CN112537797A - Ferroferric oxide/carbon nano tube/sulfur-loaded composite material with one-dimensional chain-like core-shell structure, preparation method and application - Google Patents
Ferroferric oxide/carbon nano tube/sulfur-loaded composite material with one-dimensional chain-like core-shell structure, preparation method and application Download PDFInfo
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 141
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 82
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 82
- 239000011258 core-shell material Substances 0.000 title claims abstract description 74
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 56
- 239000011593 sulfur Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 45
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 15
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 15
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- 238000003958 fumigation Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 18
- 239000002086 nanomaterial Substances 0.000 claims description 16
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 13
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 13
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 12
- 239000007983 Tris buffer Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 17
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 abstract description 10
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 239000007774 positive electrode material Substances 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 229960003638 dopamine Drugs 0.000 abstract description 5
- 230000001965 increasing effect Effects 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 238000005530 etching Methods 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 230000003746 surface roughness Effects 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 description 19
- 238000003756 stirring Methods 0.000 description 17
- 238000001816 cooling Methods 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000001035 drying Methods 0.000 description 16
- 238000004140 cleaning Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 238000005303 weighing Methods 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000005987 sulfurization reaction Methods 0.000 description 7
- 239000011149 active material Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 238000013329 compounding Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 5
- 229920001021 polysulfide Polymers 0.000 description 5
- 239000005077 polysulfide Substances 0.000 description 5
- 150000008117 polysulfides Polymers 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 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 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229940069428 antacid Drugs 0.000 description 1
- 239000003159 antacid agent Substances 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
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- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
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Abstract
The invention provides a ferroferric oxide/carbon nano tube/sulfur-loaded composite material with a one-dimensional chain-like core-shell structure, a preparation method and application thereof.A sodium borohydride and cyclohexane are mixed, a ferric trichloride aqueous solution is added to obtain ferroferric oxide by an ice bath method, and the optimal sample morphology and the optimal size of the chain-like ferroferric oxide are obtained by improving the dosage of the sodium borohydride and the concentration of the ferric trichloride aqueous solution and improving the reaction temperature and the reaction time; coating a carbon layer on ferroferric oxide by taking dopamine as a carbon source, carbonizing the carbon layer in a nitrogen atmosphere, etching the carbon layer under the action of dilute hydrochloric acid, and finally loading sulfur particles by using sulfur fumigation to obtain the carbon-sulfur-loaded chain-like core-shell structure composite material. The core-shell structure is beneficial to enhancing the specific surface area of the composite material, and the carbon can increase the surface roughness of ferroferric oxide and is also beneficial to increasing the conductivity of a sample. The material is applied to the positive electrode material of the lithium-sulfur battery, has good cycle performance and stability, and has higher specific capacity.
Description
Technical Field
The invention belongs to the technical field of new energy material lithium sulfur batteries, and particularly relates to a ferroferric oxide/carbon nano tube/sulfur-loaded composite material with a one-dimensional chain-like core-shell structure, a preparation method and application.
Background
In recent years, due to the increasingly severe environment and the increasing shortage of fossil fuels, the storage amount of non-renewable energy sources is increasingly reduced, and ecosystems are also increasingly fragile, the demand for clean energy sources such as solar energy, water energy and wind energy and renewable energy sources is increasingly urgent. Therefore, the development of a secondary battery with high capacity, high energy density, long cycle life, high safety, environmental protection and low cost has great significance in the field of new energy.
The known lithium-sulfur battery is a high-energy-density battery with elemental sulfur as the battery anode and a metal lithium sheet as the battery cathode, and the theoretical specific energy of the battery reaches up to (2600Wh Kg)-1) And a higher theoretical specific capacity (1675mAh g)-1). The elemental sulfur of the electrode material in the lithium-sulfur battery is cheap, and the lithium-sulfur battery has abundant natural resources and a friendly ecological environment; and the lithium-sulfur battery system has commercial value due to the advantages of simple and convenient manufacturing process, low cost and the like.
However, lithium sulfur batteries have certain problems and challenges that have been limiting their further development, namely elemental sulfur and discharge products (Li)2S), and the problems of severe volume expansion and dissolution of an intermediate polysulfide in an electrolyte in the charge-discharge process, which lead to low utilization rate of sulfur in the battery, so that the battery has poor cycle performance, poor rate performance and rapid capacity attenuation.
Disclosure of Invention
The invention provides a ferroferric oxide/carbon nano tube/sulfur-loaded composite material with a one-dimensional chain-shaped core-shell structure, wherein the core-shell structure has a larger specific surface area, is beneficial to electron transmission and can load more active substances.
The invention also aims to provide a preparation method of the ferroferric oxide/carbon nano tube/sulfur-loaded composite material with the one-dimensional chain-shaped core-shell structure, which comprises the steps of preparing chain-shaped ferroferric oxide by using simple operation steps, wrapping carbon by using dopamine as a carbon source, calcining under the condition of nitrogen to obtain a carbon nano tube wrapped ferroferric oxide material, etching by using dilute hydrochloric acid to obtain a core-shell ferroferric oxide/carbon nano tube nano material, and then loading sulfur to obtain a lithium-sulfur battery anode material; the preparation process is simple, the yield is high, and the cost is low.
The last purpose of the invention is to provide the application of the ferroferric oxide/carbon nano tube/sulfur-loaded composite material with the one-dimensional chain-shaped core-shell structure to the preparation of the lithium-sulfur battery.
The specific technical scheme of the invention is as follows:
the preparation method of the ferroferric oxide/carbon nano tube/sulfur-loaded composite material with the one-dimensional chain-like core-shell structure comprises the following steps:
1) uniformly mixing sodium borohydride and cyclohexane, adding a trivalent ferric salt solution, uniformly mixing, and carrying out ice bath reaction to obtain a chain ferroferric oxide material;
2) dispersing the chain ferroferric oxide material prepared in the step 1) in water, adding trihydroxymethyl aminomethane, adding dopamine hydrochloride, reacting, and obtaining the chain ferroferric oxide/carbon nano material after the reaction is finished;
3) roasting the chain ferroferric oxide/carbon nano material prepared in the step 2) to prepare chain ferroferric oxide/carbon nano tubes;
4) dispersing the chain ferroferric oxide/carbon nano tube prepared in the step 3) in a dilute hydrochloric acid solution, and reacting to obtain chain ferroferric oxide/carbon nano tube with a core-shell structure;
5) uniformly mixing the ferroferric oxide/carbon nano tube with the chain-like core-shell structure prepared in the step 4) with sulfur powder, and carrying out sulfur fumigation to obtain the ferroferric oxide/carbon nano tube/sulfur-loaded composite material with the one-dimensional chain-like core-shell structure.
In step 1), the solution of the ferric salt is preferably FeCl3A solution; the volume ratio of the ferric iron salt solution to the cyclohexane is 1-1.3: 1.
In the step 1), the concentration of the ferric salt solution is 0.05-0.2M.
In the step 1), the dosage ratio of the sodium borohydride to the cyclohexane is 0.3-0.5 mol/L.
In the step 1), the ice-bath reaction is carried out at 0-10 ℃ for 1h, preferably at 5-9 ℃ for 1 h.
In the step 1), the step of uniformly mixing refers to stirring the solution for 30-60min under the condition of magnetic force.
In the step 1), after the reaction is finished, cooling the product to room temperature, centrifuging, washing and drying to obtain the chain ferroferric oxide material.
In the reaction of the step 1), cyclohexane is used as a dispersing agent and mainly plays a role in dispersing, ferric ions and sodium borohydride react to generate ferroferric oxide particles, and the ferroferric oxide particles are used as magnetic particles and can attract each other to be automatically assembled to generate a chain structure. And removing cyclohexane and other soluble products by cleaning to obtain a chain ferroferric oxide sample. The chain structure can increase the surface area contacted by the active material, thereby increasing the occupied site of the active material.
In the step 2), the mass ratio of the chain ferroferric oxide material to the trihydroxymethyl aminomethane to the dopamine hydrochloride is 1: (8-15): (0.4-0.8), preferably 1: (10-13): (0.5-0.7). Dopamine hydrochloride is used as a carbon source and can be loaded on the surface of ferroferric oxide.
In the step 2), the chain-shaped ferroferric oxide material is dispersed in water, and the concentration of the chain-shaped ferroferric oxide material in the water is 2-6g/L, preferably 3-5 g/L.
The step 2) also comprises the following steps: adding trihydroxymethyl aminomethane, adjusting pH of the system to 6.5-10, and adding dopamine hydrochloride; preferably the pH is 8-9.5. Further, hydrochloric acid is used for adjusting the pH. The conversion rate of dopamine hydrochloride in the solution can be improved by adjusting the pH value. Tris-HCl acts as an antacid and prevents the pH of the solution from dropping significantly. In the reaction, Tris (hydroxymethyl) aminomethane is added as a solvent for crystal growth under different pH conditions, and hydrochloric acid is added to form a Tris-HCl buffer solution, so that the conversion rate of dopamine hydrochloride can be improved, dopamine serving as a carbon source uniformly covers the surface of chain ferroferric oxide, a layer of organic matter is coated on the surface of the chain ferroferric oxide, and then the chain ferroferric oxide is calcined under inert gas to be converted into amorphous carbon, so that the conductivity of a sample is improved, and the cycle stability of a battery is improved.
In the step 2), the reaction time is 18-30h, preferably 20-26h, and the reaction temperature is 25-30 ℃.
In the step 2), after the reaction is finished, cooling the product to room temperature, and then centrifuging, washing and drying to obtain the chain ferroferric oxide/carbon nano material.
In the step 3), the roasting is carried out in a nitrogen atmosphere;
in the step 3), the roasting condition is roasting at 800 ℃ for 2-8h and at 550 ℃ and 750 ℃ for 3-6 h. And naturally cooling to room temperature after roasting. Roasting to carbonize and convert dopamine organic matter into amorphous carbon; and at the same time, the conductivity of the material can be increased.
In the step 4), the concentration of the dilute hydrochloric acid is 0.1-0.3mol/L, preferably 0.15-0.25 mol/L.
In the step 4), the reaction time is 10-60min, preferably 15-45 min; the reaction temperature is 25-30 ℃. The hydrochloric acid reacts with the ferroferric oxide, and the part is etched by controlling the reaction time and the concentration of the hydrochloric acid, so that a core-shell structure is formed.
In the step 4), hydrochloric acid obtained by controlling the reaction concentration and the reaction time with hydrochloric acid reacts with the ferroferric oxide part, so that the core-shell structure is obtained. The carbon nano tube wraps the chain-shaped ferroferric oxide material, and the original chain-shaped structure is still kept after etching.
In the step 4), after the reaction is finished, centrifuging, washing and drying a product to obtain chain-shaped ferroferric oxide/carbon nano tubes with core-shell structures; the drying is vacuum drying, and the vacuum drying condition is drying at 40-80 ℃ for 4-18h, preferably drying at 50-70 ℃ for 6-12 h.
In the step 5), the mass ratio of the chain-like core-shell structure ferroferric oxide/carbon nano tube to the sulfur powder is 1: 1-5; the sulfuring condition is 140-180 ℃ sulfuring for 12-18h, preferably 145-175 ℃ sulfuring for 14-16 h.
In step 5), preferably, the sulfuration is performed under an argon atmosphere.
The ferroferric oxide/carbon nano tube/sulfur-loaded composite material with the one-dimensional chain-like core-shell structure is prepared by the method, and the width of the chain is 100-300 nm.
The application of the ferroferric oxide/carbon nano tube/sulfur-loaded composite material with the one-dimensional chain-like core-shell structure is used for manufacturing a lithium-sulfur battery; the lithium-sulfur battery positive electrode is manufactured by taking the ferroferric oxide/carbon nano tube/sulfur-loaded composite material with the one-dimensional chain-shaped core-shell structure as the lithium-sulfur battery positive electrode material, and then the lithium-sulfur battery is assembled, so that the lithium-sulfur battery has good cycle performance and stability.
The invention discloses a composite material with a core-shell structure, aiming at improving the electrochemical performance of a lithium-sulfur battery. The composite material with the core-shell structure, which is reasonably designed, has a large specific surface area, is beneficial to the transmission of electrons in the charge and discharge process, and can load more active substances. The generation of the carbon nano tube can improve the whole conductivity of the sulfur anode, and meanwhile, the core-shell structure can inhibit the dissolution of polysulfide to a certain extent, and also plays a buffering role for forming a polysulfate compound for sulfur chains of the polysulfide, so that the problem of volume expansion in the charging and discharging process is reduced, the loss of active mass is reduced, and the shuttle of polysulfide is inhibited, thereby improving the electrochemical performance of the anode.
Mixing sodium borohydride and cyclohexane, adding an aqueous solution of ferric trichloride, and obtaining ferroferric oxide by an ice bath method, wherein the optimal sample morphology and the optimal size of chain ferroferric oxide are obtained by improving the dosage of the sodium borohydride, the concentration of the aqueous solution of the ferric trichloride, and the reaction temperature and the reaction time; a carbon layer is wrapped on ferroferric oxide by taking dopamine as a carbon source, carbonization is carried out under the nitrogen atmosphere, etching is carried out under the action of dilute hydrochloric acid, and finally sulfur particles are loaded in a sulfur smoking manner, so that the chain-shaped core-shell structure composite material with sulfur loaded by carbon is finally obtained. The core-shell structure is beneficial to enhancing the specific surface area of the composite material, and the carbon can increase the surface roughness of ferroferric oxide and is also beneficial to increasing the conductivity of a sample. The material is applied to the positive electrode material of the lithium-sulfur battery, has good cycle performance and stability, and has higher specific capacity.
Compared with the prior art, the ferroferric oxide precursor is prepared by an ice bath method, a layer of carbon is wrapped on the precursor, a part of ferroferric oxide in the carbon nano tube is reacted by using dilute hydrochloric acid, the synthesized ferroferric oxide/carbon nano tube material is in a chain-shaped core-shell structure, the specific surface area of the structure is large, and more active substances can be loaded. Meanwhile, the chain-shaped core-shell structure is beneficial to electron transportation, effectively relieves the volume expansion in the charging and discharging process, effectively inhibits the dissolution of polysulfide, and improves the cycle stability of the lithium-sulfur battery. In addition, the experiment has simple operation process, and the raw materials are cheap and easy to obtain.
Drawings
FIG. 1 is an SEM image of a chain type ferroferric oxide material prepared in example 3;
fig. 2 is an SEM image of the chain ferriferrous oxide/carbon nanotube prepared in example 3.
FIG. 3 is an SEM image of a one-dimensional chain-like core-shell ferroferric oxide/carbon nanotube prepared in example 3;
FIG. 4 is a TEM image of the one-dimensional chain-like core-shell ferroferric oxide/carbon nanotube prepared in example 3.
FIG. 5 is an SEM image of the sulfur-loaded ferroferric oxide/carbon nanotube composite material with a one-dimensional chain-like core-shell structure prepared in example 3;
FIG. 6 is a TEM image of the one-dimensional chain-like core-shell ferroferric oxide/carbon nanotube sulfur-loaded composite material prepared in example 3;
FIG. 7 is an XRD (X-ray diffraction) pattern of the sulfur-loaded ferroferric oxide/carbon nanotube composite material with the one-dimensional chain-like core-shell structure prepared in example 3;
FIG. 8 is an XPS plot of a one-dimensional chain-like core-shell ferroferric oxide/carbon nanotube sulfur-loaded composite material prepared in example 3;
FIG. 9 is a BET diagram of the sulfur-loaded ferroferric oxide/carbon nanotube composite material with one-dimensional chain-like core-shell structure prepared in example 3;
fig. 10 is a cycling stability test chart of the one-dimensional chain-like core-shell structure ferroferric oxide/carbon nanotube sulfur-loaded composite material prepared in example 3 as a lithium sulfur battery positive electrode material at a current density of 0.2C;
fig. 11 is a charge-discharge curve diagram of the one-dimensional chain-like core-shell-structured ferroferric oxide/carbon nanotube sulfur-loaded composite material prepared in example 3 as a lithium sulfur battery cathode material at a current density of 0.2C.
Fig. 12 is a cycle stability test chart of the one-dimensional chain-structure ferroferric oxide sulfur-loaded composite material prepared in the comparative example 1 as a lithium sulfur battery positive electrode material at a current density of 0.2C.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
The preparation method of the ferroferric oxide/carbon nano tube/sulfur-loaded composite material with the one-dimensional chain-like core-shell structure comprises the following steps:
1) an ice bath process: taking 50mL of deionized water and 1.35g of ferric trichloride hexahydrate, stirring for 10min under the action of magnetic stirring until the materials are completely dissolved to obtain FeCl3A solution; 0.7566g of sodium borohydride is put into 50mL of cyclohexane, ice blocks are put into a magnetic pan after magnetic stirring is carried out for 30min,cooling to 6 ℃, mixing with a ferric trichloride solution, carrying out ice bath reaction for 1h, collecting precipitates after the reaction is finished, centrifuging, alternately cleaning water and ethanol, and drying in vacuum at 40 ℃ for 18h to finally obtain a chain ferroferric oxide material;
2) a compounding procedure: taking 0.1g of the chain ferroferric oxide material prepared in the step 1) into 50mL of deionized water, stirring and dispersing, adding 1.0g of Tris (hydroxymethyl) aminomethane (Tris), adding hydrochloric acid to adjust the pH value to 6.5, adding 50mg of dopamine hydrochloride, stirring and reacting for 18 hours, taking out a product after the reaction is finished, centrifuging, alternately cleaning with deionized water and ethanol, and vacuum-drying at 40 ℃ for 18 hours to obtain a chain ferroferric oxide/carbon nano material;
3) a roasting process: roasting the chain ferroferric oxide/carbon nano material prepared in the step 3) for 3 hours at 500 ℃ in a nitrogen atmosphere, and naturally cooling to room temperature to prepare the chain ferroferric oxide/carbon nano tube with the core-shell structure;
4) a growth procedure: weighing 0.1g of ferroferric oxide/carbon nano tube with the core-shell structure prepared in the step 3), dispersing in 20mL of 0.15mol/L hydrochloric acid solution, reacting for 60min at 25 ℃, centrifuging, cleaning, and vacuum drying for 18 hours at 40 ℃ to obtain the ferroferric oxide/carbon nano tube with the chain-like core-shell structure.
5) A sulfuration procedure: weighing 0.1g of the chain-like core-shell structure ferroferric oxide/carbon nano tube prepared in the step 4) and 0.1g of sulfur powder, uniformly mixing, putting into a polytetrafluoroethylene plastic bottle, filling argon gas into the bottle, keeping the temperature at 140 ℃ for 18 hours, and naturally cooling to obtain the one-dimensional chain-like core-shell structure ferroferric oxide/carbon nano tube/sulfur-loaded composite material.
Example 2
The preparation method of the ferroferric oxide/carbon nano tube/sulfur-loaded composite material with the one-dimensional chain-like core-shell structure comprises the following steps:
1) an ice bath process: taking 50mL of deionized water and 1.35g of ferric trichloride hexahydrate, stirring for 10min under the action of magnetic stirring until the deionized water and the ferric trichloride are completely dissolved to obtain a ferric trichloride solution, then taking 0.7566g of sodium borohydride, putting the sodium borohydride into 50mL of cyclohexane, stirring for 30min, putting ice blocks into a magnetic cooker, reducing the temperature to 7 ℃, mixing the ice blocks with the ferric trichloride solution, carrying out ice bath reaction for 1h, collecting, centrifuging and cleaning precipitates after the reaction is finished, and carrying out vacuum drying for 16h at 50 ℃ to finally obtain a chain-shaped ferroferric oxide material;
2) a compounding procedure: taking 0.1g of the chain ferroferric oxide material prepared in the step 1) into 50mL of deionized water, stirring and dispersing, adding 1.1g of Tris (hydroxymethyl) aminomethane (Tris), adding hydrochloric acid to adjust the pH value to 7.5, adding 55mg of dopamine hydrochloride, stirring and reacting for 22 hours, taking out a product after the reaction is finished, centrifuging, alternately cleaning with deionized water and ethanol, and vacuum drying at 50 ℃ for 16 hours to obtain the chain ferroferric oxide/carbon nano material.
3) A roasting process: roasting the chain ferroferric oxide/carbon nano material prepared in the step 3) for 3 hours at 550 ℃ in a nitrogen atmosphere, and naturally cooling to room temperature to prepare the chain ferroferric oxide/carbon nano tube.
4) A growth procedure: weighing 0.1g of the chain ferroferric oxide/carbon nano tube prepared in the step 3), respectively dispersing in 20mL of 0.20mol/L hydrochloric acid solution, reacting for 10min, centrifuging, cleaning, and vacuum drying at 50 ℃ for 16 hours to obtain the chain core-shell ferroferric oxide/carbon nano tube.
5) A sulfuration procedure: weighing 0.1g of the chain-like core-shell structure ferroferric oxide/carbon nano tube prepared in the step 4) and 0.2g of sulfur powder, uniformly mixing, putting into a polytetrafluoroethylene plastic bottle, filling argon gas into the bottle, keeping the temperature at 145 ℃ for 16 hours, and naturally cooling to obtain the one-dimensional chain-like core-shell structure ferroferric oxide/carbon nano tube/sulfur-loaded composite material.
Example 3
The preparation method of the ferroferric oxide/carbon nano tube/sulfur-loaded composite material with the one-dimensional chain-like core-shell structure comprises the following steps:
1) an ice bath process: 50mL of deionized water and 1.35g of ferric trichloride hexahydrate are taken, and stirred for 10min under the action of magnetic stirring until the ferric trichloride is completely dissolved, so as to obtain a ferric trichloride solution. 0.7566g of sodium borohydride is put into 50mL of cyclohexane, ice blocks are put into a magnetic cooker after stirring for 30min, the temperature is reduced to 8 ℃, then the ice blocks are mixed with a ferric trichloride solution for ice bath reaction, the ice bath reaction lasts for 1h, after the reaction is finished, precipitates are collected, centrifuged and cleaned, and vacuum drying is carried out for 12h at 60 ℃, so that a chain ferroferric oxide material is finally obtained, wherein an SEM of the chain ferroferric oxide material is shown in figure 1, and the sample has the size of 100 plus 300nm and is in a more uniform chain structure;
2) a compounding procedure: taking 0.1g of the chain ferroferric oxide material prepared in the step 1) into 50mL of deionized water, stirring and dispersing, adding 1.2g of Tris (hydroxymethyl) aminomethane (Tris), adding hydrochloric acid to adjust the pH value to 8.5, adding 60mg of dopamine hydrochloride, stirring and reacting for 24 hours, taking out a product after the reaction is finished, centrifuging, alternately cleaning with deionized water and ethanol, and vacuum drying at 60 ℃ for 12 hours to obtain the chain ferroferric oxide/carbon nano material;
3) a roasting process: roasting the chain ferroferric oxide/carbon nano material prepared in the step 3) for 4 hours at 600 ℃ in a nitrogen atmosphere, and naturally cooling to room temperature to prepare a chain ferroferric oxide/carbon nano tube, wherein an SEM of the chain ferroferric oxide/carbon nano tube is shown in figure 2, and the SEM is a chain structure with a slightly rough surface and a particle size of 100-300 nm;
4) a growth procedure: weighing 0.1g of the chain ferroferric oxide/carbon nano tube prepared in the step 3), dispersing the chain ferroferric oxide/carbon nano tube in 20mL of 0.20mol/L hydrochloric acid solution, reacting for 30min, centrifuging, cleaning, and vacuum drying at 60 ℃ for 12h to obtain the chain core-shell ferroferric oxide/carbon nano tube, wherein SEM is shown in figure 3, a chain core-shell structure with the particle size of 100-300nm can be seen from the figure, and TEM is shown in figure 4, and the core-shell structure is further proved.
5) A sulfuration procedure: weighing 0.1g of the chain-like core-shell structure ferroferric oxide/carbon nano tube prepared in the step 4) and 0.2g of sulfur powder, uniformly mixing, putting into a polytetrafluoroethylene plastic bottle, filling argon gas into the bottle, keeping the temperature at 155 ℃ for 15 hours, naturally cooling, and cooling to obtain the one-dimensional chain-like core-shell structure ferroferric oxide/carbon nano tube sulfur-loaded composite material, wherein SEM, TEM and XRD are respectively shown in figures 5, 6 and 7.
Fig. 8 is an XPS diagram of the one-dimensional chain-like core-shell ferroferric oxide/carbon nanotube sulfur-loaded composite material in this embodiment, and it can be seen from fig. 3, 4, 5, and 6 that the one-dimensional chain-like core-shell ferroferric oxide/carbon nanotube sulfur-loaded composite material is successfully prepared in this embodiment.
Fig. 9 is a BET diagram of the one-dimensional chain-like core-shell ferroferric oxide/carbon nanotube sulfur-loaded composite material in this embodiment, and it can be seen that the composite material has a large specific surface area.
Example 4
The preparation method of the ferroferric oxide/carbon nano tube/sulfur-loaded composite material with the one-dimensional chain-like core-shell structure comprises the following steps:
1) an ice bath process: 50mL of deionized water and 1.35g of ferric trichloride hexahydrate are taken, and stirred for 10min under the action of magnetic stirring until the ferric trichloride is completely dissolved, so as to obtain a ferric trichloride solution. 0.7566g of sodium borohydride is put into 50mL of cyclohexane, ice blocks are put into a magnetic cooker after stirring for 30min, the temperature is reduced to 9 ℃, then ferric trichloride solution is mixed and subjected to ice bath reaction for 1h, after the reaction is finished, precipitate is collected, centrifuged and cleaned, and vacuum drying is carried out for 8h at 70 ℃, so that a chain ferroferric oxide material is finally obtained;
2) a compounding procedure: taking 0.1g of the chain ferroferric oxide material prepared in the step 1) into 50mL of deionized water, stirring and dispersing, adding 1.4g of Tris (hydroxymethyl) aminomethane (Tris), adding hydrochloric acid to adjust the pH value to 10, adding 70mg of dopamine hydrochloride, stirring and reacting for 30 hours, taking out a product after the reaction is finished, centrifuging, alternately cleaning with deionized water and ethanol, and drying in vacuum at 70 ℃ for 8 hours to obtain the chain ferroferric oxide/carbon nano material;
3) a roasting process: roasting the chain ferroferric oxide/carbon nano material prepared in the step 3) at 800 ℃ for 7 hours in a nitrogen atmosphere, and naturally cooling to room temperature to prepare the chain ferroferric oxide/carbon nano tube;
4) a growth procedure: weighing 0.1g of the chain ferroferric oxide/carbon nano tube prepared in the step 3), respectively dispersing in 20mL of 0.25mol/L hydrochloric acid solution, reacting for 10min, centrifuging, cleaning, and vacuum drying at 70 ℃ for 8 hours to obtain the chain core-shell ferroferric oxide/carbon nano tube;
5) a sulfuration procedure: weighing 0.1g of the chain-like core-shell structure ferroferric oxide/carbon nano tube prepared in the step 4) and 0.4g of sulfur powder, uniformly mixing, putting into a polytetrafluoroethylene plastic bottle, filling argon gas into the bottle, keeping the temperature at 165 ℃ for 14 hours, and naturally cooling to obtain the one-dimensional chain-like core-shell structure ferroferric oxide/carbon nano tube sulfur-loaded composite material.
Example 5
The preparation method of the ferroferric oxide/carbon nano tube/sulfur-loaded composite material with the one-dimensional chain-like core-shell structure comprises the following steps:
1) an ice bath process: 50mL of deionized water and 1.35g of ferric trichloride hexahydrate are taken, and stirred for 10min under the action of magnetic stirring until the ferric trichloride is completely dissolved, so as to obtain a ferric trichloride solution. 0.7566g of sodium borohydride is put into 50mL of cyclohexane, ice blocks are put into a magnetic cooker after stirring for 30min, the temperature is reduced to 10 ℃, then the ice blocks are mixed with a ferric trichloride solution to carry out ice bath reaction for 1h, after the reaction is finished, precipitates are collected, centrifuged and cleaned, and vacuum drying is carried out for 6h at 80 ℃, so that a chain ferroferric oxide material is finally obtained;
2) a compounding procedure: taking 0.1g of the chain ferroferric oxide material prepared in the step 1) into 50mL of deionized water, stirring and dispersing, adding 1.3g of Tris (hydroxymethyl) aminomethane (Tris), adding hydrochloric acid to adjust the pH value to 9, adding 65mg of dopamine hydrochloride, stirring and reacting for 26 hours, taking out a product after the reaction is finished, centrifuging, alternately cleaning with deionized water and ethanol, and vacuum drying at 80 ℃ for 6 hours to obtain the chain ferroferric oxide/carbon nano material;
3) a roasting process: roasting the chain ferroferric oxide/carbon nano material prepared in the step 3) for 6 hours at 700 ℃ in a nitrogen atmosphere, and naturally cooling to room temperature to prepare the chain ferroferric oxide/carbon nano tube;
4) a growth procedure: weighing 0.1g of the chain ferroferric oxide/carbon nano tube prepared in the step 3), respectively dispersing in 20mL of 0.25mol/L hydrochloric acid solution, reacting for 20min, centrifuging, cleaning, and vacuum drying at 80 ℃ for 6 hours to obtain the chain core-shell ferroferric oxide/carbon nano tube;
5) a sulfuration procedure: weighing 0.1g of the chain-like ferroferric oxide/carbon nano tube with the core-shell structure prepared in the step 4) and 0.3g of sulfur powder, uniformly mixing, putting into a polytetrafluoroethylene plastic bottle, filling argon gas into the bottle, keeping the temperature at 175 ℃ for 14 hours, and naturally cooling to obtain the sulfur-loaded composite material of the one-dimensional chain-like ferroferric oxide/carbon nano tube with the core-shell structure.
Example 6
The application of the ferroferric oxide/carbon nano tube/sulfur-loaded composite material with the one-dimensional chain-shaped core-shell structure is used for manufacturing a lithium-sulfur battery, and specifically comprises the following steps:
taking the final product of ferroferric oxide/carbon nano tube/sulfur-loaded composite material with one-dimensional chain-like core-shell structure obtained in the embodiment 3 as an active material of the lithium-sulfur battery anode, and mixing the obtained active material with conductive carbon black and PVDF in a ratio of 7: 2: 1, preparing uniform slurry by using N-methyl pyrrolidone (NMP) as a solvent, uniformly coating the uniform slurry on an aluminum foil, putting the prepared film in a drying oven, and drying for 2 hours at 60 ℃; after drying, transferring the mixture into a vacuum drying oven, and drying the mixture in the vacuum drying oven for 12 hours at the temperature of 60 ℃; and tabletting, cutting and weighing the dried composite material coating by a tablet machine and the like.
And (3) assembling the battery in an argon atmosphere by using a lithium sheet as a counter electrode and using a 1M LiTFSI/DME + DOL solution as an electrolyte.
Finally, a battery tester is used for testing the charge and discharge performance, the obtained product is used as the lithium-sulfur battery anode material, the cycle stability test result under the current density of 0.2C is shown in figure 10, and the battery capacity is still higher than 800mAh g after 100 cycles-1The charge and discharge curve is shown in fig. 11, and the lithium-sulfur battery positive electrode material has a stable charge and discharge platform at a current density of 0.2C.
Comparative example 1
The preparation method of the sulfur-loaded ferroferric oxide composite material with the one-dimensional chain structure comprises the following steps:
1) an ice bath process: the preparation method is the same as the step 1) of the example 3;
2) a sulfuration procedure: weighing 0.1g of ferroferric oxide with a chain structure prepared in the step 1) and 0.2g of sulfur powder, uniformly mixing, putting into a polytetrafluoroethylene plastic bottle, filling argon into the bottle, keeping the temperature at 155 ℃ for 15 hours, and naturally cooling to obtain the ferroferric oxide sulfur particle-loaded composite material with the one-dimensional chain structure.
The application of the prepared composite material of ferroferric oxide loaded sulfur particles with the one-dimensional chain structure is used for manufacturing a lithium-sulfur battery, and specifically comprises the following steps:
taking the final product of ferroferric oxide sulfur-loaded composite material with one-dimensional chain structure obtained in the comparative example 1 as the active material of the lithium-sulfur battery anode, and mixing the active material with conductive carbon black and PVDF in a ratio of 7: 2: 1, preparing uniform slurry by using N-methyl pyrrolidone (NMP) as a solvent, uniformly coating the uniform slurry on an aluminum foil, putting the prepared film in a drying oven, and drying for 2 hours at 60 ℃; after drying, transferring the mixture into a vacuum drying oven, and drying the mixture in the vacuum drying oven for 12 hours at the temperature of 60 ℃; and tabletting, cutting and weighing the dried composite material coating by a tablet machine and the like.
And (3) assembling the battery in an argon atmosphere by using a lithium sheet as a counter electrode and using a 1M LiTFSI/DME + DOL solution as an electrolyte.
The result of the cycle stability test of the obtained product as the positive electrode material of the lithium-sulfur battery at the current density of 0.2C is shown in FIG. 12, and the battery capacity is 440mAh g after 100 cycles-1And the capacity is obviously lower than that of a lithium-sulfur battery prepared from the ferroferric oxide/carbon nano tube/sulfur-loaded composite material with the one-dimensional chain-shaped core-shell structure.
The above detailed descriptions of the ferroferric oxide/carbon nanotube/sulfur-loaded composite material with one-dimensional chain core-shell structure, the preparation method thereof, the lithium-sulfur battery positive electrode and the battery, which are described above with reference to the embodiments, are illustrative and not restrictive, and several embodiments can be enumerated according to the limited scope, so that changes and modifications without departing from the general concept of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. The preparation method of the ferroferric oxide/carbon nano tube/sulfur-loaded composite material with the one-dimensional chain-shaped core-shell structure is characterized by comprising the following steps:
1) uniformly mixing sodium borohydride and cyclohexane, adding a trivalent ferric salt solution, uniformly mixing, and carrying out ice bath reaction to obtain a chain ferroferric oxide material;
2) dispersing the chain ferroferric oxide material prepared in the step 1) in water, adding trihydroxymethyl aminomethane, adding dopamine hydrochloride, reacting, and obtaining the chain ferroferric oxide/carbon nano material after the reaction is finished;
3) roasting the chain ferroferric oxide/carbon nano material prepared in the step 2) to prepare chain ferroferric oxide/carbon nano tubes;
4) dispersing the chain ferroferric oxide/carbon nano tube prepared in the step 3) in a dilute hydrochloric acid solution, and reacting to obtain chain ferroferric oxide/carbon nano tube with a core-shell structure;
5) uniformly mixing the ferroferric oxide/carbon nano tube with the chain-like core-shell structure prepared in the step 4) with sulfur powder, and carrying out sulfur fumigation to obtain the ferroferric oxide/carbon nano tube/sulfur-loaded composite material with the one-dimensional chain-like core-shell structure.
2. The method of claim 1, wherein in step 1), the ice-bath reaction is carried out at 0-10 ℃ for 1 h.
3. The method according to claim 1 or 2, wherein in step 1), the volume ratio of the ferric salt solution to the cyclohexane is 1-1.3: 1; the dosage ratio of the sodium borohydride to the cyclohexane is 0.3-0.5 mol/L.
4. The preparation method according to claim 1, wherein in the step 2), the mass ratio of the ferroferric oxide material to the tris (hydroxymethyl) aminomethane to the dopamine hydrochloride is 1: (8-15): (0.4-0.8).
5. The method according to claim 1 or 4, wherein the pH of the system is adjusted to 6.5 to 10 after the tris is added in step 2).
6. The method according to claim 1 or 4, wherein the reaction time in step 2) is 18 to 30 hours.
7. The preparation method as claimed in claim 1 or 4, wherein in step 3), the roasting condition is 500-800 ℃ for 2-8 h.
8. The method according to claim 1 or 4, wherein the reaction time in step 4) is 10 to 60 min.
9. The ferroferric oxide/carbon nano tube/sulfur-loaded composite material with the one-dimensional chain-shaped core-shell structure, which is prepared by the method in any one of claims 1 to 8, wherein the width dimension of the chain is 100-300 nm.
10. An application of the ferroferric oxide/carbon nano tube/sulfur-loaded composite material with the one-dimensional chain-like core-shell structure prepared by the method of any one of claims 1 to 8, which is characterized in that the ferroferric oxide/carbon nano tube/sulfur-loaded composite material is used for manufacturing a lithium-sulfur battery.
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| CN104987731A (en) * | 2015-07-03 | 2015-10-21 | 苏州大学 | One-dimension nanochain-typed Fe3O4/silk protein compound and preparation method thereof |
| CN107670646A (en) * | 2017-09-22 | 2018-02-09 | 中国科学院合肥物质科学研究院 | A kind of bead structure nano zero valence iron/cellulose composite material and its application |
| US20190127252A1 (en) * | 2017-10-26 | 2019-05-02 | Soochow University | Magnetic nanoparticle microbial composite with core-shell structure, preparation method thereof, and its application in the treatment of azo dyes |
| CN109119625A (en) * | 2018-09-28 | 2019-01-01 | 国网山东省电力公司电力科学研究院 | A kind of preparation method of ferroso-ferric oxide-carbon nanotube lithium cell cathode material |
| US20200152965A1 (en) * | 2018-11-12 | 2020-05-14 | Zhejiang A & F University | Nanosheet composite for cathode of lithium-sulfur battery, preparation method thereof and electrode and battery comprising the same |
| CN109935430A (en) * | 2019-03-06 | 2019-06-25 | 湖南理工学院 | A kind of preparation and application of magnetic one-dimensional chain nano-complex |
| CN110449597A (en) * | 2019-09-06 | 2019-11-15 | 哈尔滨工业大学 | A kind of chain Fe nanowire and preparation method thereof |
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