CN110289409A - A kind of cell positive material and lithium-sulfur cell - Google Patents
A kind of cell positive material and lithium-sulfur cell Download PDFInfo
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- CN110289409A CN110289409A CN201910568982.7A CN201910568982A CN110289409A CN 110289409 A CN110289409 A CN 110289409A CN 201910568982 A CN201910568982 A CN 201910568982A CN 110289409 A CN110289409 A CN 110289409A
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- cell positive
- dimensional layer
- carbon
- base composte
- cell
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- 239000000463 material Substances 0.000 title claims abstract description 168
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 110
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 98
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000005864 Sulphur Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 24
- 239000011368 organic material Substances 0.000 claims abstract description 17
- 239000003610 charcoal Substances 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract 2
- 238000000576 coating method Methods 0.000 claims abstract 2
- 238000010438 heat treatment Methods 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000011065 in-situ storage Methods 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical group 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000011295 pitch Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 2
- 229930003268 Vitamin C Natural products 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 235000019154 vitamin C Nutrition 0.000 claims description 2
- 239000011718 vitamin C Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 description 25
- 238000000227 grinding Methods 0.000 description 23
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 20
- 239000004810 polytetrafluoroethylene Substances 0.000 description 20
- 238000001816 cooling Methods 0.000 description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000010405 anode material Substances 0.000 description 11
- 229960000935 dehydrated alcohol Drugs 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000006230 acetylene black Substances 0.000 description 10
- -1 polytetrafluoroethylene Polymers 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001021 polysulfide Polymers 0.000 description 4
- 239000005077 polysulfide Substances 0.000 description 4
- 150000008117 polysulfides Polymers 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 239000002023 wood Substances 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
- 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
- H01M4/362—Composites
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to lithium-sulfur cell technical field more particularly to a kind of cell positive materials and lithium-sulfur cell.The present invention provides a kind of cell positive material, the cell positive material includes C-base composte material and the sulphur for being filled in the C-base composte material；The C-base composte material includes two-dimensional layer graphitic nitralloy carbon and the charcoal for coating the two-dimensional layer graphitic nitralloy carbon；The C-base composte material is obtained with carbonaceous organic material original position pyrolytic reaction by the two-dimensional layer graphitic nitralloy carbon or by obtaining in the two-dimensional layer graphitic nitralloy carbon surface chemical vapor deposition carbon deposit.The experimental results showed that cell positive material of the embodiment of the present invention is applied to lithium-sulfur cell, first discharge specific capacity of the lithium-sulfur cell at 0.1C is enabled to be up to 1166mAh/g, there is high specific capacity and good cycle performance.
Description
Technical field
The invention belongs to lithium-sulfur cell technical field more particularly to a kind of cell positive materials and lithium-sulfur cell.
Background technique
Lithium ion battery is always by extensive in the ever-increasing various portable digital products of demand and industrial circle
Concern, but traditional lithium ion battery energy density is already close to its theoretical value, therefore there is an urgent need to find next-generation height
The secondary cell of energy density.Lithium-sulfur cell is as the industrialized battery of next-generation most probable, and wherein element sulphur is as battery
Positive electrode has high theoretical specific capacity (1675mAh/g) and energy density (2600Wh/Kg), and elemental sulfur reserves in the earth
The advantages that abundant, cheap, environmentally friendly, a kind of very promising battery.
However, current lithium-sulfur cell faces following main problem: (1) conductivity of positive electrode elemental sulfur is extremely low, and anti-
The final product lithium sulfide answered is also electronic body, and active material is caused to be difficult to make full use of, and is unfavorable for the high magnification of battery
Performance；(2) the soluble polysulfide generated in charge and discharge process can be diffused into cathode across diaphragm, occur with lithium metal secondary anti-
It answers, lead to active material loss and destroys solid electrolyte interface film, to make capacity rapid decay；(3) lithium-sulfur cell is most
Final product polysulfide electronic isolation and electrolyte is not dissolved in, is deposited in conducting matrix grain, the disengaging of part of polysulfide is led
Electric skeleton can not decay in charge and discharge process at sulphur or polysulfide so as to cause very high capacity in reversible reaction；(4) by
In elemental sulfur and lithium sulfide density variation, there are very high volume expansion or contraction in charge and discharge process, lead to structure collapses, from
And cause serious capacity attenuation.
Summary of the invention
In view of this, the present invention provides a kind of cell positive material and lithium-sulfur cell, for solving existing lithium-sulfur cell
High rate performance is lower, problem that capacity attenuation is very fast.
The specific technical solution of the present invention is as follows:
A kind of cell positive material, the cell positive material include C-base composte material and are filled in described carbon-based compound
The sulphur of material；
The C-base composte material includes two-dimensional layer graphitic nitralloy carbon and the cladding two-dimensional layer graphitic nitralloy carbon
Charcoal；
The C-base composte material is obtained by the two-dimensional layer graphitic nitralloy carbon and carbonaceous organic material original position pyrolytic reaction
To or by being obtained in the two-dimensional layer graphitic nitralloy carbon surface chemical vapor deposition carbon deposit.
Preferably, the sulphur is filled in the C-base composte material by following steps:
The C-base composte material is mixed with elemental sulfur and is placed in vacuum condition, carrying out heat treatment makes the simple substance
Sulphur melting diffuses in the C-base composte material.
Preferably, the sulphur is filled in the C-base composte material by following steps:
It disperses the C-base composte material in sulphur source solution, after surfactant is added, adds precipitating reagent progress
Stirring deposits elemental sulfur to the C-base composte material.
Preferably, the sulphur source is selected from Na2S2O3、Na2SXWith one of thiocarbamide or a variety of；
The surfactant is selected from one of cetyl trimethylammonium bromide, neopelex and tween
Or it is a variety of；
The precipitating reagent is selected from one of hydrochloric acid, sulfuric acid and hydrogen peroxide or a variety of.
Preferably, pyrolysis specifically includes the two-dimensional layer graphitic nitralloy carbon in situ with carbonaceous organic material:
By the two-dimensional layer graphitic nitralloy carbon and the carbonaceous organic material under nitrogen and/or inert atmosphere, carry out former
Position pyrolytic reaction；
The mass ratio of the two-dimensional layer graphitic nitralloy carbon and the carbonaceous organic material is 1:0.25~2；
The carbonaceous organic material is selected from glucose, sucrose, citric acid, starch, pitch, phenolic resin, polyethylene glycol and resists
One of bad hematic acid is a variety of.
Preferably, the heating rate of the pyrolytic reaction in situ is 2 DEG C/min~10 DEG C/min；
The temperature of the original position pyrolytic reaction is 600 DEG C~900 DEG C；
The time of the original position pyrolytic reaction is 2h~4h.
Preferably, described to be specifically included in the two-dimensional layer graphitic nitralloy carbon surface chemical vapor deposition carbon deposit:
The two-dimensional layer graphitic nitralloy carbon is mixed with catalyst, is passed through carbon containing organic gas, carries out chemical gas
It mutually deposits, then removes the catalyst.
Preferably, the catalyst is metal oxide；
The carbon containing organic gas is selected from one of methane, ethane, ethylene and acetylene or a variety of；
The flow velocity of the carbon containing organic gas is 2L/min~4L/min.
Preferably, the heating rate of the chemical vapor deposition is 2 DEG C/min~10 DEG C/min；
The temperature of the chemical vapor deposition is 600 DEG C~800 DEG C；
The time of the chemical vapor deposition is 2h~4h.
The present invention also provides a kind of lithium-sulfur cell, the positive electrode of the lithium-sulfur cell includes described in above-mentioned technical proposal
Cell positive material.
In conclusion the cell positive material includes carbon-based composite wood the present invention provides a kind of cell positive material
Expect and be filled in the sulphur of the C-base composte material；The C-base composte material includes two-dimensional layer graphitic nitralloy carbon and cladding institute
State the charcoal of two-dimensional layer graphitic nitralloy carbon；The C-base composte material by the two-dimensional layer graphitic nitralloy carbon with it is carbon containing organic
Object original position pyrolytic reaction obtains or by obtaining in the two-dimensional layer graphitic nitralloy carbon surface chemical vapor deposition carbon deposit.The present invention
Carrier " close lithium " characteristic can be improved in the nitrogen adulterated in cell positive material, inhibits more lithium sulfides " shuttle effect "；Two-dimensional layer stone
The surface of black carbonitride is coated with high conductivity charcoal, improves the conductivity of cell positive material, and then improves the anti-of electrode
Answer dynamic performance, i.e. high rate performance；The cell positive material has layer structure, " can buffer " electrode charge and discharge process
Volume change stress, and then improve the cyclical stability of battery.The experimental results showed that cell positive material of the embodiment of the present invention
Applied to lithium-sulfur cell, first discharge specific capacity of the lithium-sulfur cell at 0.1C is enabled to be up to 1166mAh/g, had high
Specific capacity and good cycle performance.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 is the picture for the two-dimensional layer graphitic nitralloy carbon that the embodiment of the present invention 1 is prepared；
Fig. 2 is the picture for the C-base composte material that the embodiment of the present invention 1 is prepared；
Fig. 3 is the XRD diagram for the two-dimensional layer graphitic nitralloy carbon that the embodiment of the present invention 1 is prepared；
Fig. 4 is the Raman figure for the two-dimensional layer graphitic nitralloy carbon that the embodiment of the present invention 2 is prepared；
Fig. 5 is the battery using 3 cell positive material of the embodiment of the present invention under 0.1C multiplying power, first charge-discharge curve
Figure.
Fig. 6 is charge and discharge cycles curve graph of the battery of 4 cell positive material of the embodiment of the present invention under 0.1C multiplying power；
Fig. 7 is the charging and discharging curve figure using the battery of 1 cell positive material of comparative example under 0.1C multiplying power；
Fig. 8 is the cycle performance curve graph using the battery of 2 cell positive material of comparative example under 0.1C multiplying power.
Specific embodiment
The present invention provides a kind of cell positive material and lithium-sulfur cells, for solving the high rate performance of existing lithium-sulfur cell
Problem lower, capacity attenuation is very fast.
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
A kind of cell positive material, cell positive material include C-base composte material and are filled in C-base composte material
Sulphur；
C-base composte material includes the charcoal of two-dimensional layer graphitic nitralloy carbon and cladding two-dimensional layer graphitic nitralloy carbon；
C-base composte material is obtained or is passed through with carbonaceous organic material original position pyrolytic reaction by two-dimensional layer graphitic nitralloy carbon
It is obtained in two-dimensional layer graphitic nitralloy carbon surface chemical vapor deposition carbon deposit.
Carrier " close lithium " characteristic can be improved in the nitrogen adulterated in cell positive material of the embodiment of the present invention, inhibits more lithium sulfides
" shuttle effect "；The surface of two-dimensional layer graphitic nitralloy carbon is coated with high conductivity charcoal, improves the conductance of cell positive material
Rate, and then improve the kinetics performance of electrode, i.e. high rate performance；The cell positive material has layer structure, can be with
The volume change stress of " buffering " electrode charge and discharge process, and then improve the cyclical stability of battery.The experimental results showed that this
Inventive embodiments cell positive material is applied to lithium-sulfur cell, enables to first discharge specific capacity of the lithium-sulfur cell at 0.1C
Up to 1166mAh/g has high specific capacity and good cycle performance.
The embodiment of the present invention is by two-dimensional layer graphitic nitralloy carbon and carbonaceous organic material original position pyrolytic reaction or in two-dimensional layer
Shape graphitic nitralloy carbon surface chemical vapor deposition carbon deposit obtains C-base composte material, so that two-dimensional layer graphitic nitralloy carbon surface coats
High conductivity charcoal, improves the electric conductivity of graphitic nitralloy carbon, then sulphur is filled in C-base composte material, obtained anode material
The specific surface area of material is 300~400m2/ g, cell positive material have the advantages that high-specific surface area, high conductivity, and there are chemistry
There is defect sites " close lithium " characteristic as the positive electrode of lithium-sulfur cell can effectively improve electrode reaction dynamics,
And more lithium sulfides " shuttle effect " can be inhibited, to improve the energy density of lithium-sulfur cell, high rate performance and cyclical stability
Energy.Also, two-dimensional layer graphitic nitralloy carbon may also reach up the effect for alleviating the volume expansion of lithium reaction of Salmon-Saxl.
In the embodiment of the present invention, sulphur can be filled in C-base composte material by following steps:
C-base composte material is mixed with elemental sulfur and is placed in vacuum condition, carrying out heat treatment expands elemental sulfur melting
It is dissipated in C-base composte material.
Further, elemental sulfur is preferably sublimed sulfur；The mass ratio of elemental sulfur and C-base composte material is 9~7:1~3,
Preferably 8~7:2~3, more preferably 7:3；Mixing is specially to be fully ground in mortar, time of grinding be 30min~
60min；It is vacuumized in the reactor, obtains vacuum condition, the time vacuumized is 30min~60min, vacuum condition
Vacuum degree is -0.05MPa~-0.1MPa；Heat treatment is specially constant temperature processing 4h~14h at 120 DEG C~180 DEG C, preferably
Heated using oil bath pan.
In the embodiment of the present invention, sulphur can also be filled in C-base composte material by following steps:
It disperses C-base composte material in sulphur source solution, after surfactant is added, adds precipitating reagent and be stirred
Deposit elemental sulfur to C-base composte material.
In the embodiment of the present invention, sulphur source is selected from Na2S2O3、Na2SXWith one of thiocarbamide or a variety of, the concentration of sulphur source solution
For 0.5M~5M；
Surfactant is selected from cetyl trimethylammonium bromide (CTAB), neopelex (SDBS) and tween
One of or it is a variety of；
Precipitating reagent is selected from one of hydrochloric acid, sulfuric acid and hydrogen peroxide or a variety of, and the concentration of precipitating reagent is 0.1M~2M.
Further, sulphur source solution is stirred at room temperature to obtain into deionized water by being added sulphur source, passes through ultrasound
It disperses C-base composte material in sulphur source solution；It is added after precipitating reagent is stirred, further includes: be centrifuged/cross filtering
It washes, then is dried.
In order to spread elemental sulfur in C-base composte material uniformly, elemental sulfur is combined closely with C-base composte material,
After elemental sulfur is deposited to C-base composte material, further includes: be heat-treated under protective atmosphere, the temperature of heat treatment is
150 DEG C~180 DEG C, preferably 155 DEG C；The time of heat treatment is 6h~12h, preferably 8h.
After the heat treatment, the sulphur on C-base composte material surface is removed.
In the embodiment of the present invention, pyrolysis specifically includes two-dimensional layer graphitic nitralloy carbon in situ with carbonaceous organic material:
By two-dimensional layer graphitic nitralloy carbon and carbonaceous organic material under nitrogen and/or inert atmosphere, it is anti-to carry out pyrolysis in situ
It answers；
The mass ratio of two-dimensional layer graphitic nitralloy carbon and carbonaceous organic material is 1:0.25~2；
Carbonaceous organic material is selected from glucose, sucrose, citric acid, starch, pitch, phenolic resin, polyethylene glycol and Vitamin C
One of acid is a variety of.
In the embodiment of the present invention, the heating rate of pyrolytic reaction in situ is 2 DEG C/min~10 DEG C/min；
The temperature of pyrolytic reaction in situ is 600 DEG C~900 DEG C；
The time of pyrolytic reaction in situ is 2h~4h.
In the embodiment of the present invention, specifically included in two-dimensional layer graphitic nitralloy carbon surface chemical vapor deposition carbon deposit:
Two-dimensional layer graphitic nitralloy carbon is mixed with catalyst, is passed through carbon containing organic gas, carries out chemical vapor deposition
Product, then remove catalyst.
In the embodiment of the present invention, catalyst is metal oxide, preferably iron oxide, zinc oxide, ferrous oxide, cobalt oxide
With one of nickel oxide or a variety of；
Carbon containing organic gas is selected from one of methane, ethane, ethylene and acetylene or a variety of；
The flow velocity of carbon containing organic gas is 2L/min~4L/min.
In the embodiment of the present invention, chemical vapor deposition carries out preferably in tube furnace, the heating rate of chemical vapor deposition
For 2 DEG C/min~10 DEG C/min；
The temperature of chemical vapor deposition is 600 DEG C~800 DEG C；
The time of chemical vapor deposition is 2h~4h.
In the embodiment of the present invention, carbon containing nitrogen presoma is subjected to hot polymerization reaction, blocky g-C is prepared3N4, blocky g-C3N4
Specific surface area be 40m2/ g~80m2/ g, hot polymerization reaction preferably carry out in Muffle furnace or tube furnace, then by blocky g-C3N4It grinds
It is milled broken and is stirred in dehydrated alcohol by ultrasonic disperse, so that bulk g-C3N4Ultrasound removing obtains two-dimensional layer graphite nitrogen
Change carbon.
Carbon containing nitrogen presoma is a kind of or more in urea, melamine, dicyandiamide, cyanamide, thiocarbamide or trimerization hydrogen chlorine
Kind.
More specifically, two-dimensional layer graphitic nitralloy carbon is prepared by the following procedure method and obtains:
Carbon containing nitrogen presoma is placed in band lid crucible and is put into Muffle furnace, with 2.5 DEG C/min~5 DEG C/min heating
Rate is warming up to 500 DEG C~650 DEG C progress 4h~6h hot polymerizations and reacts, after natural cooling, through ultrasonic disperse in dehydrated alcohol
Stirring, temperature are set as room temperature, and ultrasonic time is 30min~60min, then is centrifuged or is filtered, be dried in vacuo after cleaning 6h~
12h, vacuum drying temperature are 80 DEG C~100 DEG C, obtain two-dimensional layer graphitic nitralloy carbon.
The present invention also provides a kind of lithium-sulfur cell, the positive electrode of lithium-sulfur cell includes above-mentioned technical proposal anode
Material.
In the embodiment of the present invention, cell positive material, conductive agent (acetylene black) and binder (polytetrafluoroethylene (PTFE)) are mixed
After carry out grinding slurrying, coated in obtaining lithium-sulphur cell positive electrode piece on copper foil, then make lithium-sulfur cell, cell positive material, second
The mass ratio of acetylene black and polytetrafluoroethylene (PTFE) is preferably 1:0.05~0.2:0.05~0.2.
Cell positive material of the embodiment of the present invention is applied to lithium-sulfur cell, and conductivity is high, and the reaction that can be improved electrode is dynamic
Mechanical property, i.e. high rate performance, the cell positive material have layer structure, " can buffer " volume of electrode charge and discharge process
Fluctuating stress, and then the cyclical stability of battery is improved, so that lithium-sulfur cell sulphur load capacity is high, high rate performance is high, specific capacity
High, stability height, overcomes the lithium sulfur battery anode material poorly conductive of prior art preparation, cycle performance and high rate performance are not
It is good, the defects of coulombic efficiency is low, and capacity attenuation is fast.
For a further understanding of the present invention, the present invention will be described in detail combined with specific embodiments below.
Embodiment 1
It weighs 20g urea and is put into crucible with a lid and be placed in Muffle furnace and be warming up to 500 DEG C with 2.5 DEG C/min, carry out 4h
Hot polymerization reaction, obtain flaxen bulk g-C after natural cooling3N4.By blocky g-C3N4Pass through ultrasonic disperse after grinding
It is stirred in dehydrated alcohol, temperature is set as room temperature, ultrasonic time is set as 60min, then be centrifuged or filtered, vacuum after cleaning
Dry 12h, obtains two-dimensional layer graphitic nitralloy carbon, and the specific surface area of two-dimensional layer graphitic nitralloy carbon is 64m2/ g, two-dimensional layer
The picture of graphitic nitralloy carbon please refers to Fig. 1.Referring to Fig. 3, the two-dimensional layer graphitic nitralloy being prepared for the embodiment of the present invention 1
The XRD diagram of carbon, in Fig. 3, in 13.1 ° and 27.4 ° of two position appearances, which is respectively belonging to graphitic nitralloy carbon (100)
(002) crystal face, it is related with structure filling pattern in face and the conjugation interplanar accumulation of aromatic rings respectively, show prepared material
Material is graphitic nitralloy carbon.
5g two-dimensional layer graphitic nitralloy carbon and 5g DEXTROSE ANHYDROUS are weighed, 30min grinding is carried out after mixing, is put into after taking-up
Quartz boat is placed in tube furnace plus quartz glass, under the atmosphere of argon gas, is warming up to 600 with the heating rate of 5 DEG C/min
DEG C carry out the original position 2h pyrolytic reaction, taken out after natural cooling, obtain the C-base composte material of black, the figure of C-base composte material
Piece please refers to Fig. 2.
It weighs 0.5g thiocarbamide to be added into 30mL deionized water, is stirred at room temperature, obtains thiourea solution.0.2g is carbon-based compound
Material is dispersed in thiourea solution, adds Surfactant CTAB, stirs 3h, the hydrochloric acid of 0.2mol/L is then added dropwise again, is stirred
2h is dried in vacuo 8h after centrifuge washing, obtains desciccate.Then desciccate is placed in tube furnace, in the atmosphere of nitrogen
Under, 200 DEG C of progress 2h heat treatments are warming up to the heating rate of 2.5 DEG C/min, make hole of the elemental sulfur in C-base composte material
Gap diffusion is uniformly, closely coupled with C-base composte material, and removes the sulphur on C-base composte material surface, obtains anode material
Material.The specific surface area of the cell positive material is 324m2/ g, sulphur are 68% in the mass fraction of cell positive material.
After cell positive material, binder (polytetrafluoroethylene (PTFE)) and acetylene black are mixed according to mass ratio 1:0.05:0.05
30min grinding is carried out, N-Methyl pyrrolidone is added and continues to grind 10min, is then coated on copper foil, is obtained after vacuum drying
Electrode slice, then it is fabricated to battery, test its chemical property.Using the battery of the present embodiment cell positive material in 0.1C multiplying power
Under first discharge specific capacity be 1034mAh/g, for the first time coulombic efficiency be 91%, in the charge and discharge specific volume of 50 charge and discharge cycles
Amount maintains 740mAh/g.
Embodiment 2
It weighs 20g melamine and is put into crucible with a lid and be placed in Muffle furnace and be warming up to 550 DEG C with 2.5 DEG C/min, into
The hot polymerization of row 4h reacts, and obtains flaxen bulk g-C after natural cooling3N4.By blocky g-C3N4Pass through ultrasound after grinding
It is dispersed in dehydrated alcohol and stirs, temperature is set as room temperature, ultrasonic time is set as 60min, then be centrifuged or filtered, after cleaning
It is dried in vacuo 12h, obtains two-dimensional layer graphitic nitralloy carbon, the specific surface area of two-dimensional layer graphitic nitralloy carbon is 65m2/g.It please join
Fig. 4 is read, the Raman figure for the two-dimensional layer graphitic nitralloy carbon being prepared for the embodiment of the present invention 2, in Fig. 4, g-C3N4On do not examine
Apparent Raman signal is measured, but detects two clearly Raman shift peaks on the composite, Raman shift peak is located at
1350.9cm-1And 1571.1cm-1, respectively correspond D band related with graphite material and G band.
5g two-dimensional layer graphitic nitralloy carbon and 2.5g sucrose are weighed, 30min grinding is carried out after mixing, is put into quartz after taking-up
Boat is placed in tube furnace plus quartz glass, under the atmosphere of nitrogen, with the heating rate of 5 DEG C/min be warming up to 650 DEG C into
The original position row 2h pyrolytic reaction, takes out after natural cooling, obtains the C-base composte material of black.
Weigh 0.5g NaS2O3It is added into 40mL deionized water, is stirred at room temperature, obtains thiourea solution.0.3g is carbon-based multiple
Condensation material is dispersed in thiourea solution, adds surfactant SDBS, stirs 3h, the sulfuric acid of 0.15mol/L is then added dropwise again, stirs
3h is mixed, 10h is dried in vacuo after centrifuge washing, obtains desciccate.Then desciccate is placed in tube furnace, in the gas of argon gas
Under atmosphere, 300 DEG C of progress 3h heat treatments are warming up to the heating rate of 5 DEG C/min, make hole of the elemental sulfur in C-base composte material
Gap diffusion is uniformly, closely coupled with C-base composte material, and removes the sulphur on C-base composte material surface, obtains anode material
Material.The specific surface area of the cell positive material is 378m2/ g, sulphur are 69% in the mass fraction of cell positive material.
Cell positive material, binder (polytetrafluoroethylene (PTFE)) and acetylene black is laggard according to mass ratio 1:0.1:0.1 mixing
Row 40min grinding is added N-Methyl pyrrolidone and continues to grind 10min, is then coated on copper foil, electricity is obtained after vacuum drying
Pole piece, then it is fabricated to battery, test its chemical property.Using the battery of the present embodiment cell positive material under 0.1C multiplying power
First discharge specific capacity be 1078mAh/g, for the first time coulombic efficiency be 89%, in the charging and discharging capacity of 50 charge and discharge cycles
Maintain 760mAh/g.
Embodiment 3
It weighs 20g urea and is put into crucible with a lid and be placed in Muffle furnace and be warming up to 550 DEG C with 2.5 DEG C/min, carry out 6h
Hot polymerization reaction, obtain flaxen bulk g-C after natural cooling3N4.By blocky g-C3N4Pass through ultrasonic disperse after grinding
It is stirred in dehydrated alcohol, temperature is set as room temperature, ultrasonic time is set as 60min, then be centrifuged or filtered, vacuum after cleaning
Dry 12h, obtains two-dimensional layer graphitic nitralloy carbon, and the specific surface area of two-dimensional layer graphitic nitralloy carbon is 63m2/g。
5g two-dimensional layer graphitic nitralloy carbon and 5g starch are weighed, 30min grinding is carried out after mixing, is put into quartz boat after taking-up
In addition quartz glass is placed in tube furnace, under the atmosphere of argon gas, 700 DEG C of progress are warming up to the heating rate of 5 DEG C/min
The original position 3h pyrolytic reaction, takes out after natural cooling, obtains the C-base composte material of black.
The C-base composte material and 0.7g sulphur powder for weighing 0.3g, after ground and mixed is uniform, mixture is placed in reactor,
It vacuumizes at room temperature, vacuum degree is -0.05MPa, and then reactor is put into oil bath pan and is warming up to 150 DEG C, and it is permanent to carry out 10h
Temperature processing diffuses to sublimed sulfur melting in the hole of C-base composte material, and cooled to room temperature obtains anode material
Material.The specific surface area of the cell positive material is 369m2/ g, sulphur are 70% in the mass fraction of cell positive material.
After cell positive material, binder (polytetrafluoroethylene (PTFE)) and acetylene black are mixed according to mass ratio 1:0.15:0.15
40min grinding is carried out, N-Methyl pyrrolidone is added and continues to grind 20min, is then coated on copper foil, is obtained after vacuum drying
Electrode slice, then it is fabricated to battery, test its chemical property.Referring to Fig. 5, for using 3 anode material of the embodiment of the present invention
The battery of material first charge-discharge curve graph under 0.1C multiplying power, Fig. 5 show to exist using the battery of the present embodiment cell positive material
First discharge specific capacity under 0.1C multiplying power is up to 1166mAh/g, and charge specific capacity is up to 1089mAh/g.
Embodiment 4
It weighs 20g urea and is put into crucible with a lid and be placed in Muffle furnace and be warming up to 600 DEG C with 2.5 DEG C/min, carry out 4h
Hot polymerization reaction, obtain flaxen bulk g-C after natural cooling3N4.By blocky g-C3N4Pass through ultrasonic disperse after grinding
It is stirred in dehydrated alcohol, temperature is set as room temperature, ultrasonic time is set as 60min, then be centrifuged or filtered, vacuum after cleaning
Dry 12h, obtains two-dimensional layer graphitic nitralloy carbon, and the specific surface area of two-dimensional layer graphitic nitralloy carbon is 73m2/g。
1g two-dimensional layer graphitic nitralloy carbon and 1g zinc oxide are weighed, 60min grinding is carried out after mixing, then with 500rpm's
Rate ball milling 60min, is put into quartz boat after taking-up and is placed in tube furnace, ethane is passed through with the flow velocity of 3L/min, with 10 DEG C/min
Heating rate be warming up to 650 DEG C of progress 2h chemical vapor depositions, take out and be put into beaker after natural cooling, be added 60ml's
It is centrifuged after the hydrochloric ultrasonic wave 1h of 20wt%, is then cleaned with dehydrated alcohol and deionized water to neutrality, the vacuum in 60 DEG C
It is dry, obtain the C-base composte material of black.
The C-base composte material and 0.65g sulphur powder for weighing 0.25g, after ground and mixed is uniform, are placed in reactor for mixture
In, it vacuumizes at room temperature, vacuum degree is -0.06MPa, and then reactor is put into oil bath pan and is warming up to 150 DEG C, is carried out
The processing of 10h constant temperature diffuses to sublimed sulfur melting in the hole of C-base composte material, and cooled to room temperature is obtaining battery just
Pole material.The specific surface area of the cell positive material is 334m2/ g, sulphur are 70% in the mass fraction of cell positive material.
After cell positive material, binder (polytetrafluoroethylene (PTFE)) and acetylene black are mixed according to mass ratio 1:0.18:0.18
30min grinding is carried out, N-Methyl pyrrolidone is added and continues to grind 10min, is then coated on copper foil, is obtained after vacuum drying
Electrode slice, then it is fabricated to battery, test its chemical property.
Referring to Fig. 6, being followed for charge and discharge of the battery using 4 cell positive material of the embodiment of the present invention under 0.1C multiplying power
Ring curve graph.Fig. 6 shows the ratio of electric discharge for the first time using the battery of 4 cell positive material of the embodiment of the present invention under 0.1C multiplying power
Capacity is 1166mAh/g, and coulombic efficiency is 95% for the first time, is maintained in the charging and discharging capacity of 50 charge and discharge cycles
810mAh/g or so.
Embodiment 5
It weighs 20g melamine and is put into crucible with a lid and be placed in Muffle furnace and be warming up to 600 DEG C with 2.5 DEG C/min, into
The hot polymerization of row 6h reacts, and obtains flaxen bulk g-C after natural cooling3N4.By blocky g-C3N4Pass through ultrasound after grinding
It is dispersed in dehydrated alcohol and stirs, temperature is set as room temperature, ultrasonic time is set as 60min, then be centrifuged or filtered, after cleaning
It is dried in vacuo 12h, obtains two-dimensional layer graphitic nitralloy carbon, the specific surface area of two-dimensional layer graphitic nitralloy carbon is 73m2/g。
1g two-dimensional layer graphitic nitralloy carbon and 0.5g cobalt oxide are weighed, 60min grinding is carried out after mixing, then with 550rpm
Rate ball milling 90min, be put into quartz boat after taking-up and be placed in tube furnace, ethane is passed through with the flow velocity of 3.5L/min, with 10 DEG C/
The heating rate of min is warming up to 700 DEG C of progress 2h chemical vapor depositions, takes out and is put into beaker after natural cooling, is added
It is centrifuged after the hydrochloric ultrasonic wave 1h of the 25wt% of 60ml, is then cleaned with dehydrated alcohol and deionized water to neutrality, at 60 DEG C
Middle vacuum drying obtains the C-base composte material of black.
The C-base composte material and 1.2g sulphur powder for weighing 0.3g, after ground and mixed is uniform, mixture is placed in reactor,
It vacuumizes at room temperature, vacuum degree is -0.08MPa, and then reactor is put into oil bath pan and is warming up to 180 DEG C, and it is permanent to carry out 8h
Temperature processing diffuses to sublimed sulfur melting in the hole of C-base composte material, and cooled to room temperature obtains anode material
Material.The specific surface area of the cell positive material is 387m2/ g, sulphur are 62% in the mass fraction of cell positive material.
After cell positive material, binder (polytetrafluoroethylene (PTFE)) and acetylene black are mixed according to mass ratio 1:0.19:0.19
40min grinding is carried out, N-Methyl pyrrolidone is added and continues to grind 10min, is then coated on copper foil, is obtained after vacuum drying
Electrode slice, then it is fabricated to battery, test its chemical property.Using the battery of the present embodiment cell positive material in 0.1C multiplying power
Under first discharge specific capacity be 1110mAh/g, for the first time coulombic efficiency be 88%, in the charge and discharge specific volume of 50 charge and discharge cycles
Amount maintains 690mAh/g or so.
Embodiment 6
It weighs 20g urea and is put into crucible with a lid and be placed in Muffle furnace and be warming up to 650 DEG C with 2.5 DEG C/min, carry out 4h
Hot polymerization reaction, obtain flaxen bulk g-C after natural cooling3N4.By blocky g-C3N4Pass through ultrasonic disperse after grinding
It is stirred in dehydrated alcohol, temperature is set as room temperature, ultrasonic time is set as 60min, then be centrifuged or filtered, vacuum after cleaning
Dry 12h, obtains two-dimensional layer graphitic nitralloy carbon, and the specific surface area of two-dimensional layer graphitic nitralloy carbon is 79m2/g。
Weigh 1g two-dimensional layer graphitic nitralloy carbon and 0.25g iron oxide, after mixing carry out 60min grinding, then with
The rate ball milling 90min of 600rpm, is put into quartz boat after taking-up and is placed in tube furnace, is passed through ethylene with the flow velocity of 3.5L/min,
750 DEG C of progress 2h chemical vapor depositions are warming up to the heating rate of 10 DEG C/min, takes out and is put into beaker after natural cooling,
It is centrifuged after the hydrochloric ultrasonic wave 1h of the 30wt% of 60ml is added, is then cleaned with dehydrated alcohol and deionized water to neutrality,
It is dried in vacuo in 60 DEG C, obtains the C-base composte material of black.
The C-base composte material and 1.05g sulphur powder for weighing 0.35g, after ground and mixed is uniform, are placed in reactor for mixture
In, it vacuumizes at room temperature, vacuum degree is -0.1MPa, and then reactor is put into oil bath pan and is warming up to 160 DEG C, carries out 14h
Constant temperature processing diffuses to sublimed sulfur melting in the hole of C-base composte material, and cooled to room temperature obtains anode material
Material.The specific surface area of the cell positive material is 367m2/ g, sulphur are 74% in the mass fraction of cell positive material.
Cell positive material, binder (polytetrafluoroethylene (PTFE)) and acetylene black is laggard according to mass ratio 1:0.2:0.2 mixing
Row 40min grinding is added N-Methyl pyrrolidone and continues to grind 20min, is then coated on copper foil, electricity is obtained after vacuum drying
Pole piece, then it is fabricated to battery, test its chemical property.Using the battery of the present embodiment cell positive material under 0.1C multiplying power
First discharge specific capacity be 1033mAh/g, for the first time coulombic efficiency be 90%, in the charging and discharging capacity of 50 charge and discharge cycles
Maintain 710mAh/g or so.
Comparative example 1
It weighs 20g melamine and is put into crucible with a lid and be placed in Muffle furnace and be warming up to 500 DEG C with 2.5 DEG C/min, into
The hot polymerization of row 3h reacts, and obtains flaxen bulk g-C after natural cooling3N4, grind to obtain g-C3N4Powder.
Weigh 5g g-C3N4Powder and 2.5g sucrose, mixing be placed in tube furnace, under the atmosphere of nitrogen, with 5 DEG C/
The heating rate of min is warming up to the 650 DEG C of progress original position 2h pyrolytic reactions, takes out after natural cooling, obtains the carbon-based multiple of black
Condensation material.
Weigh 0.5g NaS2O3It is added into 40mL deionized water, is stirred at room temperature, obtains thiourea solution.0.3g is carbon-based multiple
Condensation material is dispersed in thiourea solution, adds surfactant SDBS, stirs 3h, the sulfuric acid of 0.15mol/L is then added dropwise again, stirs
3h is mixed, 10h is dried in vacuo after centrifuge washing, obtains desciccate.Then desciccate is placed in tube furnace, in the gas of argon gas
Under atmosphere, 300 DEG C of progress 2h heat treatments are warming up to the heating rate of 5 DEG C/min, make hole of the elemental sulfur in C-base composte material
Gap diffusion is uniformly, closely coupled with C-base composte material, and removes the sulphur on C-base composte material surface, obtains anode material
Material.The specific surface area of the cell positive material is 323m2/ g, sulphur are 68% in the mass fraction of cell positive material.
Cell positive material, binder (polytetrafluoroethylene (PTFE)) and acetylene black is laggard according to mass ratio 1:0.1:0.1 mixing
Row 40min grinding is added N-Methyl pyrrolidone and continues to grind 10min, is then coated on copper foil, electricity is obtained after vacuum drying
Pole piece assembles lithium-sulfur cell by 2 method of embodiment and tests its chemical property.
As a result referring to Fig. 7, Fig. 7 is the charge and discharge using the battery of 1 cell positive material of comparative example under 0.1C multiplying power
Curve graph.The initial discharge specific capacity for the lithium-sulfur cell that Fig. 7 shows to use 1 cell positive material of comparative example to prepare for
896.7mAh/g, after the circle of circulation 50, capacity relative attenuation is more, specific discharge capacity 411mAh/g, in cyclic process
Capacity attenuation is very fast.
Comparative example 2
It weighs 20g melamine and is put into crucible with a lid and be placed in Muffle furnace and be warming up to 600 DEG C with 2.5 DEG C/min, into
The hot polymerization of row 6h reacts, and obtains flaxen bulk g-C after natural cooling3N4, grind to obtain g-C3N4Powder.
Weigh 1g g-C3N4Powder and 0.5g cobalt oxide carry out 60min grinding, are put into quartz boat after taking-up and are placed in after mixing
In tube furnace, ethane is passed through with the flow velocity of 3.5L/min, 700 DEG C of progress 2h chemistry gas are warming up to the heating rate of 10 DEG C/min
It mutually deposits, takes out and be put into beaker after natural cooling, be centrifuged after the hydrochloric ultrasonic wave 1h of the 25wt% of 60ml is added, then use nothing
Water-ethanol and deionized water are cleaned to neutrality, are dried in vacuo in 60 DEG C, and the C-base composte material of black is obtained.
The C-base composte material and 1.2g sulphur powder for weighing 0.3g, after ground and mixed is uniform, mixture is placed in reactor,
It vacuumizes at room temperature, vacuum degree is -0.06MPa, and then reactor is put into oil bath pan and is warming up to 180 DEG C, and it is permanent to carry out 4h
Temperature processing diffuses to sublimed sulfur melting in the hole of C-base composte material, and cooled to room temperature obtains anode material
Material.The specific surface area of the cell positive material is 313m2/ g, sulphur are 75% in the mass fraction of cell positive material.
After cell positive material, binder (polytetrafluoroethylene (PTFE)) and acetylene black are mixed according to mass ratio 1:0.19:0.19
40min grinding is carried out, N-Methyl pyrrolidone is added and continues to grind 10min, is then coated on copper foil, is obtained after vacuum drying
Electrode slice assembles lithium-sulfur cell by 2 method of embodiment and tests its chemical property.
As a result referring to Fig. 8, Fig. 8 is the cyclicity using the battery of 2 cell positive material of comparative example under 0.1C multiplying power
It can curve graph.Fig. 8 shows that the efficiency for charge-discharge of the lithium-sulfur cell prepared using 2 cell positive material of comparative example is lower, is
88.2%；Discharge capacity is lower for the first time, is 470.1mAh/g；After the circle of circulation 20, capacity attenuation is very fast.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of cell positive material, which is characterized in that the cell positive material includes C-base composte material and is filled in institute
State the sulphur of C-base composte material；
The C-base composte material includes two-dimensional layer graphitic nitralloy carbon and the charcoal for coating the two-dimensional layer graphitic nitralloy carbon；
The C-base composte material obtained by the two-dimensional layer graphitic nitralloy carbon and carbonaceous organic material original position pyrolytic reaction or
By being obtained in the two-dimensional layer graphitic nitralloy carbon surface chemical vapor deposition carbon deposit.
2. a kind of cell positive material according to claim 1, which is characterized in that the sulphur is filled in by following steps
The C-base composte material:
The C-base composte material is mixed with elemental sulfur and is placed in vacuum condition, carrying out heat treatment keeps the elemental sulfur molten
Melt and diffuses in the C-base composte material.
3. a kind of cell positive material according to claim 1, which is characterized in that the sulphur is filled in by following steps
The C-base composte material:
It disperses the C-base composte material in sulphur source solution, after surfactant is added, adds precipitating reagent and be stirred
Deposit elemental sulfur to the C-base composte material.
4. a kind of cell positive material according to claim 3, which is characterized in that the sulphur source is selected from Na2S2O3、Na2SX
With one of thiocarbamide or a variety of；
The surfactant is selected from one of cetyl trimethylammonium bromide, neopelex and tween or more
Kind；
The precipitating reagent is selected from one of hydrochloric acid, sulfuric acid and hydrogen peroxide or a variety of.
5. a kind of cell positive material according to claim 1, which is characterized in that the two-dimensional layer graphitic nitralloy carbon with
Pyrolysis specifically includes carbonaceous organic material in situ:
By the two-dimensional layer graphitic nitralloy carbon and the carbonaceous organic material under nitrogen and/or inert atmosphere, in-situ heat is carried out
Solution reaction；
The mass ratio of the two-dimensional layer graphitic nitralloy carbon and the carbonaceous organic material is 1:0.25~2；
The carbonaceous organic material is selected from glucose, sucrose, citric acid, starch, pitch, phenolic resin, polyethylene glycol and Vitamin C
One of acid is a variety of.
6. a kind of cell positive material according to claim 5, which is characterized in that the heating speed of the original position pyrolytic reaction
Rate is 2 DEG C/min~10 DEG C/min；
The temperature of the original position pyrolytic reaction is 600 DEG C~900 DEG C；
The time of the original position pyrolytic reaction is 2h~4h.
7. a kind of cell positive material according to claim 1, which is characterized in that described in the two-dimensional layer graphite nitrogen
Change carbon surface chemical vapor deposition carbon deposit to specifically include:
The two-dimensional layer graphitic nitralloy carbon is mixed with catalyst, is passed through carbon containing organic gas, carries out chemical vapor deposition
Product, then remove the catalyst.
8. a kind of cell positive material according to claim 7, which is characterized in that the catalyst is metal oxide；
The carbon containing organic gas is selected from one of methane, ethane, ethylene and acetylene or a variety of；
The flow velocity of the carbon containing organic gas is 2L/min~4L/min.
9. a kind of cell positive material according to claim 7, which is characterized in that the heating speed of the chemical vapor deposition
Rate is 2 DEG C/min~10 DEG C/min；
The temperature of the chemical vapor deposition is 600 DEG C~800 DEG C；
The time of the chemical vapor deposition is 2h~4h.
10. a kind of lithium-sulfur cell, which is characterized in that the positive electrode of the lithium-sulfur cell includes claim 1 to 9 any one
The cell positive material.
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