CN108511701B - Nickel-cobalt-sulfur hollow sphere used as positive electrode of lithium-sulfur battery, and preparation method and application thereof - Google Patents
Nickel-cobalt-sulfur hollow sphere used as positive electrode of lithium-sulfur battery, and preparation method and application thereof Download PDFInfo
- Publication number
- CN108511701B CN108511701B CN201810108692.XA CN201810108692A CN108511701B CN 108511701 B CN108511701 B CN 108511701B CN 201810108692 A CN201810108692 A CN 201810108692A CN 108511701 B CN108511701 B CN 108511701B
- Authority
- CN
- China
- Prior art keywords
- sulfur
- cobalt
- nickel
- lithium
- sulfur battery
- 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.)
- Expired - Fee Related
Links
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 title claims abstract description 35
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 239000002077 nanosphere Substances 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 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 abstract description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012935 ammoniumperoxodisulfate Substances 0.000 claims abstract description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 8
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 8
- 239000001632 sodium acetate Substances 0.000 claims abstract description 8
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 claims abstract description 8
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001291 vacuum drying Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000005543 nano-size silicon particle Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000002238 attenuated effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
Images
Classifications
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a nickel-cobalt-sulfur hollow sphere used as a lithium-sulfur battery anode, a preparation method and application thereof in preparation of a lithium-sulfur battery. The preparation method comprises the following steps: dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate, potassium peroxodisulfate or ammonium peroxodisulfate, ammonium fluoride and sodium acetate in deionized water, stirring, adding nano silicon dioxide spheres, and performing ultrasonic dispersion; heating the suspension for reaction, washing and drying; and adding the precursor powder into deionized water for ultrasonic dispersion, adding sodium sulfide nonahydrate into the dispersion liquid, heating the mixed liquid for reaction, washing and drying to obtain black nickel-cobalt-sulfur hollow nanosphere powder. According to the invention, the nano nickel-cobalt-sulfur hollow spheres are prepared by one step by using a simple hydrothermal method to serve as the sulfur fixing material, and the prepared nano nickel-cobalt-sulfur particles have good prospect as the anode load material of the lithium-sulfur battery, so that the cycle performance of the lithium-sulfur battery is improved. The method is simple and easy to implement, safe, environment-friendly and low in cost, and is suitable for large-scale production.
Description
Technical Field
The invention relates to a nickel-cobalt-sulfur hollow sphere used as a lithium-sulfur battery positive electrode, a preparation method and application, and belongs to the technical field of preparation of electrode materials of ion batteries.
Background
With the increasing demand for energy in the current society and the gradual depletion of traditional fossil energy, it puts higher demands on efficient utilization and storage of energy. During this period, lithium ion batteries enter people's lives as high-load and portable devices, and lithium sulfur batteries have very high theoretical specific capacity (1675mAh/g) which is far higher than that of the current lithium ion batteries using graphite as a negative electrode (372mAh/g), so that the lithium sulfur batteries become promising next-generation energy storage devices. However, besides the disadvantages of the conventional lithium ion battery, the lithium sulfur battery has a series of problems to be solved urgently: lithium metal can gradually generate lithium dendrite in the charging and discharging process, and finally the battery is short-circuited due to the fact that a diaphragm is pierced; because the used metal lithium is very sensitive to moisture and air, the requirement on the sealing performance of the battery is high; lithium polysulfide as a discharge intermediate product can be dissolved in electrolyte, and reacts with metal lithium along with the arrival of the electrolyte at a negative electrode in the charge-discharge process, so that the performance of the battery is seriously attenuated; the conductivity of the elemental sulfur is extremely low, so that the charging and discharging are difficult to be completely carried out, and the internal resistance of the battery is high; the density of the final product lithium sulfide is less than that of elemental sulfur, so that the volume of the positive electrode expands in the discharging process, and the structure of the battery is damaged. The current solution is mainly to coat sulfur in a conductive nano material with a sulfur fixing effect; modifying the diaphragm; changing to electrolyte with different components; a solid electrolyte is used.
Disclosure of Invention
The invention aims to solve the problems that: the sulfur has the defects on the conductivity, reduces the dissolution of intermediate products, and improves the rate capability and the cycling stability of the battery.
In order to solve the problems, the invention provides a preparation method of a nickel-cobalt-sulfur hollow sphere used as a positive electrode of a lithium-sulfur battery, which is characterized by comprising the following steps of:
step 1): dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate, potassium peroxodisulfate or ammonium peroxodisulfate, ammonium fluoride and sodium acetate in deionized water, stirring, adding nano-silica spheres, and performing ultrasonic dispersion to uniformly disperse the nano-silica spheres in the solution;
step 2): pouring the suspension obtained in the step 1) into a lining of a reaction kettle, sealing, placing in a constant-temperature oven, heating to 140 ℃ and 180 ℃ for reaction, respectively washing with deionized water and ethanol after natural cooling, centrifuging for multiple times until no impurity ions exist, and placing in a constant-temperature vacuum drying oven for drying to obtain light pink precursor powder;
step 3): adding the precursor powder into deionized water for ultrasonic dispersion to obtain dispersion liquid; adding sodium sulfide nonahydrate into the dispersion liquid, pouring the mixed liquid into the inner liner of a reaction kettle, sealing, placing in a constant-temperature oven, heating to 90-120 ℃ for reaction, respectively washing with deionized water and ethanol after natural cooling, centrifuging for many times until no impurity ions exist, and placing in a constant-temperature vacuum drying oven for drying to obtain black nickel-cobalt-sulfur hollow nanosphere powder.
Preferably, the weight ratio of cobalt nitrate hexahydrate, nickel nitrate hexahydrate, potassium or ammonium peroxodisulfate, ammonium fluoride, sodium acetate to nano-silica spheres in step 1) is 0.05-0.1: 0.1-0.3: 0.2: 1-3: 0.1-0.2; stirring for 30-60 min; the ultrasonic treatment time is 30-60 min.
Preferably, the filling rate of the suspension in the reaction kettle lining in the step 2) is 80%; the heating rate is 5-10 ℃/min, and the reaction time is 6-8 h; the temperature of the constant-temperature vacuum drying oven is 60 ℃, and the drying time is 12 h.
Preferably, the mass volume ratio of the precursor powder to the deionized water in the step 3) is 075-2.25 g/L; the ultrasonic treatment time is 15-30 min.
Preferably, the mass-to-volume ratio of the sodium sulfide nonahydrate to the dispersion liquid in the step 3) is 0.18-0.24 g/mL; the filling rate of the mixed solution in the inner liner of the reaction kettle is 80 percent; the heating rate is 5-10 ℃/min, and the reaction time is 8-24 h; the temperature of the constant-temperature vacuum drying oven is 60 ℃, and the drying time is 12-24 h.
Preferably, the diameter of the nickel-cobalt-sulfur hollow nanosphere powder obtained in the step 3) is equal to that of the silica nanosphere added in the step 1).
The invention also provides the nickel-cobalt-sulfur hollow sphere prepared by the preparation method of the nickel-cobalt-sulfur hollow sphere used as the positive electrode of the lithium-sulfur battery.
The invention also provides a preparation method of the lithium-sulfur battery, which is characterized by comprising the following steps of:
step 4): mixing the nickel-cobalt-sulfur hollow spheres with sublimed sulfur, preserving the heat at 160 ℃ under the protection of nitrogen or argon, and taking out after naturally cooling to room temperature;
step 5): mixing the mixture obtained in the step 4) with PVDF and acetylene black, grinding uniformly, dissolving with NMP, coating on a cleaned aluminum foil, and then placing in a constant-temperature vacuum drying oven for drying to obtain a positive pole piece of the lithium-sulfur battery;
step 6): and (3) placing the positive pole piece of the lithium-sulfur battery in a glove box, and assembling the battery by using metal lithium as a negative pole.
Preferably, the mass ratio of the nickel-cobalt-sulfur hollow nanosphere powder to the sublimed sulfur in the step 4) is 1: 4; the heat preservation time is 15-36 h.
Preferably, the mass ratio of the mixture obtained in the step 4) in the step 5) to PVDF and acetylene black is 6-7: 1-2: 2-3; the temperature of the constant-temperature vacuum drying oven is 60 ℃, and the drying time is at least 24 h.
The invention utilizes a simple hydrothermal method to prepare the nano nickel-cobalt-sulfur hollow sphere in one step as a sulfur fixing material, thereby improving the cycle performance of the lithium-sulfur battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts a simple one-step hydrothermal method, easily-obtained raw materials, simple preparation method and safe preparation process;
(2) the diameter of the nickel-cobalt-sulfur hollow sphere prepared by the method is consistent with that of the added silicon dioxide nanosphere, and the preparation method of the nano silicon dioxide sphere is quite mature and the size of the nano silicon dioxide sphere is easy to control, so that the nickel-cobalt-sulfur hollow sphere which is relatively difficult to control is prepared by using the silicon dioxide sphere which can conveniently control the size as a template;
(3) the hollow sphere structure prepared by the method of the invention correspondingly improves the specific surface area, and the nickel-cobalt-sulfur has good fixing effect on polysulfide, so that the shuttle effect of the battery can be obviously weakened. In addition, nickel cobalt sulfide has good conductivity compared with oxides and binary sulfides which are generally used for sulfur fixation. The cycling stability of the battery is improved under the condition of ensuring a certain specific capacity, and the lithium-sulfur battery has great potential on the aspect of solving the existing problems of the lithium-sulfur battery.
Drawings
FIG. 1 is a scanning electron microscope image of low field emission of Ni-Co-S hollow spheres prepared in example 3;
FIG. 2 is a transmission electron microscope image of high field emission of Ni-Co-S hollow spheres prepared in example 3;
fig. 3 is a graph of rate capability tests at 0.1C, 0.2C, 0.5C, 1C, 2C, 1C, 0.5C, 0.2C, and 0.1C, respectively, for the nickel-cobalt-sulfur hollow sphere used as a positive electrode of a lithium-sulfur battery in example 4;
fig. 4 is a graph of the cycle stability performance at 1C when the nickel-cobalt-sulfur hollow sphere is used as the positive electrode of the lithium-sulfur battery in example 4.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1
A preparation method of a nickel-cobalt-sulfur hollow sphere comprises the following steps:
(1) weighing 75mg of cobalt nitrate hexahydrate, 75mg of nickel nitrate hexahydrate, 0.2g of potassium peroxodisulfate or ammonium peroxodisulfate, 0.2g of ammonium fluoride and 2g of sodium acetate, dissolving in 40mL of deionized water, stirring for 30min, adding 0.1g of nano-silica spheres with the diameter of 350nm, and performing ultrasonic dispersion for 30 min;
(2) pouring the obtained pink suspension into a lining of a 50mL polytetrafluoroethylene high-pressure reaction kettle, sealing, placing in a constant-temperature oven, heating to 160 ℃ at a heating rate of 10 ℃/min, reacting for 8h, washing with deionized water and ethanol respectively after natural cooling, centrifuging for multiple times until no impurity ions exist, and placing in a constant-temperature vacuum drying oven at 60 ℃ for 12h to obtain pink precursor powder;
(3) and (2) adding 40mL of deionized water into 30mg of the obtained fluffy dried powder, performing ultrasonic dispersion for 30min, weighing 0.96g of sodium sulfide nonahydrate to be dissolved in dispersion liquid, pouring the mixed liquid into a lining of a 50mL polytetrafluoroethylene high-pressure reaction kettle, sealing, putting the mixture into a constant-temperature oven, heating to 120 ℃ at the heating rate of 10 ℃/min to react for 12h, naturally cooling, washing with the deionized water and ethanol, centrifuging for multiple times until no foreign ions exist, and putting the mixture into a constant-temperature vacuum drying oven at 60 ℃ for 24h to obtain black Ni1.5Co1.5S4 hollow sphere powder with the diameter of 350 nm.
Example 2
A preparation method of a nickel-cobalt-sulfur hollow sphere comprises the following steps:
(1) weighing 100mg of cobalt nitrate hexahydrate, 50mg of nickel nitrate hexahydrate, 0.2g of potassium peroxodisulfate or ammonium peroxodisulfate, 0.2g of ammonium fluoride and 2g of sodium acetate, dissolving in 40mL of deionized water, stirring for 30min, adding 0.1g of nano-silica spheres with the diameter of 350nm, and performing ultrasonic dispersion for 30 min;
(2) pouring the obtained pink solution into a lining of a 50mL polytetrafluoroethylene high-pressure reaction kettle, sealing, placing in a constant-temperature oven, heating to 160 ℃ at a heating rate of 10 ℃/min, reacting for 8h, washing with deionized water and ethanol respectively after natural cooling, centrifuging for multiple times until no impurity ions exist, and placing in a constant-temperature vacuum drying oven at 60 ℃ for 12h to obtain pink precursor powder;
(3) taking 30mg of the obtained fluffy dry powder, adding 40mL of deionized water, performing ultrasonic dispersion for 30min, weighing 0.96g of sodium sulfide nonahydrate to be dissolved in dispersion liquid, pouring the mixed liquid into a lining of a 50mL polytetrafluoroethylene high-pressure reaction kettle, sealing, placing in a constant-temperature oven, heating to 120 ℃ at a heating rate of 10 ℃/min to react for 12h, after natural cooling, respectively washing with the deionized water and ethanol, centrifuging for many times until no foreign ions exist, and placing in a constant-temperature vacuum drying oven at 60 ℃ for 24h to obtain black NiCo2S4 hollow sphere powder with the diameter of 350 nm;
example 3
A preparation method of a nickel-cobalt-sulfur hollow sphere comprises the following steps:
(1) weighing 100mg of cobalt nitrate hexahydrate, 50mg of nickel nitrate hexahydrate, 0.3g of potassium peroxodisulfate or ammonium peroxodisulfate, 0.2g of ammonium fluoride and 3g of sodium acetate, dissolving in 40mL of deionized water, stirring for 30min, adding 0.1g of nano-silica spheres with the diameter of 270nm, and performing ultrasonic dispersion for 30 min;
(2) pouring the obtained pink solution into a lining of a 50mL polytetrafluoroethylene high-pressure reaction kettle, sealing, placing in a constant-temperature oven, heating to 160 ℃ at a heating rate of 10 ℃/min, reacting for 8h, washing with deionized water and ethanol respectively after natural cooling, centrifuging for multiple times until no impurity ions exist, and placing in a constant-temperature vacuum drying oven at 60 ℃ for 12h to obtain pink precursor powder;
(3) taking 30mg of the fluffy dry powder obtained above, adding 40mL of deionized water, performing ultrasonic dispersion for 30min, weighing 0.96g of sodium sulfide nonahydrate, dissolving in the dispersion, pouring the mixed solution into a 50mL polytetrafluoroethylene high-pressure reaction kettle lining, sealing, placing in a constant-temperature oven, and heating at a speed of 10 ℃/minHeating to 120 ℃ for reaction for 12h, respectively washing with deionized water and ethanol after natural cooling, centrifuging for many times until no impurity ions exist, placing in a constant-temperature vacuum drying oven at 60 ℃ for 24h to obtain black NiCo with the diameter of 270nm2S4Hollow sphere powder, as shown in fig. 1 and 2.
Example 4
A preparation method of a lithium-sulfur battery comprises the following steps:
(1) mixing 40mg of the nickel-cobalt-sulfur hollow sphere powder in the embodiment 2 with 80mg of sublimed sulfur, preserving the heat for 24 hours at the temperature of 155 ℃ under the protection of nitrogen, and naturally cooling to room temperature to obtain a sulfur/nickel-cobalt-sulfur composite material;
(2) mixing 49mg of the sulfur/nickel-cobalt-sulfur composite material in the step (1), PVDF7mg and acetylene black 14mg, uniformly grinding, dissolving with NMP, coating on a clean aluminum foil, and then placing in a constant-temperature vacuum drying oven at 60 ℃ for 24 hours to obtain a positive pole piece of the lithium-sulfur battery;
(3) and (3) placing the pole piece in the step (2) in a glove box, assembling the battery by using metal lithium as a negative electrode, and testing the rate performance and the cycling stability.
As can be seen from fig. 3, the battery has higher capacity when charged and discharged at low rates of 0.1C, 0.2C, 0.5C, and the charge and discharge energy keeps the capacity stable at high rates of 1C, 2C.
As can be seen from FIG. 4, after the battery is charged and discharged for 200 circles at 1C, the specific capacity is reduced from 410mAh/g to 216mAh/g, which is equivalent to that the capacity of each charging and discharging cycle is attenuated by 0.23%, and the coulombic efficiency is close to 100%, which shows that the battery has better cycle stability.
Claims (10)
1. A preparation method of a nickel-cobalt-sulfur hollow sphere used as a positive electrode of a lithium-sulfur battery is characterized by comprising the following steps:
step 1): dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate, potassium peroxodisulfate or ammonium peroxodisulfate, ammonium fluoride and sodium acetate in deionized water, stirring, adding nano-silica spheres, and performing ultrasonic dispersion to uniformly disperse the nano-silica spheres in the solution;
step 2): pouring the suspension obtained in the step 1) into a lining of a reaction kettle, sealing, placing in a constant-temperature oven, heating to 140 ℃ and 180 ℃ for reaction, respectively washing with deionized water and ethanol after natural cooling, centrifuging for multiple times until no impurity ions exist, and placing in a constant-temperature vacuum drying oven for drying to obtain light pink precursor powder;
step 3): adding the precursor powder into deionized water for ultrasonic dispersion to obtain dispersion liquid; adding sodium sulfide nonahydrate into the dispersion liquid, pouring the mixed liquid into the inner liner of a reaction kettle, sealing, placing in a constant-temperature oven, heating to 90-120 ℃ for reaction, respectively washing with deionized water and ethanol after natural cooling, centrifuging for many times until no impurity ions exist, and placing in a constant-temperature vacuum drying oven for drying to obtain black nickel-cobalt-sulfur hollow nanosphere powder.
2. The method of claim 1, wherein the weight ratio of cobalt nitrate hexahydrate, nickel nitrate hexahydrate, potassium or ammonium peroxodisulfate, ammonium fluoride, sodium acetate and nano-silica spheres in step 1) is 0.05-0.1: 0.1-0.3: 0.2: 1-3: 0.1-0.2; stirring for 30-60 min; the ultrasonic treatment time is 30-60 min.
3. The method for preparing the nickel-cobalt-sulfur hollow sphere used as the positive electrode of the lithium-sulfur battery according to claim 1, wherein the filling rate of the suspension in the reaction kettle lining in the step 2) is 80%; the heating rate is 5-10 ℃/min, and the reaction time is 6-8 h; the temperature of the constant-temperature vacuum drying oven is 60 ℃, and the drying time is 12 h.
4. The method according to claim 1, wherein the mass-to-volume ratio of the precursor powder to the deionized water in step 3) is 0.75-2.25 g/L; the ultrasonic treatment time is 15-30 min.
5. The method for preparing the nickel-cobalt-sulfur hollow sphere used as the positive electrode of the lithium-sulfur battery according to claim 1, wherein the mass-to-volume ratio of the sodium sulfide nonahydrate to the dispersion liquid in the step 3) is 0.18 to 0.24 g/mL; the filling rate of the mixed solution in the inner liner of the reaction kettle is 80 percent; the heating rate is 5-10 ℃/min, and the reaction time is 8-24 h; the temperature of the constant-temperature vacuum drying oven is 60 ℃, and the drying time is 12-24 h.
6. The method for preparing a nickel-cobalt-sulfur hollow sphere used as a positive electrode of a lithium-sulfur battery according to claim 1, wherein the nickel-cobalt-sulfur hollow nanosphere powder obtained in the step 3) has an inner diameter equal to that of the silica nanospheres added in the step 1).
7. The nickel-cobalt-sulfur hollow sphere used as the positive electrode of the lithium-sulfur battery according to any one of claims 1 to 6.
8. A method for preparing a lithium-sulfur battery, comprising the steps of:
step 4): mixing the nickel-cobalt-sulfur hollow sphere of claim 7 with sublimed sulfur, preserving the heat at 160 ℃ under the protection of nitrogen or argon, and taking out the nickel-cobalt-sulfur hollow sphere after naturally cooling to room temperature;
step 5): mixing the mixture obtained in the step 4) with PVDF and acetylene black, grinding uniformly, dissolving with NMP, coating on a cleaned aluminum foil, and then placing in a constant-temperature vacuum drying oven for drying to obtain a positive pole piece of the lithium-sulfur battery;
step 6): and (3) placing the positive pole piece of the lithium-sulfur battery in a glove box, and assembling the battery by using metal lithium as a negative pole.
9. The method of claim 8, wherein the mass ratio of the nickel cobalt sulfur hollow nanosphere powder to the sublimed sulfur in step 4) is 1: 4; the heat preservation time is 15-36 h.
10. The method for preparing a lithium-sulfur battery according to claim 8, wherein the mass ratio of the mixture obtained in step 4) in step 5) to PVDF and acetylene black is 6-7: 1-2: 2-3; the temperature of the constant-temperature vacuum drying oven is 60 ℃, and the drying time is at least 24 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810108692.XA CN108511701B (en) | 2018-02-02 | 2018-02-02 | Nickel-cobalt-sulfur hollow sphere used as positive electrode of lithium-sulfur battery, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810108692.XA CN108511701B (en) | 2018-02-02 | 2018-02-02 | Nickel-cobalt-sulfur hollow sphere used as positive electrode of lithium-sulfur battery, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108511701A CN108511701A (en) | 2018-09-07 |
| CN108511701B true CN108511701B (en) | 2020-08-11 |
Family
ID=63375672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810108692.XA Expired - Fee Related CN108511701B (en) | 2018-02-02 | 2018-02-02 | Nickel-cobalt-sulfur hollow sphere used as positive electrode of lithium-sulfur battery, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108511701B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109378449B (en) * | 2018-09-13 | 2021-05-18 | 天津大学 | NiCo for positive electrode material of lithium-sulfur battery2S4Preparation method of coated porous carbon skeleton |
| CN112086295A (en) * | 2019-06-14 | 2020-12-15 | 同济大学 | Preparation method of nano nickel thiocobalate/carbon composite electrode material |
| CN110311135A (en) * | 2019-06-19 | 2019-10-08 | 东北大学 | A kind of metal sulfide hollow ball that can load sulphur, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103280601A (en) * | 2013-05-27 | 2013-09-04 | 浙江大学 | Method for manufacturing lithium-sulfur battery |
| CN106784740A (en) * | 2017-02-16 | 2017-05-31 | 盐城工学院 | A kind of hollow ball positive electrode and preparation method thereof |
| CN107248457A (en) * | 2017-07-26 | 2017-10-13 | 徐靖才 | One kind has caged NiCo2S4The preparation method of@carbon ball electrode materials |
-
2018
- 2018-02-02 CN CN201810108692.XA patent/CN108511701B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103280601A (en) * | 2013-05-27 | 2013-09-04 | 浙江大学 | Method for manufacturing lithium-sulfur battery |
| CN106784740A (en) * | 2017-02-16 | 2017-05-31 | 盐城工学院 | A kind of hollow ball positive electrode and preparation method thereof |
| CN107248457A (en) * | 2017-07-26 | 2017-10-13 | 徐靖才 | One kind has caged NiCo2S4The preparation method of@carbon ball electrode materials |
Non-Patent Citations (3)
| Title |
|---|
| Design and synthesis of 3D hierarchical NiCo2S4@MnO2 core–shell nanosheet arrays for high-performance pseudocapacitors;Kaibing Xu, Qilong Ren，Qian Liu等;《RSC Advances》;20150511;全文 * |
| Formation of nickel cobalt sulfide ball-in-ball hollow spheres with enhanced electrochemical pseudocapacitive properties;Laifa Shen，Le Yu，Hao Bin Wu等;《NATURE COMMUNICATIONS》;20150323;全文 * |
| NiCo2S4 hollow microsphere decorated by acetylene black for high-performance asymmetric supercapacitor;Yirong Zhu,Xiaobo Ji,Zhibin Wu等;《Electrochimica Acta》;20151101;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108511701A (en) | 2018-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105742602B (en) | A kind of sodium-ion battery cathode Sn/MoS2/ C composite and preparation method thereof | |
| CN105609730B (en) | A kind of preparation method of silicon/carbon graphite composite negative pole material | |
| CN102201576B (en) | Porous carbon in situ composite lithium iron phosphate cathode material and preparation method thereof | |
| CN105226285B (en) | A kind of porous Si-C composite material and preparation method thereof | |
| CN110380030B (en) | Preparation method of lithium-sulfur battery positive electrode material | |
| CN106099110B (en) | A method of making carbon source using algae and prepares Li-S cell positive materials | |
| CN105789584A (en) | Cobalt selenide/carbon sodium ion battery composite negative electrode material as well as preparation method and application of cobalt selenide/carbon-sodium ion battery composite negative electrode material | |
| CN102502889A (en) | Co3O4 microsphere flower-like material as well as preparation method and application thereof | |
| CN108511701B (en) | Nickel-cobalt-sulfur hollow sphere used as positive electrode of lithium-sulfur battery, and preparation method and application thereof | |
| CN107123790A (en) | A kind of porous silicon-base composite negative pole material, preparation method and lithium ion battery | |
| CN112174220B (en) | Titanium dioxide coated cobaltosic oxide honeycomb pore nanowire material and preparation and application thereof | |
| CN108199011B (en) | Preparation method of lithium titanate negative electrode material | |
| CN109360953A (en) | A kind of method synthesizing vulcanization lithium/carbon composite material and the lithium-sulfur cell using the material | |
| CN106252661A (en) | Bismuth sulfide/carbon nano tube compound material and its preparation method and application | |
| CN108400320B (en) | Method for vulcanizing surface of spinel lithium nickel manganese oxide positive electrode material | |
| CN112968173A (en) | Porous carbon-coated sulfur vacancy composite electrode material, preparation method thereof and circular electrode adopting material | |
| CN107579212A (en) | A kind of method that silica/graphite/carbon composite lithium ion battery cathode material is prepared using silicon tetrachloride | |
| CN105481004B (en) | A kind of high electric property tin dioxide nanometer tube and preparation method thereof | |
| CN108091874B (en) | Preparation method of nano nickel-cobalt-sulfur particles used as lithium-sulfur battery positive electrode | |
| CN103730664B (en) | A kind of lithium sulfur battery anode material and its preparation method and application | |
| CN113651359B (en) | Preparation method and application of antimony sulfide nanorod | |
| CN111180704A (en) | Sodium-ion battery positive electrode material and preparation method and application thereof | |
| CN105047870A (en) | Nitrogen-doped carbon-coated silicon composite material and preparation method thereof | |
| CN106025180A (en) | Lithium-ion battery cathode material GeO2/C with core-shell structure and preparation method thereof | |
| WO2021051908A1 (en) | Negative electrode material for sodium ion battery, preparation method therefor and use 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200811 |