CN114074952B - Synthesis method of flower-like microsphere with fluorine doped heterostructure - Google Patents
Synthesis method of flower-like microsphere with fluorine doped heterostructure Download PDFInfo
- Publication number
- CN114074952B CN114074952B CN202111363870.1A CN202111363870A CN114074952B CN 114074952 B CN114074952 B CN 114074952B CN 202111363870 A CN202111363870 A CN 202111363870A CN 114074952 B CN114074952 B CN 114074952B
- Authority
- CN
- China
- Prior art keywords
- sns
- reaction
- fluorine
- flower
- heterostructure
- 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
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 67
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000011737 fluorine Substances 0.000 title claims abstract description 46
- 239000004005 microsphere Substances 0.000 title claims abstract description 26
- 238000001308 synthesis method Methods 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 23
- 239000011593 sulfur Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 36
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 12
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 12
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000001338 self-assembly Methods 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 229940079864 sodium stannate Drugs 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 229910001887 tin oxide Inorganic materials 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000005077 polysulfide Substances 0.000 description 3
- 229920001021 polysulfide Polymers 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020923 Sn-O Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000034964 establishment of cell polarity Effects 0.000 description 1
- QNIHZKIMYOTOTA-UHFFFAOYSA-N fluoroform;lithium Chemical compound [Li].FC(F)F.FC(F)F QNIHZKIMYOTOTA-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000014233 sulfur utilization Effects 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the technical field of lithium sulfur batteries, in particular to a method for synthesizing flower-like microspheres with fluorine doped heterostructure, which comprises the steps of dissolving sulfur source and soluble tin salt in water, adding fluorine source, mixing uniformly to obtain reaction liquid, placing the obtained reaction liquid in a polytetrafluoroethylene reaction kettle for carrying out hydrothermal reaction, naturally cooling and centrifugally separating after the reaction is finished, washing for several times, and drying to obtain the flower-like microspheres with fluorine doped heterostructure.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur batteries, in particular to a method for synthesizing flower-shaped microspheres with fluorine doped heterostructures.
Background
SnS 2 /SnO 2 Heterostructures are a new type of functional material. SnS (SnS) 2 /SnO 2 When the heterostructure is used as a battery cathode material, snO 2 Has a theoretical capacity of 783mAh/g, and SnS 2 Can alleviate SnO by introducing 2 The volume change in the charge and discharge process improves the overall conductivity and the rate capability of the anode material. Research by a teacher Guo Ruisong at Tianjin university shows that SnS 2 /SnO 2 Interfacial interactions between oxides and sulfides in heterostructures can accelerate lithium ion expansionBulk rate, snO 2 The strong chemical bond interaction (S-Sn-O bond) with sulfur is SnS 2 Electrocatalytic conversion of polysulfides creates conditions (10.1002/celc.202100138). Thus, snS 2 /SnO 2 The construction of the heterostructure is of great significance to the improvement of the performance of the lithium-sulfur battery.
Patent CN113073355a through SnS 2 SnS is prepared by a surface local oxidation method 2 /SnO 2 Heterostructures, which can exhibit better photocatalytic activity and stability during photoelectrochemistry. Patent CN111450847a uses montmorillonite as carrier, on which fluorine doped SnO is carried out 2 Is vulcanized to prepare montmorillonite SnS 2 /SnO 2 The heterostructure has good organic adsorption performance and good photocatalytic degradation performance. However, these oxidation-before-sulfiding or sulfiding-before-oxidizing processes on tin sources often require multiple chemical reactions to achieve, which can lead to increased synthesis costs and experimental difficulties. Patent CN110028097A adopts stannous chloride as a tin source and thiourea as a sulfur source to prepare SnO 2 /SnS 2 Heterostructure, however, this method requires the introduction of sodium hydroxide to adjust the reaction solution to a strong basicity to ensure SnO 2 Phase generation.
Fluorine doping is an important method of changing the crystal structure of crystalline materials. Researches of the university of south and middle school show that fluorine doping can ensure MnO 2 Under the condition of constant phase, mnO is compressed by strong bonding action with Mn ions 2 Is improved in MnO 2 Electrochemical cycling stability of crystals (DOI: 10.1016/j. Mtener. 2021.100851). Research at the university of Harbin industry also shows that, because fluorine atoms are smaller in diameter than oxygen atoms, when fluorine atoms enter the lattice of an oxygenate to replace oxygen atoms, this results in a reduction in the unit cell volume of the oxygenate (DOI: 10.1016/j. Jelechem. 2021.115597). The doping of fluorine atoms not only affects the lattice size of the material, but may also cause changes in the microscopic morphology of the material. Studies at university of North China theory observed TiO due to fluorine doping 2 The crystal is transformed from no specific shape to a spherical structure (DOI: 10.1016/j. Ceramine. 2021).07.013 But the phase of the material is anatase TiO before and after doping 2 . Therefore, the previous studies are limited to the effect of fluorine atom doping on the lattice size and morphology of the material, and have not been directed to the role that fluorine atom doping plays in sulfide phase change and heterostructure formation.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for synthesizing flower-shaped microspheres with fluorine doped heterostructures.
The method is realized by the following technical scheme:
a method for synthesizing flower-like microspheres with fluorine doped heterostructure,
and (3) dissolving a sulfur source and a soluble tin salt in water, adding a fluorine source, uniformly mixing to obtain a reaction solution, placing the obtained reaction solution in a polytetrafluoroethylene reaction kettle for carrying out a hydrothermal reaction, naturally cooling and centrifugally separating after the reaction is finished, washing for a plurality of times, and drying to obtain the flower-shaped microsphere with a fluorine doped heterostructure.
The sulfur source is one or a mixture of more of thiourea and thioacetamide.
The soluble tin salt is one or a mixture of more of tin tetrachloride and sodium stannate.
The fluorine source is one or a mixture of more of ammonium fluoride and sodium fluoride.
The molar concentration of the sulfur source in the reaction liquid is 0.2-0.6 mol/L.
The molar concentration of the soluble tin salt in the reaction liquid is 0.05-0.15 mol/L.
The molar concentration of the fluorine source in the reaction liquid is 0.2-0.5 mol/L.
The high-temperature hydrothermal reaction temperature is 160-200 ℃ and the reaction time is 8-24 h.
The flower-shaped microsphere with the fluorine doped heterostructure is used as a positive electrode active material of a lithium-sulfur battery.
The flower-shaped microsphere with the fluorine doped heterostructure is used for manufacturing a positive electrode of a lithium-sulfur battery.
The invention uses the vulcanization process of tin sourceIn order to influence the precipitation process of the tin source. The addition of the fluorine source changes the morphological characteristics of the tin sulfide on one hand and induces the self-assembly process of the tin sulfide; on the other hand, the sulfuration process of the tin source is limited, and part of the tin source is oxidized to form a tin oxide phase, thereby obtaining fluorine doped SnS with a flower-sphere self-assembly structure 2 /SnO 2 In other words, the invention realizes that the phase composition of the material is changed through fluorine doping for the first time, plays a key role in the formation of the heterostructure, and finally is used as a sulfur carrying material of a lithium sulfur battery.
The beneficial effects are that:
the synthesis process of the invention only needs one step, is simple and easy to operate, does not need to adjust the pH value of the solution, does not need to calcine the product at high temperature, and can be directly used as sulfur-carrying material.
The invention can realize the process of forming the flower ball by self-assembly of the flaky structure in the one-step hydrothermal reaction process, and can control the phase of the product to form fluorine doped SnO 2 /SnS 2 A heterostructure; the main reason for this is: the introduction of the fluorine source can promote the flaky self-assembly process and inhibit SnS 2 Promoting the formation of SnO 2 The appearance of the phase.
The flower-shaped microsphere material with the fluorine-doped heterostructure has the advantages that a plurality of pore channels are reserved between the mutually-inserted sheets in the flower-shaped hierarchical structure, so that the sulfur loading, ion transmission and electrocatalytic conversion are facilitated, the polarity of the sulfur-loaded material is realized, and the adsorption capacity of sulfur simple substances and polysulfides is high.
According to the invention, the polarity of the sulfur-carrying material can be enhanced by introducing fluorine, and the adsorption capacity of the sulfur-carrying material to sulfur simple substances and polysulfides can be improved.
Drawings
FIG. 1 is SnS obtained in comparative example 1 2 Sheet structural material and fluorine doped SnS obtained in example 1 2 /SnO 2 XRD spectra of flower-like microspheres of heterostructure; wherein a is comparative example 1 and b is example 1;
FIG. 2 is SnS obtained in comparative example 1 2 Sheet structural material and fluorine doped SnS obtained in example 1 2 /SnO 2 Heterogeneous materialSEM image of flower-like microspheres of structure; wherein a is comparative example 1 and b is example 1;
FIG. 3 is S@SnS 2 Lamellar structure and S@ fluorine doped SnS 2 /SnO 2 Cyclic voltammograms of heterostructures;
FIG. 4 shows S@SnS after cyclic voltammetry 2 Lamellar structure and S@ fluorine doped SnS 2 /SnO 2 Electrochemical impedance spectrogram of heterostructure;
FIG. 5 is S@SnS 2 Charge-discharge curve graphs of the sheet structure under different multiplying powers;
FIG. 6 is S@ fluorine doped SnS 2 /SnO 2 A charge-discharge curve diagram of the heterostructure under different multiplying powers;
FIG. 7 is S@SnS 2 Lamellar structure and S@ fluorine doped SnS 2 /SnO 2 A ratio performance comparison graph of the heterostructure;
FIG. 8 is S@SnS 2 Lamellar structure and S@ fluorine doped SnS 2 /SnO 2 Comparison of the cyclic performance of heterostructures at 0.1C.
Detailed Description
The following detailed description of the invention is provided in further detail, but the invention is not limited to these embodiments, any modifications or substitutions in the basic spirit of the present examples, which still fall within the scope of the invention as claimed.
Example 1
A method for synthesizing flower-like microspheres with fluorine doped heterostructures comprises the following steps:
hydrothermal reaction: dissolving tin tetrachloride and thiourea into deionized water to obtain a mixed aqueous solution, wherein the concentration of the tin tetrachloride is 0.1mol/L and the concentration of the thiourea is 0.5mol/L; then adding ammonium fluoride into the mixed aqueous solution to make the concentration of the ammonium fluoride be 0.4mol/L, so as to prepare a reaction solution; and adding the obtained reaction solution into a reaction kettle, reacting for 10 hours at 180 ℃, naturally cooling to room temperature, then repeatedly washing for three times by centrifugation, water and ethanol, and standing at room temperature for vacuum drying overnight to obtain the flower-like microsphere product with fluorine doped heterostructure.
Comparative example 1
A synthesis method of an SnS2 lamellar structure comprises the following steps:
hydrothermal reaction: dissolving tin tetrachloride and thiourea into deionized water to obtain a mixed aqueous solution, wherein the concentration of the tin tetrachloride is 0.1mol/L and the concentration of the thiourea is 0.5mol/L; adding the obtained mixed aqueous solution into a reaction kettle, reacting for 10 hours at 180 ℃, naturally cooling to room temperature, then repeatedly washing for three times by centrifugation, water and ethanol, and standing at room temperature for vacuum drying overnight to obtain the SnS2 lamellar structure product.
Experimental example 1
Sulfur injection treatment: respectively taking samples of the example 1 and the comparative example 1, respectively mixing the samples with elemental sulfur in a mass ratio of 1:2, grinding, and sieving with a 200-mesh sieve to obtain uniform and fine sulfur-containing powder; putting the obtained sulfur-containing powder into a 50mL reaction kettle, heating the sulfur-containing powder in an oven at 155 ℃ for 8 hours, naturally cooling the powder to room temperature after the reaction is finished, taking out the powder, grinding the powder to be uniform, putting a sample into a 20mL quartz boat, heating the sample to 300 ℃ in a tube furnace filled with argon at a rate of 5 ℃ per minute, and keeping the temperature for 1 hour; taking out the powder, grinding and sieving with a 200-mesh sieve to obtain the sulfur-containing anode material, wherein the sulfur-containing anode material is S@SnS respectively 2 Lamellar structure and S@ fluorine doped SnS 2 /SnO 2 Heterostructures.
And (3) assembling a button cell: uniformly mixing and dispersing two sulfur-containing anode materials with polyvinylidene fluoride (PVDF) and conductive carbon black according to the mass ratio of 8:1:1 respectively in N-methyl pyrrolidone (NMP), uniformly stirring to form slurry, taking carbon-coated aluminum foil as a current collector, and carrying out coating, drying and cutting to prepare a round anode piece; in the process of assembling the button cell, a pure lithium sheet is taken as a negative electrode, a mixed solution of 1, 3-Dioxolane (DOL) and 1, 2-glycol dimethyl ether (DME) which contain 1.0M of lithium bistrifluoromethane yellow imide (LiTFSI) and 3.5% of LiNO3 is taken as an electrolyte, celgard2325 is taken as a diaphragm, a 2016 type cell shell is used, and the button cell is assembled in a glove box with water and oxygen content of less than 1 ppm; the electrode was prepared using the flower-shaped microsphere material with fluorine-doped heterostructure prepared in example 1 as a sulfur-carrying material, and a lithium sheet as a counter electrode thereof, and a CR 2016-type button cell was assembled, at a temperature of 30C, a voltage range of 1.7 to 2.8V and different current intensities of 0.05 to 1C (1c=1675 mA/g) and performing charge and discharge test; control group SnS prepared in comparative example 1 2 The sheet-shaped structural material is a sulfur-carrying material for preparing an electrode, the lithium sheet is a counter electrode of the electrode, the CR2016 type button cell is assembled, and the charge and discharge test is carried out under the conditions of the temperature of 30 ℃, the voltage range of 1.7-2.8V and different current intensities of 0.05-1C (1 C=1675 mA/g);
the results were as follows:
as can be seen from the X-ray diffraction pattern of FIG. 1, the main phase component obtained without adding a fluorine source is tin sulfide free of oxide phase (FIG. 1a, snS 2 PDF # 83-1706); after introduction of the fluorine source, under similar conditions, a mixture of tin oxide (FIG. 1b, snO 2 PDF # 41-1445) and tin sulfide (SnS 2 PDF # 83-1706) phase. Thus, the introduction of the fluorine source has an important effect on the phase of the product, namely SnO 2 /SnS 2 Important reasons for heterostructure formation.
Pure SnS 2 (FIG. 2 a) and SnO 2 /SnS 2 Comparing the scanning electron micrographs of heterostructures (FIG. 2 b) shows that pure SnS 2 Mainly shows a dispersed hexagonal lamellar structure (the size is about 300 nanometers), while SnO 2 /SnS 2 Heterostructures are self-assembled structures (sizes exceeding 2 microns) formed by interpenetration of lamellar structures. Between these self-assemblies, there are also a few hundred nanometric particles whose morphology differs greatly from that of the lamellar self-assemblies, due to SnO 2 /SnS 2 Having SnO in heterostructures 2 And SnS (sulfur-doped sulfur) 2 Resulting from two different phases. Therefore, the scanning electron microscope photo shows that fluorine doping can trigger the self-assembly process of tin sulfide lamellar structures, so that micron-sized flower ball structures are generated, the flower ball structures are formed by interpenetration of lamellar structures, a large number of macroporous structures are formed, and the sulfur carrying capacity and the dispersibility of elemental sulfur of the material can be improved.
As can be seen from the cyclic voltammogram results of FIG. 3, S@ fluorine doped SnO 2 /SnS 2 Area ratio S@SnS of graph surrounded by cyclic voltammetry curve of heterostructure 2 Is larger, indicating that S@ fluorine doped SnO 2 /SnS 2 The heterostructure has a greater electrochemical activity.
As can be seen from the electrochemical impedance spectroscopy of FIG. 4, S@ fluorine doped SnO 2 /SnS 2 The heterostructure has a smaller near circular radius, indicating that it is more than s@sns 2 The electrochemical impedance of the material is smaller, so that the material is more beneficial to the transmission of lithium ions in the battery.
From S@SnS of FIGS. 5 and 6 2 And S@ fluorine doped SnO 2/ SnS 2 The charge-discharge curve structure of the heterostructure shows that S@ fluorine is doped with SnO 2 /SnS 2 The heterostructure has a voltage difference between the charge curve and the discharge curve of 0.05C of 0.14V, ratio S@SnS 2 Is smaller, indicating S@ fluorine doped SnO (0.15V) 2 /SnS 2 Cell polarization in the heterostructure is improved; in the case of 1C discharge, S@SnS 2 The second discharge plateau of (2) almost completely disappeared, while S@ fluorine doped SnO 2 /SnS 2 The heterostructure is still able to present two distinct discharge plateaus, which is indicative of a significant difference from s@sns 2 Compared with S@ fluorine doped SnO 2 /SnS 2 The multiplying power performance of the heterostructure is obviously improved.
FIG. 7 shows a graph of the rate performance of S@ fluorine doped SnO 2 /SnS 2 The heterostructure can still maintain the discharge performance similar to that at 0.5C under the condition of 1C, and S@SnS 2 The discharge performance in the case of 1C is greatly different from the discharge performance of 0.5C. S@SnS 2 Specific discharge capacities at 0.05C, 0.1C, 0.2C, 0.5C and 1C are 1136, 827, 717, 584 and 279mAh/g, respectively; while S@ fluorine is doped with SnO 2 /SnS 2 The specific discharge capacities of the heterostructures at 0.05C, 0.1C, 0.2C, 0.5C and 1C were 1207, 877, 764, 670 and 547mAh/g, respectively. This further shows that relative to S@SnS 2 Structure, S@ fluorine doped SnO 2 /SnS 2 Heterostructures have a more pronounced discharge performance advantage at high rates.
Figure 8 shows the electrochemical cycling performance of the two materials at 0.1C. S@SnS 2 The specific capacity of the first week discharge is 1134mAh/g, and the first week discharge lasts for 120 weeksAfter the charge-discharge cycle, the specific discharge capacity is 552mAh/g, and the capacity retention rate is 48.7%; s@ fluorine doped SnO 2 /SnS 2 The heterostructure has a specific discharge capacity of 1206mAh/g at the first week, and after 120 weeks of charge-discharge cycles, the heterostructure has a specific discharge capacity of 674mAh/g and a capacity retention rate of 55.9%. With S@SnS 2 Compared with S@ fluorine doped SnO 2 /SnS 2 The sulfur utilization rate, specific discharge capacity and cycle performance of the heterostructure are all improved; the above results show that fluorine doping plays a significant role in changing the phase composition and morphology structure of the material and optimizing the electrochemical performance of the material.
Example 2
A method for synthesizing flower-like microspheres with fluorine doped heterostructures comprises the following steps:
hydrothermal reaction: dissolving tin tetrachloride and thiourea into deionized water to obtain a mixed aqueous solution, wherein the concentration of the tin tetrachloride is 0.15mol/L and the concentration of the thiourea is 0.6mol/L; then adding ammonium fluoride into the mixed aqueous solution to make the concentration of the ammonium fluoride be 0.5mol/L, so as to prepare a reaction solution; adding the obtained reaction solution into a reaction kettle, reacting for 24 hours at 200 ℃, naturally cooling to room temperature, then repeatedly washing for three times by centrifugation, water and ethanol, and standing at room temperature for vacuum drying overnight to obtain a flower-like microsphere product with a fluorine doped heterostructure;
the product is visible in the X-ray diffraction pattern and has two phases of tin sulfide and tin oxide;
the scanning electron microscope image finding shows that the product is a self-assembled body structure (the size is more than 2 microns) formed by interpenetration of sheet structures, and a large number of macroporous structures exist.
Example 3
A method for synthesizing flower-like microspheres with fluorine doped heterostructures comprises the following steps:
hydrothermal reaction: dissolving tin tetrachloride and thiourea into deionized water to obtain a mixed aqueous solution, wherein the concentration of the tin tetrachloride is 0.05mol/L and the concentration of the thiourea is 0.2mol/L; then adding sodium fluoride into the mixed aqueous solution to make the concentration of the sodium fluoride be 0.2mol/L, so as to prepare a reaction solution; adding the obtained reaction solution into a reaction kettle, reacting for 8 hours at 160 ℃, naturally cooling to room temperature, then repeatedly washing for three times by centrifugation, water and ethanol, and standing at room temperature for vacuum drying overnight to obtain a flower-like microsphere product with a fluorine doped heterostructure;
the product is visible in the X-ray diffraction pattern and has two phases of tin sulfide and tin oxide;
the scanning electron microscope image finding shows that the product is a self-assembled body structure (the size is more than 2 microns) formed by interpenetration of sheet structures, and a large number of macroporous structures exist.
Example 4
A method for synthesizing flower-like microspheres with fluorine doped heterostructures comprises the following steps:
hydrothermal reaction: dissolving tin tetrachloride and thioacetamide into deionized water to obtain a mixed aqueous solution, wherein the concentration of the tin tetrachloride is 0.05mol/L and the concentration of the thioacetamide is 0.5mol/L; then adding ammonium fluoride into the mixed aqueous solution to make the concentration of the ammonium fluoride be 0.3mol/L, so as to prepare a reaction solution; adding the obtained reaction solution into a reaction kettle, reacting for 20 hours at 190 ℃, naturally cooling to room temperature, then repeatedly washing for three times by centrifugation, water and ethanol, and standing at room temperature for vacuum drying overnight to obtain a flower-like microsphere product with a fluorine doped heterostructure;
the product is visible in the X-ray diffraction pattern and has two phases of tin sulfide and tin oxide;
the scanning electron microscope image finding shows that the product is a self-assembled body structure (the size is more than 2 microns) formed by interpenetration of sheet structures, and a large number of macroporous structures exist.
Example 5
A method for synthesizing flower-like microspheres with fluorine doped heterostructures comprises the following steps:
hydrothermal reaction: dissolving sodium stannate and thiourea into deionized water to obtain a mixed aqueous solution, wherein the concentration of sodium stannate is 0.15mol/L and the concentration of thiourea is 0.3mol/L; then adding ammonium fluoride into the mixed aqueous solution to make the concentration of the ammonium fluoride be 0.2mol/L, so as to prepare a reaction solution; adding the obtained reaction solution into a reaction kettle, reacting for 15 hours at 170 ℃, naturally cooling to room temperature, then repeatedly washing for three times by centrifugation, water and ethanol, and standing at room temperature for vacuum drying overnight to obtain a flower-like microsphere product with a fluorine doped heterostructure;
the product is visible in the X-ray diffraction pattern and has two phases of tin sulfide and tin oxide;
the scanning electron microscope image finding shows that the product is a flower ball structure (the size exceeds 2 microns) formed by interpenetration of sheet structures, and a large number of macroporous structures exist.
From the XRD patterns and SEM patterns of example 1 and example 5, it is understood that the product obtained by the method of the present invention has two phases, and the microstructure is a lattice structure (size exceeding 2 μm) formed by interpenetration of lamellar structures and a large number of macroporous structures exist; the method has feasibility and reproducibility.
Claims (1)
1. A method for synthesizing flower-sphere-shaped microspheres with fluorine doped heterostructure is characterized in that after a sulfur source and soluble tin salt are dissolved in water together, a fluorine source is added and mixed uniformly to prepare a reaction solution, the obtained reaction solution is placed in a polytetrafluoroethylene reaction kettle to perform high-temperature hydrothermal reaction, after the reaction is finished, natural cooling, centrifugal separation and washing are performed for a plurality of times, and after drying, the fluorine doped SnS with flower-sphere-shaped self-assembly structure is obtained 2 /SnO 2 Microspheres of heterostructure;
the molar concentration of the sulfur source in the reaction liquid is 0.2-0.6 mol/L;
the molar concentration of the soluble tin salt in the reaction solution is 0.05-0.15 mol/L;
the molar concentration of the fluorine source in the reaction liquid is 0.2-0.5 mol/L;
the high-temperature hydrothermal reaction temperature is 160-200 ℃ and the reaction time is 8-24 h;
the sulfur source is one or a mixture of more of thiourea and thioacetamide;
the soluble tin salt is one or a mixture of more of tin tetrachloride and sodium stannate;
the fluorine source is one or a mixture of more of ammonium fluoride and sodium fluoride.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111363870.1A CN114074952B (en) | 2021-11-17 | 2021-11-17 | Synthesis method of flower-like microsphere with fluorine doped heterostructure |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111363870.1A CN114074952B (en) | 2021-11-17 | 2021-11-17 | Synthesis method of flower-like microsphere with fluorine doped heterostructure |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114074952A CN114074952A (en) | 2022-02-22 |
CN114074952B true CN114074952B (en) | 2023-12-22 |
Family
ID=80283656
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111363870.1A Active CN114074952B (en) | 2021-11-17 | 2021-11-17 | Synthesis method of flower-like microsphere with fluorine doped heterostructure |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114074952B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115849435A (en) * | 2022-12-26 | 2023-03-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of tin dioxide nano material for gas detection, product and application thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102773110A (en) * | 2012-08-17 | 2012-11-14 | 扬州大学 | Method for preparing SnS2/SnO2 composite photocatalyst material of numismatics-shaped hollow structure |
WO2017139985A1 (en) * | 2016-02-19 | 2017-08-24 | 肖丽芳 | Preparation method for fluorine-doped lithium-sulfur battery anode material having three-dimensional structure |
CN111346595A (en) * | 2020-03-09 | 2020-06-30 | 浙江理工大学 | SnS2@SnO2Heterojunction and preparation method |
CN111450847A (en) * | 2020-04-30 | 2020-07-28 | 姚国财 | F-doped SnO2-SnS2Heterojunction-supported montmorillonite photocatalytic material and preparation method thereof |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10680242B2 (en) * | 2016-05-18 | 2020-06-09 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing positive electrode active material, and lithium ion battery |
CN107890876A (en) * | 2017-10-27 | 2018-04-10 | 苏州大学 | A kind of visible light-responded CC@SnS2/SnO2The preparation method and applications of composite catalyst |
-
2021
- 2021-11-17 CN CN202111363870.1A patent/CN114074952B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102773110A (en) * | 2012-08-17 | 2012-11-14 | 扬州大学 | Method for preparing SnS2/SnO2 composite photocatalyst material of numismatics-shaped hollow structure |
WO2017139985A1 (en) * | 2016-02-19 | 2017-08-24 | 肖丽芳 | Preparation method for fluorine-doped lithium-sulfur battery anode material having three-dimensional structure |
CN111346595A (en) * | 2020-03-09 | 2020-06-30 | 浙江理工大学 | SnS2@SnO2Heterojunction and preparation method |
CN111450847A (en) * | 2020-04-30 | 2020-07-28 | 姚国财 | F-doped SnO2-SnS2Heterojunction-supported montmorillonite photocatalytic material and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
One-step hydrothermal synthesis of high-performancevisible-light-driven SnS2/SnO2 nanoheterojunction photocatalyst forthe reduction of aqueous Cr(VI);Yong Cai Zhang等;Applied Catalysis B: Environmental;第第144卷卷;第730– 738页 * |
硫化物的合成制备及汞敏感性能研究;唐明聪;中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑;第4章 * |
Also Published As
Publication number | Publication date |
---|---|
CN114074952A (en) | 2022-02-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107369825B (en) | Nitrogen-doped carbon-coated manganese oxide lithium ion battery composite negative electrode material and preparation method and application thereof | |
CN104362296B (en) | A kind of new sulfur sill electrode and the preparation method and application thereof | |
Wan et al. | Pillow-shaped porous CuO as anode material for lithium-ion batteries | |
CN108352528B (en) | Positive electrode active material for lithium secondary battery and method for producing same | |
US11728467B2 (en) | Method of producing cathode active material, and method of producing lithium ion battery | |
CN109273691B (en) | Molybdenum disulfide/nitrogen-doped carbon composite material and preparation method and application thereof | |
CN110931741A (en) | Tin sulfide quantum dot loaded titanium carbide composite nano material and preparation method thereof | |
JP2013235786A (en) | Positive electrode active material and method for producing the same, positive electrode active material precursor, positive electrode for lithium secondary battery, and lithium secondary battery | |
CN101704681B (en) | Method for preparing lithium titanate with spinel structure | |
JP6930015B1 (en) | Precursor, positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery and lithium secondary battery | |
CN110808368A (en) | SnS/TiO for potassium ion battery cathode2rGO composite material, preparation method and electrolyte matched with same | |
TWI811499B (en) | Precursor for positive electrode active material of lithium secondary battery, method for producing the same and method for producing lithium complex metal compound | |
TWI651272B (en) | Process for producing lr-lnmo composite materials and use the same | |
CN107026263B (en) | Sea urchin-shaped bismuth sulfide/macroporous graphene composite material, preparation method and application thereof | |
CN113845152A (en) | Lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery | |
CN110400918B (en) | Preparation method of cobalt-sulfur compound/sulfur-doped carbon composite material | |
CN114074952B (en) | Synthesis method of flower-like microsphere with fluorine doped heterostructure | |
Li et al. | Role of Hydrothermal parameters on phase purity of orthorhombic LiMnO2 for use as cathode in Li ion battery | |
CN113772718A (en) | SnS-SnS2@ GO heterostructure composite material and preparation method and application thereof | |
US9656243B2 (en) | Mesoporous silicon synthesis and applications in Li-ion batteries and solar hydrogen fuel cells | |
CN112573503A (en) | Preparation method of nitrogen-doped porous carbon material, prepared porous carbon material and application thereof | |
CN110120519B (en) | Precursor of lithium-rich manganese-based positive electrode material with stacking structure and preparation method of lithium-rich manganese-based positive electrode material with stacking structure | |
Xu et al. | Exploration of Na 2.65 Ti 3.35 Fe 0.65 O 9 as anode materials for Na-ion batteries | |
Long et al. | A facile synthesis of heteroatom-doped carbon framework anchored with TiO 2 nanoparticles for high performance lithium ion battery anodes | |
CN113206226B (en) | Double-transition metal carbide compound and preparation method 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 |