CN108511701A - A kind of nickel cobalt sulphur hollow ball as lithium-sulphur cell positive electrode, preparation method and application - Google Patents
A kind of nickel cobalt sulphur hollow ball as lithium-sulphur cell positive electrode, preparation method and application Download PDFInfo
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- CN108511701A CN108511701A CN201810108692.XA CN201810108692A CN108511701A CN 108511701 A CN108511701 A CN 108511701A CN 201810108692 A CN201810108692 A CN 201810108692A CN 108511701 A CN108511701 A CN 108511701A
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- sulphur
- lithium
- nickel cobalt
- hollow ball
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- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 title claims abstract description 37
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 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 16
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 8
- 235000019395 ammonium persulphate Nutrition 0.000 claims abstract description 8
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-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 7
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims abstract description 6
- 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 5
- 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 5
- 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 5
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 4
- 239000001632 sodium acetate Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 5
- 238000003756 stirring Methods 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
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000005030 aluminium foil Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000002077 nanosphere Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 235000011091 sodium acetates Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical class [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 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
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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
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- 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
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
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Abstract
The invention discloses a kind of nickel cobalt sulphur hollow ball, preparation method and its application in preparing lithium-sulfur cell as lithium-sulphur cell positive electrode.The preparation method is that：Cabaltous nitrate hexahydrate, Nickelous nitrate hexahydrate, potassium persulfate or ammonium peroxydisulfate, ammonium fluoride and sodium acetate are dissolved in deionized water and are stirred, nanometer titanium dioxide silicon ball, ultrasonic disperse are added；It is dry after washing by suspension temperature reaction；Ultrasonic disperse in deionized water is added in predecessor powder, Sodium Sulphate Nine Hydroxide is added in dispersion liquid, it is dry after washing then by mixed liquor temperature reaction, obtain the nickel cobalt sulphur nano-hollow ball powder of black.The present invention prepares nanometer nickel-cobalt sulphur hollow ball as solid sulfur materials using a kind of one step of simple hydro-thermal method, and the nanometer nickel-cobalt sulphur particle being prepared has the good foreground as lithium-sulphur cell positive electrode support materials, improves the cycle performance of lithium-sulfur cell.Simple and practicable, safety and environmental protection of the invention, it is at low cost, it is suitable for large-scale production.
Description
Technical field
The nickel cobalt sulphur hollow ball that the present invention relates to a kind of as lithium-sulphur cell positive electrode, preparation method and application, belong to ion
The preparing technical field of battery electrode material.
Background technology
Increasingly exhaustion with current social to the growing demand and traditional fossil energy of the energy, this is for energy
More stringent requirements are proposed for the efficient utilization and storage in source.During this period, lithium ion battery as a kind of high load, portable set
Standby to get their way into people's lives, lithium-sulfur cell has very high theoretical specific capacity (1675mAh/g), is much higher by current stone
Ink makees the lithium ion battery (372mAh/g) of cathode, therefore as very promising next-generation energy storage device.However, lithium-sulfur cell
Other than having the shortcomings that conventional lithium ion battery, also a series of urgent problems：Lithium metal is in charge and discharge process
Li dendrite can be increasingly generated, the final diaphragm that pierces through leads to battery short circuit；Due to the use of lithium metal it is very quick to moisture, air
Sense, therefore the sealing performance of battery is required very high；The electric discharge more lithium sulfides of intermediate product can be dissolved in electrolyte, and in charge and discharge
It is reacted with lithium metal in journey as electrolyte reaches cathode, leads to battery performance deep fades；The conductivity pole of sulphur simple substance
It is low, cause charge and discharge to be difficult to carry out completely, and make the internal resistance of cell very big；Final product lithium sulfide density is less than sulphur simple substance,
So anode volume expands in discharge process, battery structure is destroyed.Sulphur is mainly coated on by current solution to be had
In the electrical-conductive nanometer material of captured sulfur result；Diagram modification；Use the electrolyte of heterogeneity instead；Use solid electrolyte.
Invention content
Problem to be solved by this invention is：Sulphur simple substance is in defect present on electric conductivity and reduces intermediate product
Dissolving, promotes high rate performance, the cyclical stability of battery.
To solve the above-mentioned problems, the preparation of the present invention provides a kind of nickel cobalt sulphur hollow ball as lithium-sulphur cell positive electrode
Method, which is characterized in that include the following steps：
Step 1)：By cabaltous nitrate hexahydrate, Nickelous nitrate hexahydrate, potassium persulfate or ammonium peroxydisulfate, ammonium fluoride and second
Sour sodium is dissolved in deionized water and stirs, and adds nanometer titanium dioxide silicon ball, and ultrasonic disperse keeps nanometer titanium dioxide silicon ball uniform
It is scattered in solution；
Step 2)：The suspension that step 1) obtains is poured into inner liner of reaction kettle, is sealed and is placed in constant temperature oven, is risen
Temperature is washed respectively with deionized water and ethyl alcohol after natural cooling, is centrifuged repeatedly to no heteroion to 140-180 DEG C of reaction
Afterwards, it is placed in drying in vacuum drying oven, obtains the predecessor powder of pale pink；
Step 3)：Ultrasonic disperse in deionized water is added in predecessor powder, obtains dispersion liquid；Nine are added in dispersion liquid
Then hydrated sodium sulfide pours into mixed liquor in inner liner of reaction kettle, be sealed and be placed in constant temperature oven, is warming up to 90-120 DEG C
Reaction is washed respectively with deionized water and ethyl alcohol after natural cooling, is centrifuged repeatedly to after no heteroion, is placed in constant-temperature vacuum
It is dry in drying box, obtain the nickel cobalt sulphur nano-hollow ball powder of black.
Preferably, cabaltous nitrate hexahydrate, Nickelous nitrate hexahydrate, potassium persulfate or ammonium peroxydisulfate in the step 1),
The weight ratio of ammonium fluoride, sodium acetate and nanometer titanium dioxide silicon ball is 0.05-0.1: 0.05-0.1：0.1-0.3：0.2：1-3：0.1-
0.2；Mixing time is 30-60min；Ultrasonic time is 30-60min.
Preferably, filling rate of the suspension in inner liner of reaction kettle is 80% in the step 2)；Heating rate is 5-10
DEG C/min, reaction time 6-8h；The temperature of vacuum drying oven is 60 DEG C, drying time 12h.
Preferably, predecessor powder and the mass volume ratio of deionized water are 075-2.25g/L in the step 3)；Ultrasound
Time is 15-30min.
Preferably, the mass volume ratio of Sodium Sulphate Nine Hydroxide and dispersion liquid is 0.18-0.24g/mL in the step 3)；It is mixed
It is 80% to close filling rate of the liquid in inner liner of reaction kettle；Heating rate is 5-10 DEG C/min, reaction time 8-24h；Constant temperature is true
The temperature of empty drying box is 60 DEG C, drying time 12-24h.
Preferably, the diameter for the nickel cobalt sulphur nano-hollow ball powder that the step 3) obtains and the dioxy being added in step 1)
The diameter of SiClx nanosphere is equal.
Nickel cobalt prepared by the preparation method of the present invention also provides the above-mentioned nickel cobalt sulphur hollow ball as lithium-sulphur cell positive electrode
Sulphur hollow ball.
The present invention also provides a kind of preparation methods of lithium-sulfur cell, which is characterized in that includes the following steps：
Step 4)：Above-mentioned nickel cobalt sulphur hollow ball is mixed with sublimed sulfur, under nitrogen or argon in 150-160 DEG C of guarantor
Temperature, after naturally cool to being taken out after room temperature；
Step 5)：The mixture that step 4) obtains is mixed with PVDF, acetylene black, grinding is uniform, is applied after being dissolved with NMP
It is dry on the aluminium foil of wash clean, being subsequently placed in vacuum drying oven, obtain positive pole plate of lithium-sulfur cell；
Step 6)：By positive pole plate of lithium-sulfur cell in glove box, use lithium metal as cathode assembled battery.
Preferably, the mass ratio of nickel cobalt sulphur nano-hollow ball powder and sublimed sulfur is 1: 4 in the step 4)；Soaking time
For 15-36h.
Preferably, the mixture that step 4) obtains in the step 5) and the mass ratio of PVDF, acetylene black are 6-7: 1-2:
2-3；The temperature of vacuum drying oven is 60 DEG C, and drying time is at least for 24 hours.
The present invention prepares nanometer nickel-cobalt sulphur hollow ball as solid sulfur materials using a kind of one step of simple hydro-thermal method, improves
The cycle performance of lithium-sulfur cell.
Compared with prior art, the beneficial effects of the present invention are：
(1) present invention is with simple one step hydro thermal method, and the raw material being easy to get, preparation method is simple, safe preparation process；
(2) the silica nanosphere diameter for the hollow bulb diameter of nickel cobalt sulphur and addition being prepared with the method for the present invention
Consistent, and the preparation method of nanometer titanium dioxide silicon ball is quite ripe, size is also easily controlled, therefore this method is using can be with
Facilitate the silica spheres as template of control size that the nickel cobalt sulphur hollow ball of size relatively more difficult to control has been made；
(3) hollow ball structure is made in method of the invention, has been correspondingly improved specific surface area, and nickel cobalt sulphur to vulcanizing more
Object has good fixed function, can significantly weaken the shuttle effect of battery.In addition, compared to the oxidation commonly used to solid sulphur
Object, binary sulfide, nickel cobalt sulphur have good electric conductivity.The cycle of battery is improved in the case where ensureing certain specific capacity
Stability, solving the problems, such as lithium-sulfur cell, presently, there are this aspect huge potentiality.
Description of the drawings
Fig. 1 is nickel cobalt sulphur hollow ball low power field emission scanning electron microscope picture prepared by embodiment 3；
Fig. 2 is nickel cobalt sulphur hollow ball high power Flied emission transmission electron microscope picture prepared by embodiment 3；
Fig. 3 be embodiment 4 in nickel cobalt sulphur hollow ball be used as lithium-sulphur cell positive electrode when respectively 0.1C, 0.2C, 0.5C, 1C,
High rate performance test chart under 2C, 1C, 0.5C, 0.2C, 0.1C；
Fig. 4 is that stable circulation performance when nickel cobalt sulphur hollow ball is used as lithium-sulphur cell positive electrode in embodiment 4 at 1C is tested
Figure.
Specific implementation mode
In order to make the present invention more obvious and understandable, hereby with preferred embodiment, and attached drawing is coordinated to be described in detail below.
Embodiment 1
A kind of preparation method of nickel cobalt sulphur hollow ball：
(1) weigh 75mg cabaltous nitrate hexahydrates, 75mg Nickelous nitrate hexahydrates, 0.2g potassium persulfates or ammonium peroxydisulfate,
0.2g ammonium fluorides and 2g sodium acetates, which are dissolved in 40mL deionized waters, stirs 30min, adds the nanometer two of 0.1g diameters 350nm
Silicon oxide ball and ultrasonic disperse 30min；
(2) obtained pink colour suspension is poured into 50mL polytetrafluoroethylene (PTFE) autoclave liners, is sealed and is placed on
In constant temperature oven, with the heating rate of 10 DEG C/min be warming up to 160 DEG C reaction 8h, after natural cooling respectively use deionized water and
Ethyl alcohol washing centrifuges repeatedly to no heteroion, is placed in 12h in 60 DEG C of vacuum drying ovens, obtains the predecessor of pink colour
Powder；
(3) powder of the fluffy drying of the above-mentioned acquisitions of 30mg is taken, 40mL deionized waters and ultrasonic disperse 30min is added, is claimed
It takes 0.96g Sodium Sulphate Nine Hydroxides to be dissolved in dispersion liquid, mixed liquor is poured into 50mL polytetrafluoroethylene (PTFE) autoclave liners, it is close
It seals and is placed in constant temperature oven, 120 DEG C of reaction 12h are warming up to the heating rate of 10 DEG C/min, after natural cooling respectively
It washed, centrifuged repeatedly to no heteroion with deionized water and ethyl alcohol, be placed in 60 DEG C of vacuum drying ovens for 24 hours, obtain
The Ni1.5Co1.5S4 hollow spherical powders of a diameter of 350nm of black.
Embodiment 2
A kind of preparation method of nickel cobalt sulphur hollow ball：
(1) weigh 100mg cabaltous nitrate hexahydrates, 50mg Nickelous nitrate hexahydrates, 0.2g potassium persulfates or ammonium peroxydisulfate,
0.2g ammonium fluorides and 2g sodium acetates, which are dissolved in 40mL deionized waters, stirs 30min, adds the nanometer two of 0.1g diameters 350nm
Silicon oxide ball and ultrasonic disperse 30min；
(2) obtained pink solution is poured into 50mL polytetrafluoroethylene (PTFE) autoclave liners, is sealed and is placed on
In constant temperature oven, with the heating rate of 10 DEG C/min be warming up to 160 DEG C reaction 8h, after natural cooling respectively use deionized water and
Ethyl alcohol washing centrifuges repeatedly to no heteroion, is placed in 12h in 60 DEG C of vacuum drying ovens, obtains the predecessor of pink colour
Powder；
(3) powder of the fluffy drying of the above-mentioned acquisitions of 30mg is taken, 40mL deionized waters and ultrasonic disperse 30min is added, is claimed
It takes 0.96g Sodium Sulphate Nine Hydroxides to be dissolved in dispersion liquid, mixed liquor is poured into 50mL polytetrafluoroethylene (PTFE) autoclave liners, it is close
It seals and is placed in constant temperature oven, 120 DEG C of reaction 12h are warming up to the heating rate of 10 DEG C/min, after natural cooling respectively
It washed, centrifuged repeatedly to no heteroion with deionized water and ethyl alcohol, be placed in 60 DEG C of vacuum drying ovens for 24 hours, obtain
The NiCo2S4 hollow spherical powders of a diameter of 350nm of black；
Embodiment 3
A kind of preparation method of nickel cobalt sulphur hollow ball：
(1) weigh 100mg cabaltous nitrate hexahydrates, 50mg Nickelous nitrate hexahydrates, 0.3g potassium persulfates or ammonium peroxydisulfate,
0.2g ammonium fluorides and 3g sodium acetates, which are dissolved in 40mL deionized waters, stirs 30min, adds the nanometer two of 0.1g diameters 270nm
Silicon oxide ball and ultrasonic disperse 30min；
(2) obtained pink solution is poured into 50mL polytetrafluoroethylene (PTFE) autoclave liners, is sealed and is placed on
In constant temperature oven, with the heating rate of 10 DEG C/min be warming up to 160 DEG C reaction 8h, after natural cooling respectively use deionized water and
Ethyl alcohol washing centrifuges repeatedly to no heteroion, is placed in 12h in 60 DEG C of vacuum drying ovens, obtains the predecessor of pink colour
Powder；
(3) powder of the fluffy drying of the above-mentioned acquisitions of 30mg is taken, 40mL deionized waters and ultrasonic disperse 30min is added, is claimed
It takes 0.96g Sodium Sulphate Nine Hydroxides to be dissolved in dispersion liquid, mixed liquor is poured into 50mL polytetrafluoroethylene (PTFE) autoclave liners, it is close
It seals and is placed in constant temperature oven, 120 DEG C of reaction 12h are warming up to the heating rate of 10 DEG C/min, after natural cooling respectively
It washed, centrifuged repeatedly to no heteroion with deionized water and ethyl alcohol, be placed in 60 DEG C of vacuum drying ovens for 24 hours, obtain
The NiCo of a diameter of 270nm of black2S4Hollow spherical powder, as shown in Figure 1, 2.
Embodiment 4
A kind of preparation method of lithium-sulfur cell：
(1) the nickel cobalt sulphur hollow spherical powder 40mg of embodiment 2 and sublimed sulfur 80mg are mixed, is in temperature under nitrogen protection
For 24 hours, cooled to room temperature obtains sulphur/nickel cobalt sulphur composite material for 155 DEG C of heat preservations；
(2) sulphur in step (1)/nickel cobalt sulphur composite material 49mg and Kynoar PVDF7mg, acetylene black 14mg is mixed
It closes, grinding is uniform, coated on clean aluminium foil after being dissolved with NMP, is subsequently placed in 60 DEG C of vacuum drying ovens for 24 hours, obtains
To positive pole plate of lithium-sulfur cell；
(3) by pole piece in step (2) in glove box, use lithium metal as cathode assembled battery, test high rate performance and
Cyclical stability.
As seen from Figure 3, battery charge and discharge at low range 0.1C, 0.2C, 0.5C have higher capacity, and in high magnification
Charge and discharge electric energy keeps capacity to stablize under 1C, 2C.
From fig. 4, it can be seen that battery at 1C charge and discharge 200 enclose after, specific capacity is reduced to 216mAh/g from 410mAh/g, quite
In each charge-discharge cycle capacity attenuation 0.23%, coulombic efficiency illustrates that the battery has preferable stable circulation close to 100%
Property.
Claims (10)
1. a kind of preparation method of the nickel cobalt sulphur hollow ball as lithium-sulphur cell positive electrode, which is characterized in that include the following steps：
Step 1)：By cabaltous nitrate hexahydrate, Nickelous nitrate hexahydrate, potassium persulfate or ammonium peroxydisulfate, ammonium fluoride and sodium acetate
It is dissolved in deionized water and stirs, add nanometer titanium dioxide silicon ball, ultrasonic disperse keeps nanometer titanium dioxide silicon ball evenly dispersed
In solution；
Step 2)：The suspension that step 1) obtains is poured into inner liner of reaction kettle, is sealed and is placed in constant temperature oven, is warming up to
140-180 DEG C of reaction is washed respectively with deionized water and ethyl alcohol after natural cooling, is centrifuged repeatedly to after no heteroion, set
It is dry in vacuum drying oven, obtain the predecessor powder of pale pink；
Step 3)：Ultrasonic disperse in deionized water is added in predecessor powder, obtains dispersion liquid；Nine hydrations are added in dispersion liquid
Then vulcanized sodium pours into mixed liquor in inner liner of reaction kettle, be sealed and be placed in constant temperature oven, is warming up to 90-120 DEG C instead
Answer, washed respectively with deionized water and ethyl alcohol after natural cooling, centrifuge repeatedly it is dry to constant-temperature vacuum after no heteroion, is placed in
It is dry in dry case, obtain the nickel cobalt sulphur nano-hollow ball powder of black.
2. the preparation method of the nickel cobalt sulphur hollow ball as lithium-sulphur cell positive electrode as described in claim 1, which is characterized in that institute
It states cabaltous nitrate hexahydrate in step 1), Nickelous nitrate hexahydrate, potassium persulfate or ammonium peroxydisulfate, ammonium fluoride, sodium acetate and receives
The weight ratio of rice silica spheres is 0.05-0.1: 0.05-0.1: 0.1-0.3: 0.2: 1-3: 0.1-0.2；Mixing time is 30-
60min；Ultrasonic time is 30-60min.
3. the preparation method of the nickel cobalt sulphur hollow ball as lithium-sulphur cell positive electrode as described in claim 1, which is characterized in that institute
It is 80% to state filling rate of the suspension in inner liner of reaction kettle in step 2)；Heating rate is 5-10 DEG C/min, and the reaction time is
6-8h；The temperature of vacuum drying oven is 60 DEG C, drying time 12h.
4. the preparation method of the nickel cobalt sulphur hollow ball as lithium-sulphur cell positive electrode as described in claim 1, which is characterized in that institute
It is 0.75-2.25g/L to state predecessor powder and the mass volume ratio of deionized water in step 3)；Ultrasonic time is 15-30min.
5. the preparation method of the nickel cobalt sulphur hollow ball as lithium-sulphur cell positive electrode as described in claim 1, which is characterized in that institute
It is 0.18-0.24g/mL to state the mass volume ratio of Sodium Sulphate Nine Hydroxide and dispersion liquid in step 3)；Mixed liquor is in inner liner of reaction kettle
In filling rate be 80%；Heating rate is 5-10 DEG C/min, reaction time 8-24h；The temperature of vacuum drying oven is
60 DEG C, drying time 12-24h.
6. the preparation method of the nickel cobalt sulphur hollow ball as lithium-sulphur cell positive electrode as described in claim 1, which is characterized in that institute
State the diameter of the diameter and the silica nanosphere being added in step 1) of the nickel cobalt sulphur nano-hollow ball powder that step 3) obtains
It is equal.
7. a kind of preparation method system of the nickel cobalt sulphur hollow ball as lithium-sulphur cell positive electrode described in claim 1-6 any one
Standby nickel cobalt sulphur hollow ball.
8. a kind of preparation method of lithium-sulfur cell, which is characterized in that include the following steps：
Step 4)：Nickel cobalt sulphur hollow ball described in claim 7 is mixed with sublimed sulfur, under nitrogen or argon in 150-
160 DEG C of heat preservations, after naturally cool to being taken out after room temperature；
Step 5)：The mixture that step 4) obtains is mixed with PVDF, acetylene black, grinding is uniform, is coated on and washes after being dissolved with NMP
On clean aluminium foil, it is subsequently placed in drying in vacuum drying oven, obtains positive pole plate of lithium-sulfur cell；
Step 6)：By positive pole plate of lithium-sulfur cell in glove box, use lithium metal as cathode assembled battery.
9. the preparation method of lithium-sulfur cell as claimed in claim 8, which is characterized in that nickel cobalt sulphur nanometer is empty in the step 4)
The mass ratio of bulbus cordis powder and sublimed sulfur is 1: 4；Soaking time is 15-36h.
10. the preparation method of lithium-sulfur cell as claimed in claim 8, which is characterized in that step 4) obtains in the step 5)
Mixture and PVDF, acetylene black mass ratio be 6-7: 1-2: 2-3；The temperature of vacuum drying oven is 60 DEG C, when dry
Between be at least for 24 hours.
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| 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 |
| CN112086295A (en) * | 2019-06-14 | 2020-12-15 | 同济大学 | Preparation method of nano nickel thiocobalate/carbon composite electrode material |
| CN115911329A (en) * | 2022-12-02 | 2023-04-04 | 中南民族大学 | Titanium dioxide microsphere loaded by sulfur hollow sphere and preparation method and application thereof |
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| 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 |
| CN115911329A (en) * | 2022-12-02 | 2023-04-04 | 中南民族大学 | Titanium dioxide microsphere loaded by sulfur hollow sphere and preparation method and application thereof |
| CN115911329B (en) * | 2022-12-02 | 2024-06-07 | 中南民族大学 | Sulfur hollow sphere-loaded titanium dioxide microsphere and preparation method and application thereof |
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