (1).
FIG. 2 shows manganese tetraphenylporphyrin C44H30ClMnN4Carbon tube sulfur-carried composite positive electrode material for lithium sulfur battery and manganese C without tetraphenylporphyrin44H30ClMnN4The charge-discharge platform contrast diagram of the lithium-sulfur battery under 1C is obvious from the figure, and the lithium-sulfur battery contains tetraphenylporphyrinmanganese C44H30ClMnN4The lithium-sulfur battery of the positive electrode material has higher discharge capacity.
FIG. 3 shows manganese tetraphenylporphyrin C44H30ClMnN4The carbon tube sulfur-carried composite positive material is used for lithium-sulfur battery and does not contain tetraphenylporphyrin manganese C44H30ClMnN4The lithium-sulfur batteries were compared, and a cycle stability test was carried out, from which it can be seen that manganese C, a tetraphenylporphyrin, was contained44H30ClMnN4The battery has good stability and capacity.
Example 2: (1S,2S) - (+) - [1, 2-cyclohexanediaminazine-N, N' -bis (3, 5-di-tert-butylsalicylidene)]Manganese (III) chloride C36H52ClMnN2O2Preparation of carbon tube-carried sulfur composite anode material and application of anode material in lithium-sulfur battery
(1) Preparing a carbon tube sulfur-carrying composite material: 200mg of the carbon tube composite material obtained above and 400mg of elemental sulfur are put into a mortar, porous carbon and sulfur are fully and uniformly ground, the obtained mixture is transferred into a 25mL weighing bottle, and 6mL of CS is added2Stirring thoroughly until CS is obtained2Completely volatilizing, transferring the mixture to a 150 ℃ oven, preserving the temperature for 10h, then cooling to room temperature, and collecting the obtained product to obtain the carbon tube sulfur-carrying composite material;
(2) (1S,2S) - (+) - [1, 2-cyclohexanediaminazine-N, N' -bis (3, 5-di-tert-butylsalicylidene)]Manganese (III) chloride C36H52ClMnN2O2Preparing a carbon tube sulfur-carrying composite anode material: 400mg of carbon tube-carried sulfur composite material, 50mg of conductive additive carbon black, 50mg of adhesive polyvinylidene fluoride, 4-5 mg of (1S,2S) - (+) - [1, 2-cyclohexanediamine nitrogen-N, N' -bis (3, 5-di-tert-butylsalicylidene)]Manganese (III) chloride C36H52ClMnN2O2Mixing, adding 3.5mL NMP, ultrasonic dispersing, stirring thoroughly, controlling the viscosity of the slurry at 6000cps, and coating on the current collector aluminum foil with a scraper at 150 μm thickness (the aluminum foil is cleaned with NMP and alcohol twice to remove surface oxide layer and impurities, air drying naturally, the aluminum foil thickness is 30 μm). Then transferring the aluminum foil into a 50 ℃ oven, and drying to obtain the required anode material;
(3) assembling the battery: cutting the composite electrode material prepared in the step (2) into round pieces with the diameter of 14mm, weighing in a dry environment, and deductingAnd (5) preparing the blank aluminum sheet into a positive pole piece for later use. As a contrast experiment, the carbon tube sulfur-carrying composite positive electrode material without containing various manganese compounds is also prepared into a contrast positive electrode piece for standby by the same method; the cell assembly was carried out in a glove box filled with argon, water and oxygen, each less than lpm. Commercial lithium metal sheets were used as reference and counter electrodes, and LiTFSI/DOL.DMC (1: 1) was used with 1% LiNO dissolved3After a diaphragm of the liquid electrolyte is assembled into a CR2025 button cell by adopting Celgard2400, standing for 24 hours, and then carrying out charge and discharge tests;
(4) the Xinwei battery testing system performs battery charge and discharge tests under different multiplying powers, the testing conditions are room temperature environment, the window initial voltage is 1.5V, and the termination voltage is 3.0V;
FIG. 4 contains (1S,2S) - (+) - [1, 2-cyclohexanediaminazepine-N, N' -bis (3, 5-di-tert-butylsalicylidene)]Manganese (III) chloride C36H52ClMnN2O2The carbon tube sulfur-loaded composite cathode material is used for a comparison graph of the rate performance of a lithium sulfur battery and a lithium sulfur battery without a manganese compound material, and the graph shows that the lithium sulfur battery containing the cathode material of the manganese compound has higher discharge capacity under various rates.
Example 3: manganese tris (2,2,6, 6-tetramethyl-3, 5-heptenoic acid) Mn (C)11H19O2)3Preparation of carbon tube-carried sulfur composite anode material and application of anode material in lithium-sulfur battery
(1) Preparing a carbon tube sulfur-carrying composite material: 200mg of the carbon tube composite material obtained above and 400mg of elemental sulfur are put into a mortar, porous carbon and sulfur are fully and uniformly ground, the obtained mixture is transferred into a 25mL weighing bottle, and 6mL of CS is added2Stirring thoroughly until CS is obtained2Completely volatilizing, transferring the mixture to a 150 ℃ oven, preserving the temperature for 10h, then cooling to room temperature, and collecting the obtained product to obtain the carbon tube sulfur-carrying composite material;
(2) manganese tris (2,2,6, 6-tetramethyl-3, 5-heptenoic acid) Mn (C)11H19O2)3Preparing a carbon tube sulfur-carrying composite anode material: 400mg of carbon tube sulfur-carrying composite material, 50mg of conductive additive carbon black and adhesive50mg of polyvinylidene fluoride and 4-5 mg of manganese (Mn) (C) tris (2,2,6, 6-tetramethyl-3, 5-heptenoic acid)11H19O2)3Mixing, adding 3.5mL NMP, ultrasonic dispersing, stirring thoroughly, controlling the viscosity of the slurry at 6000cps, and coating on the current collector aluminum foil with a scraper at 150 μm thickness (the aluminum foil is cleaned with NMP and alcohol twice to remove surface oxide layer and impurities, air drying naturally, the aluminum foil thickness is 30 μm). Then transferring the aluminum foil into a 50 ℃ oven, and drying to obtain the required anode material;
(3) assembling the battery: and (3) cutting the composite electrode material prepared in the step (2) into round pieces with the diameter of 14mm, weighing in a dry environment, and deducting the mass of blank aluminum pieces to prepare a positive electrode piece for later use. As a contrast experiment, the carbon tube sulfur-carrying composite positive electrode material without the manganese compound is also prepared into a contrast positive electrode piece for standby by the same method; the cell assembly was carried out in a glove box filled with argon, water and oxygen, each less than lpm. Commercial lithium metal sheets were used as reference and counter electrodes, and LiTFSI/DOL.DMC (1: 1) was used with 1% LiNO dissolved3After a diaphragm of the liquid electrolyte is assembled into a CR2025 button cell by adopting Celgard2400, standing for 24 hours, and then carrying out charge and discharge tests;
(4) the Xinwei battery testing system performs battery charge and discharge tests under different multiplying powers, the testing conditions are room temperature environment, the window initial voltage is 1.5V, and the termination voltage is 3.0V;
FIG. 4 contains manganese tris (2,2,6, 6-tetramethyl-3, 5-heptenoic acid) Mn (C)11H19O2)3The graph for comparing the rate performance of the carbon tube sulfur-loaded composite cathode material used for the lithium sulfur battery with that of the lithium sulfur battery without the manganese compound material shows that the carbon tube sulfur-loaded composite cathode material contains manganese Mn (C) which is tris (2,2,6, 6-tetramethyl-3, 5-heptenoic acid)11H19O2)3The lithium-sulfur battery of the cathode material has higher discharge capacity under various multiplying powers.
Example 4: manganese (III) acetylacetonate C15H21MnO6Preparation of carbon tube-carried sulfur composite anode material and application of anode material in lithium-sulfur battery
（1) Preparing a carbon tube sulfur-carrying composite material: 200mg of the carbon tube composite material obtained above and 400mg of elemental sulfur are put into a mortar, porous carbon and sulfur are fully and uniformly ground, the obtained mixture is transferred into a 25mL weighing bottle, and 6mL of CS is added2Stirring thoroughly until CS is obtained2Completely volatilizing, transferring the mixture to a 150 ℃ oven, preserving the temperature for 10h, then cooling to room temperature, and collecting the obtained product to obtain the carbon tube sulfur-carrying composite material;
(2) manganese (III) acetylacetonate C15H21MnO6Preparing a carbon tube sulfur-carrying composite anode material: 400mg of carbon tube sulfur-carrying composite material, 50mg of conductive additive carbon black, 50mg of adhesive polyvinylidene fluoride and 4-5 mg of acetylacetone manganese (III) C15H21MnO6Mixing, adding 3.5mL NMP, ultrasonic dispersing, stirring thoroughly, controlling the viscosity of the slurry at 6000cps, and coating on the current collector aluminum foil with a scraper at 150 μm thickness (the aluminum foil is cleaned with NMP and alcohol twice to remove surface oxide layer and impurities, air drying naturally, the aluminum foil thickness is 30 μm). Then transferring the aluminum foil into a 50 ℃ oven, and drying to obtain the required anode material;
(3) assembling the battery: and (3) cutting the composite electrode material prepared in the step (2) into round pieces with the diameter of 14mm, weighing in a dry environment, and deducting the mass of blank aluminum pieces to prepare a positive electrode piece for later use. As a contrast experiment, the carbon tube sulfur-carrying composite positive electrode material without containing various manganese compounds is also prepared into a contrast positive electrode piece for standby by the same method; the cell assembly was carried out in a glove box filled with argon, water and oxygen, each less than lpm. Commercial lithium metal sheets were used as reference and counter electrodes, and LiTFSI/DOL.DMC (1: 1) was used with 1% LiNO dissolved3After a diaphragm of the liquid electrolyte is assembled into a CR2025 button cell by adopting Celgard2400, standing for 24 hours, and then carrying out charge and discharge tests;
(4) the Xinwei battery testing system performs battery charge and discharge tests under different multiplying powers, the testing conditions are room temperature environment, the window initial voltage is 1.5V, and the termination voltage is 3.0V;
FIG. 4 shows manganese (III) acetylacetonate C15H21MnO6The carbon tube sulfur-carried composite positive electrode material is respectively used for the rate performance comparison graph of a lithium sulfur battery and a lithium sulfur battery without manganese compound materials, and the graph obviously shows that the carbon tube sulfur-carried composite positive electrode material contains manganese (III) acetylacetonate C15H21MnO6The lithium-sulfur battery of the cathode material has higher discharge capacity under various multiplying powers.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811521713.7A CN109755503B (en) | 2018-12-13 | 2018-12-13 | Preparation method of manganese compound/carbon tube sulfur-supported composite material and its application in lithium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811521713.7A CN109755503B (en) | 2018-12-13 | 2018-12-13 | Preparation method of manganese compound/carbon tube sulfur-supported composite material and its application in lithium-sulfur battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109755503A CN109755503A (en) | 2019-05-14 |
| CN109755503B true CN109755503B (en) | 2021-09-07 |
Family
ID=66402618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811521713.7A Active CN109755503B (en) | 2018-12-13 | 2018-12-13 | Preparation method of manganese compound/carbon tube sulfur-supported composite material and its application in lithium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109755503B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115368567A (en) * | 2022-09-30 | 2022-11-22 | 上海屹锂新能源科技有限公司 | Reverse vulcanized copolymer positive active material and all-solid-state battery thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8183030B2 (en) * | 2006-10-13 | 2012-05-22 | Archer Daniels Midland Company | Use of cell surface displays in yeast cell catalyst supports |
| CN102683659A (en) * | 2012-05-31 | 2012-09-19 | 中国科学院物理研究所 | Lithium-sulphur battery anode material and preparation method thereof |
| CN105609707A (en) * | 2016-02-21 | 2016-05-25 | 钟玲珑 | Preparation method of manganese dioxide hollow sphere cathode material for lithium-sulfur battery |
| CN106129384A (en) * | 2016-09-07 | 2016-11-16 | 中南大学 | The complex of carbon/sulfur of a kind of manganese dioxide nano-plates cladding, preparation method and applications |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303708C (en) * | 2002-07-31 | 2007-03-07 | 曹喜峰 | Air electride |
| US8907133B2 (en) * | 2008-07-14 | 2014-12-09 | Esionic Es, Inc. | Electrolyte compositions and electrochemical double layer capacitors formed there from |
| US20110165497A1 (en) * | 2010-01-06 | 2011-07-07 | Gm Global Technology Operations, Inc. | Method for Mitigating Fuel Cell Chemical Degradation |
| CN104393259B (en) * | 2014-10-13 | 2017-01-25 | 同济大学 | Preparation method of porous carbon ball-supported MxOy nanoparticle composite material |
| JP6390582B2 (en) * | 2015-10-21 | 2018-09-19 | トヨタ自動車株式会社 | Flow battery |
| CN108269978B (en) * | 2017-12-27 | 2020-12-08 | 温州大学 | Quantum dot/carbon tube sulfur-supported composite cathode material, preparation method and application thereof |
-
2018
- 2018-12-13 CN CN201811521713.7A patent/CN109755503B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8183030B2 (en) * | 2006-10-13 | 2012-05-22 | Archer Daniels Midland Company | Use of cell surface displays in yeast cell catalyst supports |
| CN102683659A (en) * | 2012-05-31 | 2012-09-19 | 中国科学院物理研究所 | Lithium-sulphur battery anode material and preparation method thereof |
| CN105609707A (en) * | 2016-02-21 | 2016-05-25 | 钟玲珑 | Preparation method of manganese dioxide hollow sphere cathode material for lithium-sulfur battery |
| CN106129384A (en) * | 2016-09-07 | 2016-11-16 | 中南大学 | The complex of carbon/sulfur of a kind of manganese dioxide nano-plates cladding, preparation method and applications |
Non-Patent Citations (1)
| Title |
|---|
| Coating of sulfur particles with manganese oxide nanowires as a cathode material in lithium-sulfur batteries;Jeongyeon Lee et al;《Materials Letters》;20151130;第158卷;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109755503A (en) | 2019-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103928672B (en) | A kind of positive electrode active material for lithium ion battery and preparation method thereof | |
| CN108269978B (en) | Quantum dot/carbon tube sulfur-supported composite cathode material, preparation method and application thereof | |
| CN107946564B (en) | Rich in Na4Mn2O5/Na0.7MnO2Composite material and preparation method and application thereof | |
| CN105428637A (en) | Lithium ion battery, positive electrode material of lithium ion battery and preparation method for positive electrode material | |
| CN102324513A (en) | Lithium nickel manganese oxygen composite cathode material and preparation method thereof | |
| CN102244233B (en) | Method for preparing composite cathode material of graphene-like doped-cladded lithium titanate | |
| CN109755504B (en) | Preparation method of iron-containing porphyrin/carbon nanotube composite cathode material and its application in lithium-sulfur battery cathode | |
| CN110034342B (en) | Water system zinc-tellurium secondary battery | |
| CN105810920A (en) | A kind of preparation method of negative electrode material of organic system sodium ion battery | |
| CN106876699A (en) | A composite electrode and its preparation and application | |
| CN112259722A (en) | Aqueous mixed ion secondary battery, preparation method and application thereof | |
| CN107104246A (en) | Voltage drop suppression type lithium-rich manganese-based full battery and preparation method thereof | |
| CN105742695A (en) | Lithium-ion battery and preparation method thereof | |
| CN109742439A (en) | A kind of novel lithium-sulfur cell porous interlayer material, preparation method and application | |
| CN113871611A (en) | A kind of high entropy oxide material composite ternary material and preparation method thereof | |
| CN112467233B (en) | High-performance aqueous electrolyte for chargeable and dischargeable zinc-manganese battery | |
| CN107910522A (en) | The synthesis and its application in lithium ion battery of a kind of expanded graphite oxidation tin composite material | |
| CN110336026A (en) | Preparation method of water-based sodium-ion battery cathode material and water-based sodium-ion battery | |
| WO2019104948A1 (en) | Molybdenum doping-modified lithium manganese oxide composite material, preparation method therefor and lithium ion battery | |
| CN109728297A (en) | Preparation method of metal phthalocyanine/carbon tube composite material and its application in positive electrode of lithium-sulfur battery | |
| CN114300669A (en) | Rechargeable aqueous zinc-manganese battery and assembly method thereof | |
| CN109755503B (en) | Preparation method of manganese compound/carbon tube sulfur-supported composite material and its application in lithium-sulfur battery | |
| CN109473640A (en) | Silicon-based molecular sieve/carbon tube sulfur-supported composite cathode material and preparation method and application thereof | |
| CN117747799A (en) | Hollow nanocube In 2 S 3 /CoS 2 @NC composite material and preparation method and application thereof | |
| CN108565485B (en) | Sulfur-bromine rechargeable battery based on liquid electrode and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |