CN108598417A - A kind of conductive black modification aerosil sulfur loaded composite positive pole and preparation method thereof - Google Patents
A kind of conductive black modification aerosil sulfur loaded composite positive pole and preparation method thereof Download PDFInfo
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- CN108598417A CN108598417A CN201810373134.6A CN201810373134A CN108598417A CN 108598417 A CN108598417 A CN 108598417A CN 201810373134 A CN201810373134 A CN 201810373134A CN 108598417 A CN108598417 A CN 108598417A
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- conductive black
- aerosil
- sulfur
- positive pole
- composite positive
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 136
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910002012 Aerosil® Inorganic materials 0.000 title claims abstract description 102
- 238000012986 modification Methods 0.000 title claims abstract description 65
- 230000004048 modification Effects 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 239000011593 sulfur Substances 0.000 title claims abstract description 59
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 21
- 235000019441 ethanol Nutrition 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- 239000011240 wet gel Substances 0.000 claims description 16
- 239000003945 anionic surfactant Substances 0.000 claims description 15
- 239000000499 gel Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 abstract description 31
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 235000001508 sulfur Nutrition 0.000 description 55
- 210000004027 cell Anatomy 0.000 description 29
- 239000005864 Sulphur Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- 239000004965 Silica aerogel Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000005077 polysulfide Substances 0.000 description 8
- 229920001021 polysulfide Polymers 0.000 description 8
- 150000008117 polysulfides Polymers 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 6
- 235000019241 carbon black Nutrition 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000004964 aerogel Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000011800 void material Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000008247 solid mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004966 Carbon aerogel Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 206010021137 Hypovolaemia Diseases 0.000 description 1
- 229910001216 Li2S Inorganic materials 0.000 description 1
- -1 LiFePO4 Chemical class 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001291 vacuum drying 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
-
- 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
-
- 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
-
- 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
- H01M4/625—Carbon or graphite
-
- 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 a kind of conductive blacks to modify aerosil sulfur loaded composite positive pole and preparation method thereof.The composite positive pole includes the elemental sulfur that conductive black is modified aerosil and is supported in the conductive black modification aerosil；The conductive black modification aerosil includes aerosil and the conductive black being entrained in the aerosil.The method includes conductive black modification aerosil to be uniformly mixed with elemental sulfur, mixture is obtained；With under conditions of closed and inert gas shielding, obtained mixture is heat-treated at 115 DEG C~160 DEG C, conductive black is made and modifies aerosil sulfur loaded composite positive pole.Composite positive pole of the present invention has many advantages, such as excellent volumetric properties are with cyclical stability and high coulombic efficiency in lithium-sulfur cell.The method of the present invention is easy, of low cost, it is easy to accomplish mass production.
Description
Technical field
The invention belongs to battery material technical field more particularly to a kind of conductive black modifications two in lithium-sulfur cell
Silica aerogel sulfur loaded composite positive pole and preparation method thereof.
Background technology
The electrochemical energy storage device of exploitation highly effective and safe is one of the key link of new cleaning fuel industry development.With lead
Sour battery, nickel-cadmium cell, Ni-MH battery and lithium ion battery be representative secondary battery system portable electronic device,
Electric bicycle and aerospace field are widely used.Comprehensive performance commercialization lithium ion the most superior at present
The common positive electrode of battery is based on the metal oxides such as LiFePO4, cobalt acid lithium and stratiform ternary, practical energy density
Only in 200Wh/kg or so, be much difficult to meet the industries such as New-energy electric vehicle to high-energy density secondary battery (>300Wh/
Kg related request).From the 1960s is reported for the first time, lithium-sulfur cell system just causes the extensive pass of researcher
Note.Using elemental sulfur as anode, lithium-sulfur cell of the lithium metal as cathode may produce up to by polyelectron reaction
The theoretical energy density of 2600Wh/kg.And it is reported that the actual energy density of Soft Roll lithium-sulfur cell has reached 300- at present
500Wh/kg can tentatively meet the continuation of the journey requirement of 500 km of long range electric vehicle, the tradition such as far super ni-mh, lithium ion two
Primary cell system.Lithium-sulfur cell therefore be considered as at present most researching value and application prospect lithium secondary battery system it
One.
Although in energy density, use cost and environment friendly etc. all very attractives, lithium-sulfur cell at present
There is also active material utilization low (volumetric properties are poor), capacity attenuation serious (cyclical stability is poor), coulombs in operation
The problem of its practical applications of restriction such as inefficiency and high rate performance are poor.The reason of causing problem above has following several sides
Face：First, the high electrochemical inertia of elemental sulfur and its charge and discharge product；Elemental sulfur and its final discharging product are typical electronics
With the insulator of ion.Huge electrochemicaUy inert makes the electrode material prepared with bright sulfur simple substance be difficult to play available capacity.
Second, " the shuttle effect " of polysulfide；The intermediate discharging product of sulfur electrode is the polysulfide (Li of liquid2Sn, n=3-8),
It is very soluble in organic liquid electrolyte and therewith across diaphragm.Polysulfide is gone back in positive and negative interpolar by oxidation-repeatedly
Former process leads to the loss of active material and the erosion of lithium anode, and the cycle life to reduce battery is imitated with coulomb
Rate.Third, Li dendrite and volume expansion；Using lithium metal as cathode in lithium-sulfur cell, in long circulating or high power charging-discharging
Under the conditions of, nonuniform deposition of the lithium ion on lithium metal can form Li dendrite, and Li dendrite, which can constantly grow and pass through diaphragm, to be made
At short circuit, to cause the safety problems such as burning, explosion.Further, since start material (S) and final product (Li2S between) compared with
Volume contraction/expansion close to 80% can occur in charge and discharge process for big density variation, cause electrode and battery structure
It destroys.
Since porous carbon materials have the characteristics that large specific surface area and conductivity are high, at present to the performance improvement of lithium-sulfur cell
Work is focused primarily upon using the carbon material with porous structure as the carrier of elemental sulfur, is pressed down by the capillary absorption power of hole
The loss of liquid polysulfide in electrochemical reaction process processed.Although the porous carbon materials of various structures are in the electricity for improving sulfur electrode
Apparent effect has been played on conduction and cyclical stability, but has only relied on faint physical absorption power, has still been difficult to fundamentally
Inhibit slow losing issue of the polysulfide in cyclic process.For example, Chinese patent CN103107318B discloses a kind of lithium
The preparation method of sulphur battery composite positive pole, when composite anode material for lithium sulfur battery prepared by this method is as electrode
First discharge specific capacity reaches 1328mAh/g, and specific discharge capacity drops to 550mAh/g or so after recycling 50 times；Chinese patent Shen
Please CN106532043A disclose a kind of preparation method of carbon gel sulfur loaded-lithium sulfur battery anode material, prepared by this method
Initial discharge specific capacity when carbon gel sulfur loaded-lithium sulfur battery anode material is as electrode recycles 50 times up to 1100mAh/g
Near 460mAh/g or less under specific discharge capacity afterwards；Chinese patent application CN103996830A discloses a kind of graphene aerogel
The preparation method of sulfur loaded composite material, it is first when graphene aerogel sulfur loaded composite material prepared by this method is as electrode
Beginning specific discharge capacity is 900mAh/g or so, and specific discharge capacity is maintained at 660mAh/g or so after cycle 50 times, specific capacity compared with
It is low；The positive electrode of lithium-sulfur cell prepared by these methods, which is used in lithium-sulfur cell, has that volumetric properties are poor, capacity declines
Subtract the problems such as more serious.
In view of the above problems, being highly desirable to develop a kind of physics and chemisorption energy having concurrently to active sulfur species strength
The highly conductive carrier material of power, to promote the volumetric properties and cyclical stability of lithium-sulfur cell simultaneously.
Invention content
The purpose of the invention is to provide a kind of conductive black modification aerosil sulfur loaded anode composite material
Material and preparation method thereof, to solve, volumetric properties existing for lithium-sulfur cell and cyclical stability in the prior art are poor and coulomb
The problem of efficiency is low equal.In the present invention conductive black modification aerosil sulfur loaded composite positive pole with lightweight,
The high porosity and conductive black modification aerosil for having both high conductivity and strong adsorption capacity is simple substance sulfur-donor, is adopted
It uses composite positive pole in the present invention as electrode assembling at lithium-sulfur cell, it is excellent hypovolemic to may make that lithium-sulfur cell has
Can, many advantages, such as excellent cyclical stability and coulombic efficiency are high.The method of the present invention is easy, raw material manufacturing cost is low
It is honest and clean, it is easy to accomplish mass production has very high market application potential.
To achieve the goals above, the present invention provides a kind of conductive black modification aerosil in first aspect
Sulfur loaded composite positive pole, the conductive black modification aerosil sulfur loaded composite positive pole include conductive charcoal
Black modification aerosil and the elemental sulfur being supported in the conductive black modification aerosil；The conduction
Carbon black modification aerosil includes aerosil and the conductive charcoal being entrained in the aerosil
It is black.
Preferably, the conductive black modifies the quality of elemental sulfur in aerosil sulfur loaded composite positive pole
Percentage composition is 40%~80%；The grain size of the conductive black is 30~200nm；And/or the conductive black modifies dioxy
The mass percentage of conductive black is 5%~35% in SiClx aeroge.
The present invention provides a kind of conductive black modification aerosil sulfur loaded anode composite material in second aspect
The preparation method of material, described method includes following steps：
(1) conductive black modification aerosil is uniformly mixed with elemental sulfur, obtains mixture；With
(2) under conditions of closed and inert gas shielding, the mixture that step (1) is obtained is at 115 DEG C~160 DEG C
It is heat-treated, conductive black is made and modifies aerosil sulfur loaded composite positive pole.
Preferably, the temperature of the heat treatment is 145 DEG C~160 DEG C, time of the heat treatment is 12~for 24 hours.
Preferably, the conductive black modification aerosil and the mass ratio of the dosage of the elemental sulfur are 1：
(0.66~4).
Preferably, the method further includes the system for carrying out conductive black before step (1) and modifying aerosil
Standby step, which includes following sub-step：
(a) organo-silicon ester, organic solvent, water and anion surfactant are uniformly mixed, obtain mixed liquor；
(b) conductive black is added into the mixed liquor that step (a) obtains and stirs evenly, obtains mixture；
(c) catalyst is added into the mixture that step (b) obtains and stirs to gel state, obtains wet gel；With
(d) wet gel that step (c) obtains is subjected to exchange of solvent and Aging Step and more than two different temperatures successively
The normal pressure stage drying step in stage is made conductive black and modifies aerosil.
Preferably, the organo-silicon ester and the mass ratio of the dosage of the water are (3~4)：2, and the organo-silicon ester accounts for
The mass percent of the mixed liquor is 25%~50%；Contain a concentration of of anion surfactant in the mixed liquor
0.004~0.006mol/L；The grain size of the conductive black is 30~200nm；And/or the dosage of the catalyst is described mixed
Close 3wt%~5wt% of the dosage of material.
Preferably, the organo-silicon ester is methyl orthosilicate or ethyl orthosilicate；The organic solvent is selected from by methanol, second
The group of alcohol, acetone and acetonitrile composition, preferably ethyl alcohol；The anion surfactant is selected from by lauryl sodium sulfate, ten
The group of dialkyl sulfonates and neopelex composition；And/or the catalyst be selected from oxalic acid solution, hydrochloric acid solution,
It is one or more in ammonia spirit and ammonium fluoride solution.
Preferably, the rotating speed stirred described in step (b) is 200~300rpm；The rotating speed stirred described in step (c)
For 100~200rpm；And/or exchange of solvent described in step (d) is with Aging Step：The wet gel that step (c) is obtained according to
Secondary be placed in ethyl alcohol, organo-silicon ester and n-hexane is respectively impregnated 1~2 day.
Preferably, the normal pressure stage drying in more than two different temperatures stages described in step (d) includes the first temperature rank
Section is dry, the second temperature stage is dry, third temperature stage is dry and the drying of the 4th temperature stage；First temperature stage is dry
Dry temperature is 45 DEG C~55 DEG C, and the time of the first temperature stage drying is 18~30h；The second temperature stage drying
Temperature be 75 DEG C~85 DEG C, the time of second temperature stage drying is 10~15h；The third temperature stage drying
Temperature be 95 DEG C~105 DEG C, the time of third temperature stage drying is 5~8h；The 4th temperature stage drying
Temperature is 115 DEG C~150 DEG C, and the time of the 4th temperature stage drying is 3~5h.
The method of the present invention at least has following advantageous effect compared with prior art：
(1) the present invention provides a kind of high-performance conductive carbon blacks to modify aerosil sulfur loaded composite positive pole
And preparation method thereof, it is applied to lithium-sulfur cell with absorption carrier using the aerosil of conductive black modification as conductive
It is prepared by positive electrode.Aerosil (the SiO of conductive black modification2Aeroge) as elemental sulfur carrier have it is following
Advantage：Highly conductive conductive black even particulate dispersion can form good electricity in the porous structure of aerosil
Sub- transmission network；Lightweight SiO2Aeroge has high porosity and specific surface area, therefore unit mass SiO2Aeroge carrier
It can be achieved, to the uniform load of a large amount of elemental sulfurs, to improve specific energy density of the whole composite positive pole as electrode when；
SiO2Aeroge surface has a large amount of hydroxy functional group, can be to being easily soluble in the polysulfide shape of electrolyte in charge and discharge process
At the chemisorption of strength, to promote the cyclical stability of lithium sulphur battery electrode.The present invention is heat-treated by total by elemental sulfur
The evenly dispersed SiO modified to conductive black2Composite positive pole is prepared in the internal void of aeroge carrier, due to conductive charcoal
The SiO of black modification2Many characteristics of aeroge, prepared composite positive pole as electrode have excellent volumetric properties with
Cyclical stability.
(2) positive electrode provided by the invention can simultaneously by physics and chemisorption by lithium-sulfur cell in charge and discharge
The liquid polysulfide formed in the process is fixed on the SiO of conductive black modification2On aeroge carrier, lithium sulphur is effectively improved
The volumetric properties and cyclical stability of battery.In addition, being carried compared to common porous carbon materials in current composite sulfur electrode material
The preparation process of body complexity, conductive black used in the present invention modify SiO2Aeroge carrier is prepared simply, of low cost, is made
Conductive black modification aerosil sulfur loaded composite positive pole proposed by the invention is as lithium-sulfur cell anode
Material has very high market application potential.
(3) the conductive black modification aerosil (conductive black doping silicon dioxide aeroge) in the present invention is negative
Sulphur composite material is carried with lightweight, high porosity and has both the conductive black modification silica gas of high conductivity and strong adsorption capacity
Gel is simple substance sulfur-donor, has excellent volumetric properties, excellent cyclical stability and coulombic efficiency in lithium-sulfur cell
Many advantages, such as high；Positive electrode in the present invention has higher initial charge and specific discharge capacity in lithium-sulfur cell,
High coulombic efficiency is maintained in cyclic process, and specific capacity is charged and discharged after recycling 50 times and is held in the left sides 983mAh/g
It is right.
Description of the drawings
Fig. 1 is the scanning electron microscope image (SEM figures) of conductive black modification aerosil in the embodiment of the present invention 1.
Fig. 2 is that conductive black modifies aerosil sulfur loaded composite positive pole in lithium in the embodiment of the present invention 1
Electrochemistry cycle performance curve in sulphur battery and coulombic efficiency curve graph.
Fig. 3 is that conductive black modifies aerosil sulfur loaded composite positive pole in lithium in the embodiment of the present invention 1
The graph of relation of first charge-discharge specific capacity and voltage in sulphur battery.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached in the embodiment of the present invention
Figure, is clearly and completely described technical scheme of the present invention, it is clear that described embodiment is the part of the present invention
Embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making wound
The every other embodiment that the property made is obtained under the premise of working, shall fall within the protection scope of the present invention.
The present invention provides a kind of conductive black modification aerosil sulfur loaded anode composite material in first aspect
Material, the conductive black modification aerosil sulfur loaded composite positive pole include that conductive black modifies silica gas
Gel and the elemental sulfur being supported in the conductive black modification aerosil；The conductive black modifies silica
Aeroge includes aerosil and the conductive black being entrained in the aerosil.Particularly, in this hair
In bright, the elemental sulfur is selected from the group being made of rhombic sulfur, amorphous sulphur and sublimed sulfur, preferably sublimed sulfur；The titanium dioxide
Silica aerogel (SiO2Aeroge) surface be rich in hydroxy functional group.
According to some preferred embodiments, the conductive black modifies aerosil sulfur loaded anode composite material
Material is by conductive black modification aerosil and the simple substance being supported in the conductive black modification aerosil
Sulphur forms；The conductive black modification aerosil is by aerosil and is entrained in the silica airsetting
Conductive black composition in glue.
According to some preferred embodiments, the conductive black modifies aerosil sulfur loaded anode composite material
In material the mass percentage of elemental sulfur be 40%~80% (such as 40%, 45%, 50%, 55%, 60%, 65%, 70%,
75% or 80%).
According to some preferred embodiments, the grain size of the conductive black be 30~200nm (such as 30,40,50,60,
70,80,90,100,110,120,130,140,150,160,170,180,190 or 200nm)；And/or the conductive black is repaiied
Adorn aerosil in conductive black mass percentage be 5%~35% (such as 5%, 10%, 15%, 20%,
25%, 30% or 35%).
Conductive black in the present invention modifies aerosil sulfur loaded composite positive pole with lightweight, high porosity
And the conductive black modification aerosil for having both high conductivity and strong adsorption capacity is simple substance sulfur-donor, as lithium sulphur electricity
When the electrode in pond with excellent volumetric properties, excellent cyclical stability and coulombic efficiency are high many advantages, such as.
The present invention provides a kind of conductive black modification aerosil sulfur loaded anode composite material in second aspect
The preparation method of material, described method includes following steps：
(1) conductive black modification aerosil is uniformly mixed with elemental sulfur, obtains mixture；With
(2) under conditions of closed and inert gas shielding, the mixture that step (1) is obtained is in 115 DEG C~160 DEG C
Hot place is carried out under (such as 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C, 155 DEG C or 160 DEG C)
Reason is made conductive black and modifies aerosil sulfur loaded composite positive pole.
In the present invention, the inert gas for example can be nitrogen gas, argon gas or helium atmosphere, preferably nitrogen
Gas gas；Such as in the closed container (such as closed tank body) full of nitrogen, make elemental sulfur with liquid shape by heat treatment
Formula enters conductive black modification SiO2The internal void of aeroge obtains the conductive black modification two that can be used for lithium-sulfur cell
Silica aerogel sulfur loaded composite positive pole.In the present invention, when the temperature of heat treatment is 115 DEG C or more, the list
Matter sulphur can be melt into liquid form and modify SiO into the conductive black2In the internal void of aeroge.
According to some, more specifically embodiment, the conductive black modification aerosil sulfur loaded are compound just
The preparation process of pole material is：By conductive black modification aerosil (conductive black doping silicon dioxide aeroge) with
Elemental sulfur is uniformly mixed according to a certain percentage, obtains mixture；Then the mixture is placed in canister, is passed through
After enough nitrogen replaces original air in container, canister is sealed；The canister is placed in hot environment again
(such as in heat-treatment furnace) is uniformly heat-treated, and elemental sulfur is made to enter conductive black modification two with the lower liquid form of viscosity
The internal void of silica aerogel；Finally, the mixture in canister is taken out after to be heated, obtains the conduction
Carbon black modifies aerosil sulfur loaded composite positive pole.In order to further obtain the more uniform conductive black of granularity
Aerosil sulfur loaded composite positive pole is modified, the composite positive pole can suitably be ground.
According to some preferred embodiments, the temperature of the heat treatment be 145 DEG C~160 DEG C (such as 145 DEG C, 150
DEG C, 155 DEG C or 160 DEG C), time of the heat treatment is 12~for 24 hours (such as 12,13,14,15,16,17,18,19,20,21,
22,23 or for 24 hours).In the present invention, when the temperature of the heat treatment is 145 DEG C~160 DEG C, the elemental sulfur of liquid form glues
Spend it is most suitable, it is relatively small, be conducive to conductive black aerosil carrier and realize to the uniform loads of a large amount of elemental sulfurs, from
And promote specific energy density of the composite positive pole as electrode when.In the present invention, the time of the heat treatment is preferred
For 12~for 24 hours, if heat treatment time is insufficient, it can cause elemental sulfur in conductive black modification aerosil carrier
It cannot achieve evenly dispersed, the chemical property so as to cause the composite positive pole is bad.
According to some preferred embodiments, the use of conductive black the modification aerosil and the elemental sulfur
The mass ratio of amount is 1：(0.66~4).
In the present invention, highly conductive conductive black even particulate dispersion is in the porous structure of aerosil,
Good electron-transport network (conductive network) can be formed；Lightweight SiO2Aeroge has high porosity and specific surface area,
Therefore unit mass SiO2Aeroge carrier can realize the uniform load to a large amount of elemental sulfurs, improve whole composite positive pole
Specific energy density when as electrode；SiO2Aeroge surface has a large amount of hydroxy functional group, can be to easy in charge and discharge process
The polysulfide for being dissolved in electrolyte forms the chemisorption of strength, realizes the steady load to elemental sulfur, so as to improve
The volumetric properties and cyclical stability of lithium-sulphur cell positive electrode.
In order to have both large specific surface area and the high feature of conductivity, usually using with porous structure carbon material (such as
Carbon aerogels) carrier as elemental sulfur, and the present invention directly uses conductive black to modify aerosil as simple substance
The carrier of sulphur is overcoming on the insufficient basis of aerosil self-conductive performance, can have concurrently to active sulfur object
The physics and chemical adsorption capacity of matter strength so that the conductive black modification aerosil sulfur loaded in the present invention is compound
There is appearance more superior than other porous carbon materials sulfur loaded composite positive poles when anode of the positive electrode as lithium-sulfur cell
Measure performance and cyclical stability.Further, since conductive black modification aerosil has strong physics and chemisorption
Effect, under easy heat treatment operation, you can be easily achieved the uniform load to a large amount of elemental sulfurs, this is largely
On simplify the preparation process of the present invention so that the method for the present invention is easily achieved mass production, and there is very high market to apply
Potentiality.
According to some preferred embodiments, the method further includes that conductive black modification two is carried out before step (1)
The preparation process of silica aerogel, the preparation process include following sub-step：
(a) organo-silicon ester, organic solvent, water (such as deionized water) and anion surfactant are uniformly mixed, are obtained
To mixed liquor；
(b) conductive black is added into the mixed liquor that step (a) obtains and stirs evenly, obtains mixture；
(c) catalyst is added into the mixture that step (b) obtains and stirs to gel state, obtains wet gel；With
(d) wet gel that step (c) obtains is subjected to exchange of solvent and Aging Step and more than two different temperatures successively
The normal pressure stage drying step in stage is made conductive black and modifies aerosil.
In the present invention, the addition of the anion surfactant is conducive to also have while obtaining stable wet gel
It is evenly dispersed in aerosil structure conducive to conductive black, exist to be also beneficial to follow-up elemental sulfur uniform load
Conductive black is modified in aerosil, obtains the volumetric properties lithium-sulfur cell more excellent with stable circulation performance with leading
Electric carbon black modifies aerosil sulfur loaded composite positive pole.In the present invention, contributed to by normal pressure stage drying
The specific surface area and porosity for promoting final conductive black modification aerosil modify dioxy to improve conductive black
The physics and chemical adsorption capacity of SiClx aeroge.In the present invention, it is preferred to adulterate conductive black before gel process to prepare
Conductive black modify aerosil, this method prepare conductive black modify aerosil to elemental sulfur
Load effect is more preferable, so that conductive black obtained modifies aerosil sulfur loaded composite positive pole in lithium sulphur
Volumetric properties and stable circulation performance in battery are more excellent.
According to some preferred embodiments, the mass ratio of the organo-silicon ester and the dosage of the water is (3~4)：2
(such as 3:2、3.5:2 or 4:2), preferably 3:2, and the organo-silicon ester account for the mixed liquor mass percent be 25%~
50% (such as 25%, 30%, 35%, 40%, 45% or 50%)；Contain anion surfactant in the mixed liquor
A concentration of 0.004~0.006mol/L (such as 0.004,0.005 or 0.006mol/L), preferably 0.005mol/L；It is described
The grain size of conductive black is 30~200nm；And/or the 3wt% for the dosage that the dosage of the catalyst is the mixture~
5wt% (such as 3wt%, 3.5wt%, 4wt%, 4.5wt% or 5wt%).It illustrates, contains in the mixed liquor
The concentration of anion surfactant refers to that organo-silicon ester, organic solvent, water (such as deionized water) and anionic surface are lived
Property agent when being uniformly mixed, the concentration that the anion surfactant of addition contains in entire mixture system.
In the present invention, the grain size of the conductive black is preferably 30~200nm, when conductive black grain size be 30~
When 200nm, grain size is close with aerosil skeleton scale, is conducive to conductive black in aerosil skeleton
It is evenly dispersed in structure, to contribute to subsequent conductive carbon black to modify aerosil uniform load active elemental sulphur.
In the present invention, it is preferred to modify silica to prepare the conductive black that the mass percentage of conductive black is 5%~35%
Aeroge, when content is less than 5%, the electric conductivity of the conductive black modification aerosil is poor, when content height
When 35%, the conductive black modification aerosil can be caused to reduce the chemisorption performance of elemental sulfur, to
Influence conductive black obtained modify volumetric properties of the aerosil sulfur loaded composite positive pole as electrode when with
Cyclical stability and reduce its coulombic efficiency.In the present invention, the coulombic efficiency, is also discharging efficiency, refers to that battery is put
Capacitance with the ratio between charging capacity in cyclic process, the i.e. percentage of discharge capacity and charging capacity.
According to some preferred embodiments, the organo-silicon ester is methyl orthosilicate or ethyl orthosilicate；It is described organic
Solvent is selected from the group being made of methanol, ethyl alcohol, acetone and acetonitrile, preferably ethyl alcohol；The anion surfactant be selected from by
The group of lauryl sodium sulfate, dodecyl sodium sulfate and neopelex composition；And/or the catalyst is selected from grass
One or both of acid solution, hydrochloric acid solution, ammonia spirit and ammonium fluoride solution.Particularly, when using two kinds of catalyst,
Second of catalyst need to be added after the completion of former catalyst is added.
According to some preferred embodiments, when the organo-silicon ester is methyl orthosilicate, the conductive black and institute
The mass ratio for stating the dosage of methyl orthosilicate is 1：(4.7~48.1), to make conductive black obtained modify silica gas
The mass percentage of conductive black is 5%~35% in gel；It is described to lead when the organo-silicon ester is ethyl orthosilicate
Electric carbon black and the mass ratio of the dosage of the ethyl orthosilicate are 1：(6.4~65.9), to make conductive black modification obtained
The mass percentage of conductive black is 5%~35% in aerosil.
According to some preferred embodiments, the rotating speed that is stirred described in step (b) be 200~300rpm (such as 200,
250 or 300rpm)；The rotating speed stirred described in step (c) is 100~200rpm (such as 100,150 or 200rpm)；Wherein,
Unit " rpm " indicates the unit " rev/min " of rotating speed.
According to some preferred embodiments, exchange of solvent described in step (d) is with Aging Step：Step (c) is obtained
To wet gel be sequentially placed into ethyl alcohol, organo-silicon ester and n-hexane and respectively impregnate 1~2 day.I.e. in the present invention, first by step
(c) wet gel obtained, which is placed in ethyl alcohol to impregnate 1~2 day, carries out exchange of solvent, using diffusion, moisture in wet gel by
Gradually replaced by ethyl alcohol, tentatively remove moisture removal, obtains alcogel；Then the alcogel is sequentially placed into organo-silicon ester and impregnates 1
~2 days, other than carrying out aging, also further on aeroge skeleton deposited monomer to enhance the effect of frame strength；
It finally places it in n-hexane and impregnates 1~2 day, be finally to use the lower solvent filling pore of surface-active, in favor of follow-up
Normal pressure stage drying.
Normal pressure segmentation according to some preferred embodiments, more than two different temperatures stages described in step (d) is dry
Dry includes that the first temperature stage is dry, the second temperature stage is dry, third temperature stage is dry and the drying of the 4th temperature stage；Institute
The temperature for stating the drying of the first temperature stage is 45 DEG C~55 DEG C (such as 45 DEG C, 50 DEG C or 55 DEG C), preferably 50 DEG C, described the
The time of one temperature stage drying is 18~30h (such as 18,24 or 30h)；The temperature of the second temperature stage drying is 75
DEG C~85 DEG C (such as 75 DEG C, 80 DEG C or 85 DEG C), preferably 80 DEG C, the time of the second temperature stage drying is 10~15h
(such as 10,12 or 15h)；The temperature of third temperature stage drying is 95 DEG C~105 DEG C (such as 95 DEG C, 100 DEG C or 105
DEG C), preferably 100 DEG C, the time of the third temperature stage drying is 5~8h (such as 5,6,7 or 8h)；4th temperature
The temperature for spending stage drying is 115 DEG C~150 DEG C (such as 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C
Or 150 DEG C), preferably 120 DEG C, the time of the 4th temperature stage drying is 3~5h (such as 3,4 or 5h).
According to some, more specifically embodiment, the conductive black modify the preparation process of aerosil
For：Ethyl orthosilicate, ethyl alcohol, deionized water and anion surfactant are configured to uniform mixed liquor according to a certain ratio；
Wherein the mass ratio of ethyl orthosilicate and deionized water is 3:2, and be adjusted so that ethyl orthosilicate by ethyl alcohol additive amount
Quality accounting in mixture system is 25%~50%；Then conductive black is added in the mixed liquor, and 200
1~2h is stirred under~300rpm rotating speeds, obtains mixture；Gel is added dropwise to catalyst in the mixture again, 100~
Standing obtains wet gel after stirring 10~15min under 200rpm rotating speeds, and wherein catalyst loading is the mixture dosage
3wt%~5wt%；Gained wet gel is respectively impregnated in ethyl alcohol, ethyl orthosilicate and hexane solution respectively again and is carried out for 24 hours
Exchange of solvent and Aging Step, obtain gel；Finally by obtained gel within the temperature range of 50~150 DEG C in two or more
The different temperatures stage obtains the conductive black modification SiO after carrying out normal pressure stage drying processing2Aeroge.
Hereafter the present invention will be further detailed by way of example, but protection scope of the present invention is unlimited
In these embodiments.
Embodiment 1
1. ethyl orthosilicate, ethyl alcohol, deionized water and lauryl sodium sulfate are configured to uniform mixed liquor, wherein
Ethyl orthosilicate, ethyl alcohol and deionized water quality ratio are 3:5:2, lauryl sodium sulfate in mixed liquor a concentration of 5 × 10- 3mol/L；Then the conductive black that grain size is 50nm is added in the mixed liquor, and 1h is stirred under 200rpm rotating speeds, obtained
Mass ratio to mixture, wherein conductive black addition and ethyl orthosilicate in mixed liquor is 1:19.7；It again will be a concentration of
The hydrochloric acid solution of 1mol/L is added in the mixture, and addition is the 4% of the mixture quality, then in 150rpm rotating speeds
It is stood after lower stirring 10min and obtains wet gel；Again by obtained wet gel respectively in ethyl alcohol, ethyl orthosilicate and n-hexane
In respectively impregnate and carry out exchange of solvent and Aging Step for 24 hours, obtain gel；Finally by obtained gel be placed in baking oven successively in
At 50 DEG C it is dry for 24 hours, dry 12h at 80 DEG C, it is 6h and 120 DEG C dry at 100 DEG C at dry 4h, obtaining conductive black doping is
(conductive black modifies SiO to 15% conductive black modification aerosil2Aeroge).
2. distillation sulphur powder is modified SiO with conductive black2Aeroge is 7 in mass ratio:3 are uniformly mixed, and it is mixed to obtain solid
Close object；Then obtained solid mixture is placed in canister, it, will after being passed through original air that enough nitrogen is replaced in container
Canister seals；Finally the canister is placed in 155 DEG C of environment and carries out heat treatment 12h, is taken out after heat treatment
Solid mixture (solid) in canister, it is 70% to lead obtained after suitably grinding elemental sulfur mass percentage
Electric carbon black modifies aerosil sulfur loaded composite positive pole.
Scanning electron microscope (SEM) image of conductive black modification aerosil manufactured in the present embodiment, such as
Shown in Fig. 1.From the result of Fig. 1 it is found that conductive black is dispersed in aerosil, grain size also with aeroge bone
Frame scale is close, has no that the conductive black particle of reunion, the conductive black modify silica aerogel material in height in Fig. 1
The porous structure of degree contributes to uniform load active elemental sulphur.
The present embodiment also carries out the conductive black of preparation modification aerosil sulfur loaded composite positive pole
Electrochemical property test.Test method is：The conductive black that the elemental sulfur mass percentage is 70% is modified into silica
Aerogel carried sulphur composite positive pole powder, acetylene black and Kynoar are according to 7:2:1 mass ratio is in appropriate N- methyl
It is uniformly mixed in pyrrolidones, obtains slurry；Gained slurry is coated in aluminum foil current collector, electrode slice is obtained, waits doing
The electrode slice is struck out to the electrode slice of a diameter of 10mm after dry.Using metal lithium sheet as cathode, button is assembled into glove box
Battery (lithium-sulfur cell) carries out result such as Fig. 2 of constant current charge-discharge cycle with the multiplying power (current density 335mA/g) of 0.2C
Shown, the relation curve of first charge-discharge specific capacity and voltage is as shown in Figure 3.From the visible conductive black of the result of Fig. 2 and Fig. 3
There is higher initial charge and specific discharge capacity when modifying aerosil sulfur loaded composite positive pole as electrode,
High coulombic efficiency (coulombic efficiency is 98% or more) is maintained in cyclic process, in charge and discharge cycles 50 times (weeks), is filled
Electricity and specific discharge capacity are in 983mAh/g or so；Wherein, unit " mAh/g " is also denoted as " mAhg-1", indicate specific discharge capacity list
Position, i.e., the electricity that the battery of Unit Weight or active material can release.
Embodiment 2
Embodiment 2 is substantially the same manner as Example 1, the difference is that：
In 1.：Ethyl orthosilicate, ethyl alcohol and deionized water quality ratio are 3:2:2；The grain size 30nm of conductive black, it is conductive
Carbon black addition is 1 with ethyl orthosilicate mass ratio in mixed liquor:66；The addition of hydrochloric acid solution is the mixture quality
5%；It obtains the conductive black that conductive black doping is 5% and modifies aerosil.
In 2.：The sulphur powder that distils modifies SiO with conductive black2Aeroge mass ratio is 1:1；Heat treatment temperature is 150 DEG C；
The conductive black that elemental sulfur mass percentage is 50% modifies aerosil sulfur loaded composite positive pole.
Embodiment 3
Embodiment 3 is substantially the same manner as Example 1, the difference is that：
In 1.：Dodecyl sodium sulfate is used to replace lauryl sodium sulfate as anion surfactant；Conductive charcoal
Black grain size 100nm, conductive black addition are 1 with ethyl orthosilicate mass ratio in mixed liquor:8.1；1mol/L oxalic acid is molten
Liquid is sequentially added with 2mol/L ammonium fluoride solutions in the mixture, and addition is respectively the 2.5% of the mixture quality；
The conductive black for being 30% to conductive black doping modifies aerosil.
In 2.：The sulphur powder that distils modifies SiO with conductive black2Aeroge mass ratio is 8:2；Heat treatment temperature is 160 DEG C,
Heat treatment time is 18h；It is multiple that the conductive black that elemental sulfur mass percentage is 80% modifies aerosil sulfur loaded
Close positive electrode.
Embodiment 4
Embodiment 4 is substantially the same manner as Example 1, the difference is that：
In 1.：By changing the mass ratio of conductive black addition and ethyl orthosilicate in mixed liquor, (conductive black adds
The mass ratio for entering amount and ethyl orthosilicate in mixed liquor is 1:4.2) conductive black that conductive black doping is 45%, is obtained to repair
Adoring aerosil, (conductive black modifies SiO2Aeroge).
Embodiment 5
Embodiment 5 is substantially the same manner as Example 1, the difference is that：
In 1.：The conductive black that grain size is 15nm is added in the mixed liquor.
Embodiment 6
Embodiment 6 is substantially the same manner as Example 1, the difference is that：
In 1.：The gel obtained after exchange of solvent and Aging Step is placed in baking oven in 70 DEG C of dry 46h.
Embodiment 7
Embodiment 7 is substantially the same manner as Example 1, the difference is that：
In 1., lauryl sodium sulfate is not mixed, makes not containing anion surfactant in prepared mixed liquor.
Embodiment 8
Embodiment 8 is substantially the same manner as Example 1, the difference is that, conductive black modifies silica airsetting in 1.
The preparation process of glue is：By quality accounting be respectively 82% silica aerogel particles, (grain size is 15% conductive black
50nm) it is sufficiently mixed with 3% Kynoar binder and uniformly obtains conductive black doping and repaiied for 15% conductive black
Adoring aerosil, (conductive black modifies SiO2Aeroge).
Comparative example 1
Comparative example 1 is substantially the same manner as Example 1, the difference is that：
In 2.：The canister is placed in 150 DEG C of environment and carries out heat treatment 6h, metal is taken out after heat treatment
Solid mixture (solid) in container carries out obtaining the conductive charcoal that elemental sulfur mass percentage is 70% after suitably grinding
Black modification aerosil sulfur loaded composite positive pole.
Comparative example 2
1. take potassium hydroxide 4g and melamine 2g while being added in 1g charcoal-aero gels, it is uniformly mixed, pours into nickel crucible
In, it is placed in Muffle furnace and is heated to 800 DEG C under argon gas or nitrogen inert atmosphere, keep the temperature 2 hours.By the dilute sulphur of the solid of gained
Acid solution rinses, and is then washed till neutrality with distilled water or ethyl alcohol, and 120 DEG C of dryings obtain the charcoal of activation+nitrating synchronous process modification
Aerogel material, itrogen content of getter with nitrogen doped reach 15.8at%；Wherein, the unit of unit " at% " expression " atomic percentage ".
2. at ambient temperature, by 2g elemental sulfurs be dissolved in 40g carbon disulfide organic solvents formed sulfur content 5% it is organic
Sulphur solution is slowly added to the carbon aerogel material of 0.37g modifications, room temperature sonic oscillation 1 hour.Then solution is put into extraction kettle
In, it is extracted as extractant using postcritical ethane fluid, extraction temperature is 40 DEG C, pressure 30MPa, and the time is 40 points
The flow of clock, supercritical fluid is 1000 ml/mins, and decompression separation, separating pressure 7MPa, separation temperature is 50 DEG C, so
Ethanol elution agent is used to elute afterwards.60 DEG C of vacuum drying, obtain charcoal-aero gel-sulphur anode composite material of the modification of sulfur content 79.2%
Material.
Composite positive pole made from embodiment 2~8 and comparative example 1~2 uses mode group identical with embodiment 1
Button cell (lithium-sulfur cell) is dressed up, and carries out constant current charge-discharge under the same conditions as example 1 and recycles chemical property
Test, the results are shown in Table 1.
Table 1：Electrochemistry of the composite positive pole in lithium-sulfur cell made from Examples 1 to 8 and comparative example 1~2
It can test result.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, it will be understood by those of ordinary skill in the art that：It still may be used
With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features；
And these modifications or replacements, various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of conductive black modifies aerosil sulfur loaded composite positive pole, it is characterised in that：
The conductive black modification aerosil sulfur loaded composite positive pole includes that conductive black modifies silica
Aeroge and the elemental sulfur being supported in the conductive black modification aerosil；
The conductive black modification aerosil includes aerosil and is entrained in the silica airsetting
Conductive black in glue.
2. composite positive pole according to claim 1, it is characterised in that：
The mass percentage of elemental sulfur is in the conductive black modification aerosil sulfur loaded composite positive pole
40%~80%；
The grain size of the conductive black is 30~200nm；And/or
The mass percentage of conductive black is 5%~35% in the conductive black modification aerosil.
3. a kind of preparation method of conductive black modification aerosil sulfur loaded composite positive pole, which is characterized in that
Described method includes following steps：
(1) conductive black modification aerosil is uniformly mixed with elemental sulfur, obtains mixture；With
(2) under conditions of closed and inert gas shielding, the mixture that step (1) obtains is carried out at 115 DEG C~160 DEG C
Heat treatment is made conductive black and modifies aerosil sulfur loaded composite positive pole.
4. preparation method according to claim 3, it is characterised in that：
The temperature of the heat treatment is 145 DEG C~160 DEG C, time of the heat treatment is 12~for 24 hours.
5. preparation method according to claim 3, it is characterised in that：
The conductive black modification aerosil and the mass ratio of the dosage of the elemental sulfur are 1：(0.66~4).
6. preparation method according to claim 3, which is characterized in that the method further includes being carried out before step (1)
Conductive black modifies the preparation process of aerosil, which includes following sub-step：
(a) organo-silicon ester, organic solvent, water and anion surfactant are uniformly mixed, obtain mixed liquor；
(b) conductive black is added into the mixed liquor that step (a) obtains and stirs evenly, obtains mixture；
(c) catalyst is added into the mixture that step (b) obtains and stirs to gel state, obtains wet gel；With
(d) wet gel that step (c) obtains is subjected to exchange of solvent and Aging Step and more than two different temperatures stages successively
Normal pressure stage drying step, be made conductive black modify aerosil.
7. preparation method according to claim 6, it is characterised in that：
The organo-silicon ester and the mass ratio of the dosage of the water are (3~4)：2, and the organo-silicon ester accounts for the mixed liquor
Mass percent is 25%~50%；
A concentration of 0.004~0.006mol/L containing anion surfactant in the mixed liquor；
The grain size of the conductive black is 30~200nm；And/or
The dosage of the catalyst is 3wt%~5wt% of the dosage of the mixture.
8. preparation method according to claim 6, it is characterised in that：
The organo-silicon ester is methyl orthosilicate or ethyl orthosilicate；
The organic solvent is selected from the group being made of methanol, ethyl alcohol, acetone and acetonitrile, preferably ethyl alcohol；
The anion surfactant is selected from by lauryl sodium sulfate, dodecyl sodium sulfate and neopelex
The group of composition；And/or
The catalyst is one or more in oxalic acid solution, hydrochloric acid solution, ammonia spirit and ammonium fluoride solution.
9. preparation method according to claim 6, it is characterised in that：
The rotating speed stirred described in step (b) is 200~300rpm；
The rotating speed stirred described in step (c) is 100~200rpm；And/or
Exchange of solvent described in step (d) is with Aging Step：The wet gel that step (c) obtains is sequentially placed into ethyl alcohol, organic
It is respectively impregnated in estersil and n-hexane 1~2 day.
10. preparation method according to claim 6, it is characterised in that：
The normal pressure stage drying in more than two different temperatures stages described in step (d) includes the drying of the first temperature stage, second
Temperature stage is dry, third temperature stage is dry and the drying of the 4th temperature stage；
The temperature of first temperature stage drying is 45 DEG C~55 DEG C, time of the first temperature stage drying is 18~
30h；
The temperature of second temperature stage drying is 75 DEG C~85 DEG C, time of the second temperature stage drying is 10~
15h；
The temperature of third temperature stage drying is 95 DEG C~105 DEG C, time of the third temperature stage drying is 5~
8h；
The temperature of 4th temperature stage drying is 115 DEG C~150 DEG C, time of the 4th temperature stage drying is 3~
5h。
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