CN109721105A - Molybdenum disulfide nano floral material and preparation method thereof, molybdenum disulfide nano flower negative electrode material and preparation method thereof and battery - Google Patents
Molybdenum disulfide nano floral material and preparation method thereof, molybdenum disulfide nano flower negative electrode material and preparation method thereof and battery Download PDFInfo
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- CN109721105A CN109721105A CN201811654729.5A CN201811654729A CN109721105A CN 109721105 A CN109721105 A CN 109721105A CN 201811654729 A CN201811654729 A CN 201811654729A CN 109721105 A CN109721105 A CN 109721105A
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- molybdenum disulfide
- disulfide nano
- preparation
- battery
- negative electrode
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 122
- 239000000463 material Substances 0.000 title claims abstract description 71
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 59
- 239000002057 nanoflower Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005864 Sulphur Substances 0.000 claims abstract description 12
- 239000013049 sediment Substances 0.000 claims abstract description 12
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000003792 electrolyte Substances 0.000 claims description 20
- 239000011230 binding agent Substances 0.000 claims description 17
- 239000006258 conductive agent Substances 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 17
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000005119 centrifugation Methods 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 22
- 229910021389 graphene Inorganic materials 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 17
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 description 14
- 230000009286 beneficial effect Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 7
- 229960000935 dehydrated alcohol Drugs 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 239000006245 Carbon black Super-P Substances 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 3
- 241000208340 Araliaceae Species 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 3
- 235000003140 Panax quinquefolius Nutrition 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 235000008434 ginseng Nutrition 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 229910052961 molybdenite Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- 235000015393 sodium molybdate Nutrition 0.000 description 3
- 239000011684 sodium molybdate Substances 0.000 description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- ZYDVNTYVDVZMKF-UHFFFAOYSA-N [Cl].[Ag] Chemical compound [Cl].[Ag] ZYDVNTYVDVZMKF-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 description 1
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 1
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to battery technology fields, and in particular to molybdenum disulfide nano floral material and preparation method thereof, molybdenum disulfide nano flower negative electrode material and preparation method thereof and battery；The preparation method of molybdenum disulfide nano floral material includes that molybdate and sulphur source are dissolved in solvent in the present invention, obtains pre-mixture；After pre-mixture pyroreaction, suspension is obtained；Sediment is cleaned after suspension is centrifuged, obtains molybdenum disulfide nano floral material；Molybdenum disulfide nano flower obtained by this method has class graphene layer structure and theoretical capacity, has preferable application prospect.
Description
Technical field
The present invention relates to battery technology fields, and in particular to molybdenum disulfide nano floral material and preparation method thereof, two sulphur
Change molybdenum nano flower negative electrode material and preparation method thereof and battery.
Background technique
Fossil fuel exploitation becomes the focus of global concern using bring resource exhaustion and air pollution, to green energy resource
The development of storage system proposes urgent requirement.The energy storage device that lithium ion battery is born as the early 1990s has energy
Metric density is high, the advantages of having extended cycle life.However, lithium resource reserves are limited and uneven in distribution on global, organic electrolyte is inflammable
Security risk is formed, these problems all force people to find more cheap, safety novel energy-storing equipment, to meet electronic vapour
The demand of the large size energy storage such as vehicle, smart grid.
Before there is non-flammable aqueous electrolyte higher safety coefficient, aqueous electrolyte cell to have preferably application
Scape.
Summary of the invention
The first purpose of this invention is to provide a kind of preparation method of molybdenum disulfide nano floral material, and this method can
It prepares with the molybdenum disulfide nano of class graphene layer structure and theoretical capacity flower, and this method is simple and easy to do.
Second object of the present invention is to provide a kind of molybdenum disulfide nano floral material, with class graphene stratiform knot
Structure and theoretical capacity, and the mechanism of molybdenum disulfide nano flower has biggish specific surface area, has preferable application prospect.
Third object of the present invention is to provide a kind of preparation method of molybdenum disulfide nano flower negative electrode material, this method
It is simple and easy, and the capacitance that the molybdenum disulfide nano of this method preparation spends negative electrode material to be able to ascend battery as made from it is extensive
Reactivation power etc..
Fourth object of the present invention is to provide a kind of curing nano flower negative electrode material, and it can be used to prepare electricity
Pond, with the capacitance recovery capability etc. for improving battery.
Of the invention the 5th is designed to provide a kind of battery, and the battery capacity is preferable, and has preferable capacitor
Measure recovery capability.
What the present invention adopts the following technical solutions to realize.
The present invention proposes a kind of preparation method of molybdenum disulfide nano floral material comprising is dissolved in molybdate and sulphur source
In solvent, pre-mixture is obtained；After pre-mixture pyroreaction, suspension is obtained；To precipitating after suspension is centrifuged
Object is cleaned, and molybdenum disulfide nano floral material is obtained.
The present invention proposes a kind of molybdenum disulfide nano floral material, is by the preparation of above-mentioned molybdenum disulfide nano floral material
Method preparation.
The present invention proposes a kind of preparation method of molybdenum disulfide nano flower negative electrode material comprising: by it is dry, by above-mentioned
Molybdenum disulfide nano floral material and conductive agent, binder be mixed and made into slurries；Slurries are coated on collector, are made after dry
At cathode pole piece.
The present invention proposes a kind of molybdenum disulfide nano flower negative electrode material, is by above-mentioned molybdenum disulfide nano flower cathode material
The preparation method preparation of material.
The present invention proposes a kind of battery, and the negative electrode material of the battery includes above-mentioned molybdenum disulfide nano flower negative electrode material.
The present invention also proposes a kind of battery, and the negative electrode material of the battery includes molybdenum disulfide nano material, the electrolysis of battery
Liquid includes aqueous electrolyte containing aluminium ion；Preferably, the concentration of electrolyte is 0.2-2mol/L.
The beneficial effect of the preparation method of the molybdenum disulfide nano floral material of the embodiment of the present invention is: provided by the invention two
Suspension is made by price molybdate and sulphur source dissolution, mixing, then pyroreaction in the preparation method of molybdenum sulfide nanometer floral material,
Then to cleaning after suspension centrifugation to sediment, to obtain molybdenum disulfide nano floral material, easy behaviour is answered in above method letter
Make, and molybdenum disulfide nano floral material obtained has class graphene layer structure and theoretical capacity.
The beneficial effect of the molybdenum disulfide nano floral material of the embodiment of the present invention is: the molybdenum disulfide nano floral material is by upper
The method stated is made, with class graphene layer structure and theoretical capacity, and the mechanism of molybdenum disulfide nano flower have compared with
Big specific surface area has preferable application prospect.
The beneficial effect of the preparation method of the molybdenum disulfide nano flower negative electrode material of the embodiment of the present invention is: the preparation method
The middle cathode raw material used can improve the capacitance recovery capability of negative electrode material for above-mentioned molybdenum disulfide nano floral material.
The beneficial effect of the molybdenum disulfide nano flower negative electrode material of the embodiment of the present invention is: molybdenum disulfide nano flower cathode
Material is prepared by above-mentioned method, has preferable capacitance recovery capability.
The beneficial effect of the battery of the embodiment of the present invention is: the negative electrode material of the battery is above-mentioned molybdenum disulfide nano flower
The capacitance recovery capability of negative electrode material, molybdenum disulfide nano flower negative electrode material is preferable, restores energy to improve the capacitance of battery
Power.
The beneficial effect of the battery of the embodiment of the present invention is: the negative electrode material of the battery is molybdenum disulfide nano floral material,
Electrolyte is aqueous electrolyte containing aluminium ion, on the one hand improves the capacitance recovery capability of the battery, on the other hand improves
The security performance of battery.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is XRD (X-ray diffraction) map of the molybdenum disulfide nano flower prepared in the embodiment of the present invention 8；
Fig. 2 is forthright again in 1mol/L liquor alumini chloridi for the molybdenum disulfide nano flower prepared in the embodiment of the present invention 8
It can curve graph；
Fig. 3 is the cyclic curve in the molybdenum disulfide nano flower 1mol/L liquor alumini chloridi prepared in the embodiment of the present invention 8
Figure.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to molybdenum disulfide nano floral material of the embodiment of the present invention and preparation method thereof, molybdenum disulfide nano flower cathode
Material and preparation method thereof and battery are specifically described.
The preparation method of molybdenum disulfide nano floral material of the invention includes: that molybdate and sulphur source are dissolved in solvent,
Obtain pre-mixture；By pre-mixture pyroreaction, suspension is obtained；Sediment is carried out after suspension is centrifuged clear
It washes, obtains molybdenum disulfide nano floral material.
In detail, above-mentioned solvent includes water, molybdate and sulphur source is made an addition in solvent after stirring no less than 30min, is obtained
Beat pre-mixture.
Above-mentioned molybdate includes ammonium molybdate ((NH4)6Mo7O24·4H2O), at least one of molybdates such as sodium molybdate.
Above-mentioned sulphur source includes thiocarbamide (N2H4CS), at least one of sulphur sources such as thioacetamide.
Preferably, the molar ratio of above-mentioned molybdate and sulphur source is less than or equal to 1:7.
Above-mentioned pyroreaction can carry out in a kettle, and in detail, obtained pre-mixture is poured into reaction kettle,
6h-48h is reacted under the conditions of temperature is more than or equal to 180 DEG C.
The centrifugation rate of above-mentioned suspension centrifugation is 6000-8000r/min.
It include being no less than 3 times with deionized water and ethyl alcohol repeated washing for the sediment undergoes washing obtained after centrifugation.
Further, it after the completion of by sediment undergoes washing, is received molybdenum disulfide can be obtained after the drying precipitate after cleaning
Popped rice material；In detail, forced air drying can be carried out to sediment, dry temperature is 70-90 DEG C, and drying time is on the left side 12h
Molybdenum disulfide nano floral material can be obtained in the right side.
The preparation method of molybdenum disulfide nano flower negative electrode material of the invention includes: the volume two that will be prepared according to the method described above
Molybdenum sulfide nanometer floral material and conductive agent, binder are mixed and made into slurries；Slurries are coated on collector, are made after dry negative
Pole pole piece.
In detail, molybdenum disulfide nano floral material, conductive agent, the mass ratio between binder can be 80-90:10-20:
1-10。
Above-mentioned conductive agent includes at least one of acetylene black, conductive black (Super-P), Ketjen black or graphene.
Above-mentioned binder include polytetrafluoroethylene (PTFE) (PTFE), Kynoar (PVDF), sodium carboxymethylcellulose (CMC) or
At least one of butadiene-styrene rubber (SBR).
Above-mentioned collector includes one of carbon paper stable in the electrolytic solution, stainless steel, titanium sheet, tantalum piece etc..
Further, it after slurries being coated on collector, is put into vacuum oven and is dried with 60-120 DEG C, with system
At molybdenum disulfide nano flower negative electrode material.
The negative electrode material of battery in the present invention is using above-mentioned molybdenum disulfide nano flower negative electrode material.
Further the electrolyte in the battery includes aqueous electrolyte containing aluminium ion；Preferably, the concentration of electrolyte is
0.2-2mol/L。
In detail, the above-mentioned electrode solution of water system containing aluminium ion by include aluminium chloride, aluminum sulfate, aluminum nitrate, aluminium acetate etc. at least
A kind of solution of raw material preparation.
It should be noted that the positive electrode of the battery can select various positive electrodes in the related technology, and such as: manganese
Sour lithium, nickel cobalt aluminium ternary material, LiFePO4 etc., are not specifically limited herein.
The present invention also provides a kind of battery, the negative electrode material of the battery includes molybdenum disulfide nano floral material, electrolyte packet
Include aqueous electrolyte containing aluminium ion, it is preferable that the concentration of electrolyte is 0.2-2mol/L.It should be noted that in the battery
The molybdenum disulfide nano floral material preparation for the method preparation that negative electrode material can have prior art middle cover to provide.
It should be noted that the positive electrode of the battery can select various positive electrodes in the related technology, and such as: stone
Ink, LiMn2O4, nickel cobalt aluminium ternary material, LiFePO4 etc., are not specifically limited herein.
With reference to embodiments to molybdenum disulfide nano floral material of the invention and preparation method thereof, molybdenum disulfide nano flower
Negative electrode material and preparation method thereof and battery are described in further detail.
Embodiment 1
By (the NH of 1.412g4)6Mo7O24·4H2The N of O and 0.7g2H4CS is successively dissolved in the water of 60ml, and stirring is at least
30min is made into uniform mixed aqueous solution, is poured into the reaction kettle of 50ml, 180 DEG C of reaction 6h；After reaction, by gained
Suspension is centrifugated with the revolving speed of 7000r/min, and is cleaned repeatedly 3 times or more with deionized water and dehydrated alcohol；It will precipitating
Object obtains MoS in 80 DEG C of blast drier dry 12h2(molybdenum disulfide nano floral material).
By MoS2: acetylene black: PVDF=80:15:5 (mass ratio) carries out slurrying, is coated uniformly on graphite paper, then exists
It is dried in 60~120 DEG C of vacuum ovens, molybdenum disulfide nano flower negative electrode material is made.
It prepares battery: Aluminum Chloride Hexahydrate is dissolved into configuration 0.2mol/L liquor alumini chloridi in 250ml deionized water；And with
Above-mentioned molybdenum disulfide nano flower negative electrode material is cathode, coated graphite rod electrrodeTo be ginseng with silver-silver chloride to electrode
Compare electrode.
Embodiment 2
By (the NH of 1.412g4)6Mo7O24·4H2The N of O and 1.46g2H4CS is successively dissolved in 60ml water, stirring at least 30
Minute, it is made into uniform mixed aqueous solution, is poured into the reaction kettle of 50ml, 220 DEG C of reaction 48h；After reaction, by gained
Suspension is centrifugated with the revolving speed of 7000r/min, and is cleaned repeatedly 3 times or more with deionized water and dehydrated alcohol；It will precipitating
Object obtains MoS in 80 DEG C of blast drier dry 12h2(molybdenum disulfide nano floral material).
By MoS2: Super-P:PTFE=80:15:5 (mass ratio) carries out slurrying, is coated uniformly on stainless steel, then
It is dried in 60~120 DEG C of vacuum ovens, molybdenum disulfide nano flower negative electrode material is made.
It prepares battery: aluminum sulfate octadecahydrate being dissolved into 250ml deionized water and configures 2mol/L aluminum sulfate solution, and with
Above-mentioned molybdenum disulfide nano flower negative electrode material is cathode, coated graphite rod electrrodeTo be ginseng with silver-silver chloride to electrode
Compare electrode.
Embodiment 3
(the NH for being 1:7 by molar ratio4)6Mo7O24·4H2O and N2H4CS adds water to mix, and stirs 35min, prefabricated mixing is made
Object；Pre-mixture is poured into reaction kettle, pyroreaction 30h under the conditions of 200 DEG C after the reaction was completed exists suspension
6000r/min is centrifuged to obtain sediment, repeats to rinse 4 times with deionized water and dehydrated alcohol, with 70 DEG C in blast drier,
Dry 18h, obtains molybdenum disulfide nano floral material.
Slurries are made in molybdenum disulfide nano floral material, conductive agent and binder that weight ratio is 90:8:2, slurries are applied
It is overlying on stainless steel, is dried in 100 DEG C of vacuum ovens, molybdenum disulfide nano flower negative electrode material is made.Conductive agent is Ketjen black
With the mixture of graphene, binder is the mixture of sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR).
It prepares battery: the electrode solution of water system containing aluminium ion that concentration is 0.2mol/L is made in aluminum nitrate, with above-mentioned curing
Molybdenum nano flower negative electrode material is cathode, coated graphite rod electrrodeFor to electrode (anode), using silver-silver chloride as reference electricity
Pole.
Embodiment 4
(the NH for being 1:8 by molar ratio4)6Mo7O24·4H2O and N2H4CS adds water to mix, and stirs 40min, prefabricated mixing is made
Object；Pre-mixture is poured into reaction kettle, pyroreaction 10h under the conditions of 240 DEG C after the reaction was completed exists suspension
8000r/min is centrifuged to obtain sediment, repeats to rinse 4 times with deionized water and dehydrated alcohol, with 90 DEG C in blast drier,
Dry 11h, obtains molybdenum disulfide nano floral material.
Slurries are made in molybdenum disulfide nano floral material, conductive agent and binder that weight ratio is 80:14:6, slurries are applied
It is overlying on stainless steel, is dried in 60 DEG C of vacuum ovens, molybdenum disulfide nano flower negative electrode material is made.Conductive agent be acetylene black,
The mixture of Super-P (conductive black) and Ketjen black, binder be polytetrafluoroethylene (PTFE) (PTFE), Kynoar (PVDF) and
The mixture of sodium carboxymethylcellulose (CMC).
It prepares battery: the electrode solution of water system containing aluminium ion that concentration is 1.6mol/L is made in aluminium acetate, with above-mentioned curing
Molybdenum nano flower negative electrode material is cathode, coated graphite rod electrrodeFor to electrode (anode), using silver-silver chloride as reference electricity
Pole.
Embodiment 5
Add water to mix sodium molybdate and thioacetyl that molar ratio is 1:7.5, stirs 32min, pre-mixture is made；It will
Pre-mixture pours into reaction kettle, under the conditions of 236 DEG C pyroreaction for 24 hours, after the reaction was completed by suspension in 7500r/min
Centrifugation obtains sediment, repeats to rinse 5 times with deionized water and dehydrated alcohol, with 86 DEG C in blast drier, dry 13h,
Obtain molybdenum disulfide nano floral material.
Slurries are made in molybdenum disulfide nano floral material, conductive agent and binder that weight ratio is 80:18:2, slurries are applied
It is overlying on tantalum piece, is dried in 100 DEG C of vacuum ovens, molybdenum disulfide nano flower negative electrode material is made.Conductive agent is conductive black,
Binder is butadiene-styrene rubber (SBR).
It prepares battery: aluminium chloride and aluminum sulfate is mixed and made into the electrode solution of water system containing aluminium ion that concentration is 1.2mol/L,
Using above-mentioned molybdenum disulfide nano flower negative electrode material as cathode, coated graphite rod electrrodeFor to electrode (anode), with silver-chlorine
Changing silver is reference electrode.
Embodiment 6
(the NH for being 1:7 by molar ratio4)6Mo7O24·4H2O, sodium molybdate and N2H4CS and thioacetamide add water to mix, and stir
45min is mixed, pre-mixture is made；Pre-mixture is poured into reaction kettle, pyroreaction for 24 hours, is reacted under the conditions of 260 DEG C
Suspension is centrifuged after the completion to obtain sediment in 6500r/min, repeats to rinse 3 times with deionized water and dehydrated alcohol, in drum
It is dry with 85 DEG C in wind drying machine, obtain molybdenum disulfide nano floral material.
Slurries are made in molybdenum disulfide nano floral material, conductive agent and binder that weight ratio is 80:10:10, by slurries
It coated on titanium sheet, is dried in 100 DEG C of vacuum ovens, molybdenum disulfide nano flower negative electrode material is made.Conductive agent is acetylene black,
Binder is polytetrafluoroethylene (PTFE) (PTFE).
It prepares battery: the electrode solution of water system containing aluminium ion that concentration is 1.5mol/L is made in aluminium chloride, with above-mentioned curing
Molybdenum nano flower negative electrode material is cathode, iron phosphate lithium electrodeFor to electrode (anode), using silver-silver chloride as reference
Electrode.
Embodiment 7
Commercially available molybdenum disulfide nano floral material and conductive agent, binder is selected to be mixed and made into slurries, weight ratio 80:
Slurries are coated on titanium sheet, dried in 100 DEG C of vacuum ovens by 15:5, and molybdenum disulfide nano flower negative electrode material is made.It is conductive
Agent is acetylene black, and binder is polytetrafluoroethylene (PTFE) (PTFE).
It prepares battery: the electrode solution of water system containing aluminium ion that concentration is 1.5mol/L is made in aluminium chloride, with above-mentioned curing
Molybdenum nano flower negative electrode material is cathode, iron phosphate lithium electrodeFor to electrode (anode), using silver-silver chloride as reference
Electrode.
Embodiment 8
By (the NH of 1.412g4)6Mo7O24·4H2The N of O and 1.46g2H4CS is successively dissolved in 60ml water, stirring at least 30
Minute, it is made into uniform mixed aqueous solution, is poured into the reaction kettle of 50ml, 220 DEG C of reaction 48h；After reaction, by gained
Suspension is centrifugated with the revolving speed of 7000r/min, and is cleaned repeatedly 3 times or more with deionized water and dehydrated alcohol；It will precipitating
Object obtains MoS in 80 DEG C of blast drier dry 12h2(molybdenum disulfide nano floral material).
By MoS2: Super-P:PTFE=80:15:5 (mass ratio) carries out slurrying, is coated uniformly on stainless steel, then
It is dried in 60~120 DEG C of vacuum ovens, molybdenum disulfide nano flower negative electrode material is made.
It prepares battery: 18 water aluminium chloride being dissolved into 250ml deionized water and configures 1mol/L liquor alumini chloridi, and with
Above-mentioned molybdenum disulfide nano flower negative electrode material is cathode, coated graphite rod electrrodeTo be ginseng with silver-silver chloride to electrode
Compare electrode.
Comparative example 1
Comparative example 1 prepares molybdenum disulfide nano floral material, negative electrode material and battery using method similar to Example 3,
Wherein, when preparing molybdenum disulfide nano floral material, (NH4)6Mo7O24·4H2O and N2H4The molar ratio of CS is 1:4, other methods step
Rapid reference embodiment 3.
Comparative example 2
Comparative example 2 prepares molybdenum disulfide nano floral material, negative electrode material and battery using method similar to Example 3,
Wherein, the weight ratio of molybdenum disulfide nano floral material, conductive agent and binder is 55:28:17, and other methods step is referring to implementation
Example 3.
Comparative example 3
Comparative example 3 prepares molybdenum disulfide nano floral material, negative electrode material and battery using method similar to Example 3,
Wherein, it is electrolyte that PC (propene carbonate) is selected when preparing battery, and other methods step is referring to embodiment 3.
Comparative example 4
Comparative example 4 prepares molybdenum disulfide nano floral material, negative electrode material and battery using method similar to Example 3,
Wherein, when preparing molybdenum disulfide nano floral material, (NH4)6Mo7O24·4H2O and N2H4The molar ratio of CS is 1:4, and molybdenum disulfide is received
The weight ratio of popped rice material, conductive agent and binder is 55:28:17, selects PC (propene carbonate) for electrolysis when preparing battery
Liquid, other methods step is referring to embodiment 3.
The test of circulation electric discharge specific volume conservation rate: test side is carried out to the battery of the comparative example 1-4 preparation of embodiment 1-8 sum
Method: under conditions of 0.5C/0.5C, 2.75-4.4V charge and discharge, measuring capacitance under the multiplying power, is surveyed capacity after 100 circulations and is protected
Holdup the results are shown in Table 1.
Capacity retention ratio is surveyed after table 1 100 times circulations
As shown in Table 1, the method for preparing molybdenum disulfide nano flower of the invention, the method for preparing negative electrode material,
The method for preparing battery can make battery have preferable capacity retention ratio.
As shown in Figure 2, molybdenum disulfide nano flower specific capacity with higher under the current density of 1A/g, as electric current is close
The increase of degree, specific capacity reduce rapidly.When current density is restored to 1A/g, capacity does not significantly decrease, and illustrates curing
Molybdenum nano flower has preferable capacity restorability.
From the figure 3, it may be seen that the specific capacity of molybdenum disulfide nano flower gradually decreases, but remains to the promotion of cycle-index
Guarantee that circulation continues, this illustrates that molybdenum disulfide nano flower can be used as water system aluminium ion battery electrode material.
In conclusion the beneficial effect of the preparation method of the molybdenum disulfide nano floral material of the embodiment of the present invention is: this hair
The preparation method of the molybdenum disulfide nano floral material of bright offer passes through price molybdate and sulphur source dissolution, mixing, then pyroreaction
Suspension is made, then to cleaning after suspension centrifugation to sediment, to obtain molybdenum disulfide nano floral material, above-mentioned side
Method letter answer it is easy to operate, and molybdenum disulfide nano floral material obtained have class graphene layer structure and theoretical capacity.
The beneficial effect of the molybdenum disulfide nano floral material of the embodiment of the present invention is: the molybdenum disulfide nano floral material is by upper
The method stated is made, with class graphene layer structure and theoretical capacity, and the mechanism of molybdenum disulfide nano flower have compared with
Big specific surface area has preferable application prospect.
The beneficial effect of the preparation method of the molybdenum disulfide nano flower negative electrode material of the embodiment of the present invention is: the preparation method
The middle cathode raw material used can improve the capacitance recovery capability of negative electrode material for above-mentioned molybdenum disulfide nano floral material.
The beneficial effect of the molybdenum disulfide nano flower negative electrode material of the embodiment of the present invention is: molybdenum disulfide nano flower cathode
Material is prepared by above-mentioned method, has preferable capacitance recovery capability.
The beneficial effect of the battery of the embodiment of the present invention is: the negative electrode material of the battery is above-mentioned molybdenum disulfide nano flower
The capacitance recovery capability of negative electrode material, molybdenum disulfide nano flower negative electrode material is preferable, restores energy to improve the capacitance of battery
Power.
The beneficial effect of the battery of the embodiment of the present invention is: the negative electrode material of the battery is molybdenum disulfide nano floral material,
Electrolyte is aqueous electrolyte containing aluminium ion, on the one hand improves the capacitance recovery capability of the battery, on the other hand improves
The security performance of battery.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of molybdenum disulfide nano floral material characterized by comprising
Molybdate and sulphur source are dissolved in solvent, pre-mixture is obtained；
After the pre-mixture pyroreaction, suspension is obtained；
Sediment will be cleaned after suspension centrifugation, obtains molybdenum disulfide nano floral material.
2. the preparation method of molybdenum disulfide nano floral material according to claim 1, which is characterized in that the molybdate and
The molar ratio of the sulphur source is less than or equal to 1:7.
3. the preparation method of molybdenum disulfide nano floral material according to claim 1, which is characterized in that the pyroreaction
More than or equal to 180 DEG C.
4. the preparation method of molybdenum disulfide nano floral material according to claim 1, which is characterized in that the cleaning includes
It is no less than 3 times using deionized water and ethyl alcohol repeated washing.
5. a kind of molybdenum disulfide nano floral material, which is characterized in that it is by the described in any item molybdenum disulfide of claim 1-4
The preparation method preparation of nanometer floral material.
6. a kind of preparation method of molybdenum disulfide nano flower negative electrode material characterized by comprising by it is dry, wanted by right
Molybdenum disulfide nano floral material and conductive agent, binder described in asking 5 are mixed and made into slurries；
The slurries are coated on collector, cathode pole piece is made after dry.
7. a kind of molybdenum disulfide nano flower negative electrode material, which is characterized in that it is by molybdenum disulfide nano as claimed in claim 6
The preparation method preparation of flower negative electrode material.
8. a kind of battery, which is characterized in that the negative electrode material of the battery includes molybdenum disulfide nano flower as claimed in claim 7
Negative electrode material.
9. battery according to claim 8, which is characterized in that the electrolyte of the battery is electrolysed including water system containing aluminium ion
Liquid；Preferably, the concentration of the electrolyte is 0.2-2mol/L.
10. a kind of battery, which is characterized in that the negative electrode material of the battery includes molybdenum disulfide nano material, the battery
Electrolyte includes aqueous electrolyte containing aluminium ion；Preferably, the concentration of the electrolyte is 0.2-2mol/L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110323424A (en) * | 2019-05-29 | 2019-10-11 | 景德镇陶瓷大学 | The preparation method of titania modified molybdenum disulfide lithium ion battery negative material |
| CN112967891A (en) * | 2021-02-01 | 2021-06-15 | 湖北大学 | Flexible composite electrode and preparation method thereof |
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| CN103613137A (en) * | 2013-11-08 | 2014-03-05 | 电子科技大学 | Hydrothermal synthesis method of molybdenum disulfide nano flowers |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103613137A (en) * | 2013-11-08 | 2014-03-05 | 电子科技大学 | Hydrothermal synthesis method of molybdenum disulfide nano flowers |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110323424A (en) * | 2019-05-29 | 2019-10-11 | 景德镇陶瓷大学 | The preparation method of titania modified molybdenum disulfide lithium ion battery negative material |
| CN110323424B (en) * | 2019-05-29 | 2021-07-30 | 景德镇陶瓷大学 | Preparation method of titanium dioxide modified molybdenum disulfide lithium ion battery cathode material |
| CN112967891A (en) * | 2021-02-01 | 2021-06-15 | 湖北大学 | Flexible composite electrode and preparation method thereof |
| CN112967891B (en) * | 2021-02-01 | 2022-05-24 | 湖北大学 | Flexible composite electrode and preparation method thereof |
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Application publication date: 20190507 |