CN105789585B - A kind of foamed nickel supported compound lithium sulfur battery anode material of nano flower Spherical Carbon sulphur and preparation method thereof - Google Patents
A kind of foamed nickel supported compound lithium sulfur battery anode material of nano flower Spherical Carbon sulphur and preparation method thereof Download PDFInfo
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- CN105789585B CN105789585B CN201610186534.7A CN201610186534A CN105789585B CN 105789585 B CN105789585 B CN 105789585B CN 201610186534 A CN201610186534 A CN 201610186534A CN 105789585 B CN105789585 B CN 105789585B
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- sulphur
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 72
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 title claims abstract description 35
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 150000001875 compounds Chemical class 0.000 title claims abstract description 26
- 239000010405 anode material Substances 0.000 title claims abstract description 25
- 239000002057 nanoflower Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 49
- 239000002135 nanosheet Substances 0.000 claims abstract description 49
- 239000002131 composite material Substances 0.000 claims abstract description 37
- 241000143432 Daldinia concentrica Species 0.000 claims abstract description 36
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 36
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 239000011787 zinc oxide Substances 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 239000005864 Sulphur Substances 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- 239000006260 foam Substances 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 8
- 239000012047 saturated solution Substances 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical group C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000002077 nanosphere Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000004087 circulation Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 239000011149 active material Substances 0.000 abstract description 5
- 238000010276 construction Methods 0.000 abstract description 5
- 238000004146 energy storage Methods 0.000 abstract description 5
- 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 abstract description 3
- 239000008103 glucose Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000003763 carbonization Methods 0.000 abstract description 2
- 238000007500 overflow downdraw method Methods 0.000 abstract description 2
- 239000013077 target material Substances 0.000 abstract 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 30
- 239000004810 polytetrafluoroethylene Substances 0.000 description 30
- -1 metal oxide lithium salts Chemical class 0.000 description 18
- 229910001416 lithium ion Inorganic materials 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 239000003575 carbonaceous material Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229920001021 polysulfide Polymers 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000005077 polysulfide Substances 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- JGPSMWXKRPZZRG-UHFFFAOYSA-N zinc;dinitrate;hexahydrate Chemical class O.O.O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JGPSMWXKRPZZRG-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 229910001216 Li2S Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 2
- 125000006091 1,3-dioxolane group Chemical class 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000010406 cathode material Substances 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
- 238000004891 communication Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011530 conductive current collector Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of foamed nickel supported compound lithium sulfur battery anode material of nano flower Spherical Carbon sulphur and preparation method thereof, Zinc oxide nano sheet is generated by hydro-thermal reaction early stage and is used as sacrifice template, the glucose hydrothermal carbonization under 180~240 DEG C of temperature conditionss afterwards, reaction 3~6 hours, generate the composite construction of foamed nickel supported three-dimensional cross-linked carbon nanosheet and Nano carbon balls.Afterwards by fusion method sulfurizing, using carbon disulfide as solvent, reaction prepares target material.Wherein 100~800nm of Nano carbon balls diameter, carbon nanosheet thickness are 10~50nm.The material of the present invention has the advantages of flexible self-supporting, high electric discharge specific volume, high circulation stability and high rate capability, the mass energy density and high rate performance of active material has been significantly greatly increased, suitable for high-energy-density energy storage device, had broad application prospects in fields such as instant messaging, Aero-Space.
Description
Technical field
The present invention relates to the positive electrode field of lithium-sulfur cell, and in particular to a kind of foamed nickel supported nano flower Spherical Carbon
Compound lithium sulfur battery anode material of sulphur and preparation method thereof.
Background technology
With the fast development of social economy, resource and the energy are increasingly short, and green energy resource has turned into human society to be held
The Major Strategic selection of supervention exhibition.Electrochemical energy storage materials are the conversion of solution clean energy resource, the key for storing and utilizing with device.
The mechanism of new electrochemical power sources that lithium rechargeable battery grows up as a kind of the 1990s, has that energy density is big, circulation
Long lifespan, discharge voltage height and advantages of environment protection, have extensive in fields such as communications and transportation, national defence, aviation, military affairs
Application prospect.However, by the development in more than 20 years, based on metal oxide lithium salts positive pole system (such as cobalt acid lithium, LiFePO4,
LiMn2O4 etc.) lithium ion battery energy density have tended to close to theoretical value (300mAh/g), but with electric automobile, big
The fast development in the fields such as scale energy storage, existing system can not meet wanting for high-energy, high power, long-life and low cost
Ask, therefore urgently research and develop high-efficiency battery energy storage material and device.
In Olivine-type Cathode Material in Li-ion Batteries, sulphur positive pole is undoubtedly most one of a kind of material of attraction.Sulphur
Theoretical specific capacity can reach 1675mAh/g (being 5-10 times of traditional positive electrode), when being paired into battery with negative material lithium, its
Theoretical energy density is more up to 2600Wh/kg.Elemental sulfur also has cheap, rich reserves, environment-friendly, safe simultaneously
The advantages that reliable, therefore lithium-sulfur cell has wide commercial application prospect, is predicted to be the energy storage system of most prospect of future generation
System.But simple substance S8It is the insulator of electronics and ion, its room temperature (25 DEG C) electronic conductivity only has 5 × 10-30S/cm, without from
Sub- state is present, and causes relatively low active material utilization and low high rate performance.In addition, the intermediate product of lithium-sulfur cell electric discharge
Polysulfide has highly dissoluble in organic electrolyte, has extremely strong flowing shuttle after being dissolved in electrolyte.Wherein elemental sulfur
It is reduced to long chain Sn 2-(n >=4), the negative terminal surface Li insoluble with Li reaction generations is moved to after forming concentration difference2S2Or
Li2S, and short-chain polysulphides Sn 2-(n ＜ 4) is reduced to long-chain because concentration difference can migrate meeting positive pole.Above-mentioned shuttle effect
Not only reduce the active material of positive pole, and inside battery self discharge can be caused, cause capacity attenuation and cycle life to shorten.
Furthermore there are larger Volume Changes, S in lithium-sulfur cell cyclic process8(2.07g/cm3) and Li2S(1.66g/cm3) density not
Together, its volumetric expansion is about 76%, causes contact of the material with matrix to weaken, the surface topography and microscopic feature of sulphur positive pole are broken
It is bad, cause capacity attenuation.
By sulphur powder and conductive carbon material it is compound be improve sulphur positive electrode chemical property a kind of effective way.Due to carbon
The favourable three-dimensional network of material can improve the electric conductivity of composite, strengthen the high rate capability of sulphur positive pole.Three wieners simultaneously
The hierarchical porous structure of rice carbon material can effectively suppress the shuttle loss of polysulfide, improve the stable circulation of sulphur positive electrode
Property.
The content of the invention
It is an object of the invention to the defects of for lithium-sulfur cell shuttle effect, capacity attenuation is fast, there is provided a kind of foam
Compound lithium sulfur battery anode material of nano flower Spherical Carbon sulphur of Ni and preparation method thereof, the composite is used as lithium-sulfur cell
Positive electrode, with high charge-discharge specific capacity, long circulation life and excellent high rate performance.
A kind of foamed nickel supported compound lithium sulfur battery anode material of nano flower Spherical Carbon sulphur, including nickel foam substrate, set
Put in nickel foam substrate and the carbon nanosheet of composite crosslinking and Nano carbon balls and be filled on carbon nanosheet and Nano carbon balls
Sulphur.
Described carbon nanosheet and Nano carbon balls composite crosslinking, form three-dimensional porous structure and received as storage sulfenyl bottom, formation
The spherical structure of popped rice.The thickness of described carbon nanosheet is 10~50nm, described Nano carbon balls a diameter of 100~
800nm。
The sulphur being filled on carbon nanosheet and Nano carbon balls, not only it is evenly coated at carbon nanosheet and Nano carbon balls surface
(surface of carbon nanosheet and Nano carbon balls formation three-dimensional carbon network), has also penetrated into carbon nanosheet and Nano carbon balls composite crosslinking
In the space and interlayer of (three-dimensional carbon material), it has been sufficient filling with inside carbon material.
Foamed nickel supported nano flower Spherical Carbon sulphur composite positive pole preparation method of the present invention, including following step
Suddenly：
1) it is zinc nitrate hexahydrate, urea and ammonium fluoride is soluble in water, it is well mixed, forms uniform solution, then will bubble
Foam nickel substrate immerse uniform solution in, carry out first time hydro-thermal reaction, first time hydrothermal temperature be 90~150 DEG C, first
Secondary the hydro-thermal reaction time is 6~9 hours, and first time hydro-thermal reaction product is scrubbed, dries, after heat treatment, obtains nickel foam and bears
The Zinc oxide nano sheet of load；
2) using foamed nickel supported Zinc oxide nano sheet prepared by step 1) as template is sacrificed, it is dipped in 0.1~2mol/
The L glucose aqueous solution, second of hydro-thermal reaction is carried out, second of hydrothermal temperature is 180~240 DEG C, and second of hydro-thermal is anti-
It is 3~6 hours between seasonable, second of hydro-thermal reaction product is scrubbed, dries, after heat treatment, and foamed nickel supported carbon is made and receives
The composite of rice piece and Nano carbon balls；
3) the carbon disulfide saturated solution of sulfur-bearing is uniformly added dropwise to the foamed nickel supported carbon nanosheet prepared in step 2)
On the composite (i.e. carbon nanosheet and the composite substrate of Nano carbon balls crosslinking) of Nano carbon balls, 3 are reacted at 155~165 DEG C
~6 hours, after reacted, obtain foamed nickel supported nano flower Spherical Carbon sulphur composite positive pole.
Limited technical scheme as the present invention below：
In step 1), the mass ratio of described zinc nitrate hexahydrate, urea and ammonium fluoride is 0.6-1.8：0.6-1.8：
0.15-0.45。
Described first time hydro-thermal reaction is carried out in polytetrafluoroethylene (PTFE) high pressure hydro-thermal tank, polytetrafluoroethylene (PTFE) high pressure hydro-thermal tank
It is sealed in autoclave.
The condition of described heat treatment is：It is heat-treated 1~3 hour through 500~800 DEG C in argon gas.
Obtained foamed nickel supported Zinc oxide nano sheet is the foamed nickel supported flower shape zinc oxide nanometer being cross-linked with each other
Piece.
In step 2), using foamed nickel supported Zinc oxide nano sheet prepared by step 1) as sacrifice template.Described second
Secondary hydro-thermal reaction is carried out in polytetrafluoroethylene (PTFE) high pressure hydro-thermal tank, and polytetrafluoroethylene (PTFE) high pressure hydro-thermal tank is sealed in autoclave
In.
The condition of described heat treatment is：It is heat-treated 1~3 hour through 500~800 DEG C in argon gas.After heat treatment
It is foamed nickel supported carbon nanosheet and Nano carbon balls phase to the composite of foamed nickel supported carbon nanosheet and Nano carbon balls
The three-dimensional manometer flower ball-shaped composite construction being mutually crosslinked.
In step 3), described reaction is carried out in polytetrafluoroethylene (PTFE) high pressure hydro-thermal tank, polytetrafluoroethylene (PTFE) high pressure hydro-thermal tank
It is sealed in autoclave.The carbon disulfide saturated solution of sulfur-bearing is uniformly added dropwise in the foamed nickel supported of step 2) preparation
On the composite of carbon nanosheet and Nano carbon balls, 1~5mg/cm of unit area sulphur load quality2, react 3 at 155~165 DEG C
~6 hours, after reacted, obtaining foamed nickel supported nano flower Spherical Carbon sulphur composite positive pole, (i.e. foamed nickel supported received
The compound lithium sulfur battery anode material of popped rice Spherical Carbon sulphur).
The carbon disulfide saturated solution of sulfur-bearing refers to the saturated solution that sulphur is dissolved in carbon disulfide formation.
In the present invention, Zinc oxide nano sheet is generated by hydro-thermal reaction early stage and is used as sacrifice template, afterwards 180~240
Glucose hydrothermal carbonization under DEG C temperature conditionss, react 3~6 hours, generate foamed nickel supported three-dimensional cross-linked carbon nanosheet and carbon
The composite construction of nanosphere.Afterwards by fusion method sulfurizing, using carbon disulfide as solvent, under 155 DEG C~165 DEG C temperature conditionss
3-6h is reacted, prepares a kind of foamed nickel supported compound lithium sulfur battery anode material of three-dimensional manometer flower ball-shaped carbon sulphur.Wherein carbon
Nanometer 100~800nm of bulb diameter, carbon nanosheet thickness is 10~50nm.Three-dimensional manometer flower ball-shaped carbon sulphur complex lithium sulphur of the present invention
Cell positive material has the advantages of flexible self-supporting, high electric discharge specific volume, high circulation stability and high rate capability, is significantly greatly increased
The mass energy density and high rate performance of active material, suitable for high-energy-density energy storage device, navigated in instant messaging, aviation
The field such as it has broad application prospects.
Compared with prior art, the invention has the advantages that：
In the present invention, carbon nanosheet and Nano carbon balls composite crosslinking form three-dimensional porous structure as storage sulfenyl bottom, are formed
The composite of crosslinking, a diameter of 100~800nm of described carbon ball, described carbon nanosheet thickness degree is 10~50nm.According to
Actual demand, every response parameter can be adjusted.For example adjust reaction density, reaction time and controlling reaction temperature oxidation
Zinc, carbon nanosheet, the size and thickness of Nano carbon balls and sulphur layer.
The inventive method using the carbon nanosheet that foamed nickel supported hydro-thermal method is formed with Nano carbon balls composite construction as carrier,
Sulphur carbon composite electrode material is prepared by heated sealed.The preparation method is convenient and simple, reproducible, easily controllable.
The foamed nickel supported compound lithium sulfur battery anode material of flower ball-shaped carbon sulphur prepared by the present invention, by the carbon nanometer being crosslinked
Piece and Nano carbon balls composite construction form three-dimensional flower-shaped porous mould, have larger specific surface area, there is provided more activity
Carrier and faster ion and electron propagation ducts, while this cross linked porous model also increases basal body structure and electrolyte
Contact area.After 155 DEG C of seepage flow, uniform clad structure is formd.Sulphur is not only evenly coated at three-dimensional carbon network surface,
Also penetrated into the space and interlayer of three-dimensional carbon material, be sufficient filling with inside carbon material.The Nano carbon balls layer on surface is effective
The shuttle for blocking polysulfide, slow down the decay of capacity, improve cyclical stability.In the present invention, pass through carbon nanometer
Piece and Nano carbon balls it is compound, not only provide good electron propagation ducts, and overcome single carbon material high magnification and decline
Subtract fast inferior position, realize with high circulation stability, high rate capability, high charge-discharge capacity " three high " lithium-sulphur cell positive electrode
Material.The " three high " that the foamed nickel supported three-dimensional compound lithium sulfur battery anode material of flower ball-shaped carbon sulphur prepared by the present invention has is special
Point, performance is still good under high magnification, is worked under the conditions of the high current that is particularly suitable for use in.
The foamed nickel supported three-dimensional manometer flower ball-shaped carbon used in the present invention can be used as conductive current collector and more vulcanizations
The shuttle baffle element and electrode structure liptinite of thing, improve multiplying power and long period cycle performance.The electrode is integrated simultaneously
Combination electrode, it is not necessary to add binding agent and conductive agent, greatly reduce afflux weight, improve the load capacity of active material
And utilization rate.Therefore, the three-dimensional manometer flower ball-shaped carbon sulphur combination electrode material of synthetic foam Ni is designed to high-performance lithium sulphur
The development of battery is significant.
Brief description of the drawings
Fig. 1 is the scanning electricity of the three-dimensional carbon structure of obtained foamed nickel supported carbon nanosheet and Nano carbon balls in embodiment 1
Mirror figure；
Fig. 2 is that the foamed nickel supported compound lithium sulfur battery anode material high power of nano flower Spherical Carbon sulphur is made in embodiment 1
Rate scanning electron microscope (SEM) photograph；
Fig. 3 is that the foamed nickel supported low height of the compound lithium sulfur battery anode material of nano flower Spherical Carbon sulphur is made in embodiment 1
Multiplying power scanning electron microscope (SEM) photograph；
Fig. 4 is the transmission electron microscope picture and Elemental redistribution of obtained crosslinking nano flower ball-shaped carbon sulphur positive electrode in embodiment 1
Figure, (a) is transmission electron microscope picture in wherein Fig. 4, and (b) is C element distribution map in Fig. 4, and (c) is S distribution diagram of element in Fig. 4；
Fig. 5 is the obtained foamed nickel supported compound lithium sulfur battery anode material of nano flower Spherical Carbon sulphur in embodiment 1
Cycle performance and coulombic efficiency figure under 0.5C；
Fig. 6 is the obtained foamed nickel supported compound lithium sulfur battery anode material of nano flower Spherical Carbon sulphur in embodiment 1
High rate performance figure.
Embodiment
The present invention is described in detail with reference to embodiment, but the present invention is not limited to this.
Embodiment 1
Weigh 0.6g zinc nitrate hexahydrates, 0.6g urea and 0.15g ammonium fluorides to be dissolved in 80ml deionized waters, stir to complete
Fully dissolved is made into uniform solution to pellucidity.The uniform solution of above-mentioned formation is put into polytetrafluoroethylene (PTFE) high pressure hydro-thermal tank,
And piece of foam nickel substrate is put into advance.Hydro-thermal tank is sealed in autoclave, hydro-thermal is anti-under the conditions of 90 DEG C in an oven
Answer 6 hours.25 DEG C of room temperature is cooled to after reaction completely, places after cleaning three times with deionized water and is dried in baking oven.Afterwards in argon
Calcined 1 hour under the conditions of 500 DEG C in gas, naturally cool to 25 DEG C of room temperature, foamed nickel supported Zinc oxide nano sheet is made.
It is that 0.1mol/L D/Ws are put into polytetrafluoroethylene (PTFE) high pressure hydro-thermal tank by 80ml molar concentrations, and in advance
It is put into foamed nickel supported Zinc oxide nano sheet (substrate).Hydro-thermal tank is sealed in autoclave, in an oven 180 DEG C of bars
Hydro-thermal reaction 3 hours under part.25 DEG C of room temperature is cooled to after reaction completely, places after cleaning three times with deionized water and is dried in baking oven
It is dry.Calcined 1 hour under the conditions of 500 DEG C in argon gas afterwards, naturally cool to 25 DEG C of room temperature, foamed nickel supported carbon nanometer is made
The composite of piece and Nano carbon balls.Electronic Speculum (SEM) analysis is scanned to obtained carbon composite, as shown in Figure 1, it is seen that
Nano carbon balls 100~500nm of diameter, carbon nanosheet thickness degree are 10nm.
The carbon disulfide saturated solution of sulfur-bearing is uniformly added dropwise and is crosslinked in foamed nickel supported carbon nanosheet and Nano carbon balls
Composite substrate (i.e. foamed nickel supported carbon nanosheet and the composite of Nano carbon balls) on, sulphur unit area load capacity is
1mg/cm2.Above-mentioned electrode is positioned in polytetrafluoroethylene (PTFE) high pressure hydro-thermal tank, is sealed in autoclave, in an oven 155
Heated 3 hours under the conditions of DEG C, the foamed nickel supported compound lithium sulfur battery anode material of nano flower Spherical Carbon sulphur is made.To what is obtained
Carbon sulphur composite is scanned Electronic Speculum (SEM) and transmission electron microscope (TEM) analysis, as in Figure 2-4.It can be seen that：Sulphur uniformly wraps
It is overlying on carbon material surface.
Embodiment 2
Weigh 1.2g zinc nitrate hexahydrates, 1.2g urea and 0.3g ammonium fluorides to be dissolved in 80ml deionized waters, stir to complete
Fully dissolved is made into uniform solution to pellucidity.The uniform solution of above-mentioned formation is put into polytetrafluoroethylene (PTFE) high pressure hydro-thermal tank,
And piece of foam nickel substrate is put into advance.Hydro-thermal tank is sealed in autoclave, hydro-thermal is anti-under the conditions of 130 DEG C in an oven
Answer 7.5 hours.Room temperature is cooled to after reaction completely, places after cleaning three times with deionized water and is dried in baking oven.Afterwards in argon gas
In calcine 2 hours under the conditions of 650 DEG C, naturally cool to 25 DEG C of room temperature, foamed nickel supported Zinc oxide nano sheet be made.
It is that 1mol/L D/Ws are put into polytetrafluoroethylene (PTFE) high pressure hydro-thermal tank by 80ml molar concentrations, and puts in advance
Enter foamed nickel supported Zinc oxide nano sheet (substrate).Hydro-thermal tank is sealed in autoclave, in an oven 210 DEG C of conditions
Lower hydro-thermal reaction 4.5 hours.25 DEG C of room temperature is cooled to after reaction completely, places after cleaning three times with deionized water and is dried in baking oven
It is dry.Calcined 2 hours under the conditions of 700 DEG C in argon gas afterwards, naturally cool to 25 DEG C of room temperature, foamed nickel supported carbon nanometer is made
The composite of piece and Nano carbon balls.
The carbon disulfide saturated solution of sulfur-bearing is uniformly added dropwise and is crosslinked in foamed nickel supported carbon nanosheet and Nano carbon balls
Composite substrate (i.e. foamed nickel supported carbon nanosheet and the composite of Nano carbon balls) on, sulphur unit area load capacity is
2.5mg/cm2.Above-mentioned electrode is positioned in polytetrafluoroethylene (PTFE) high pressure hydro-thermal tank, is sealed in autoclave, in an oven
Heated 4.5 hours under the conditions of 160 DEG C, the foamed nickel supported compound lithium sulfur battery anode material of nano flower Spherical Carbon sulphur is made.
Embodiment 3
Weigh 1.8 zinc nitrate hexahydrates, 1.8g urea and 0.45g ammonium fluorides to be dissolved in 80ml deionized waters, stir to complete
Fully dissolved is made into uniform solution to pellucidity.The uniform solution of above-mentioned formation is put into polytetrafluoroethylene (PTFE) high pressure hydro-thermal tank,
And piece of foam nickel substrate is put into advance.Hydro-thermal tank is sealed in autoclave, hydro-thermal is anti-under the conditions of 150 DEG C in an oven
Answer 9 hours.Room temperature is cooled to after reaction completely, places after cleaning three times with deionized water and is dried in baking oven.Afterwards in argon gas
Calcined 3 hours under the conditions of 800 DEG C, naturally cool to 25 DEG C of room temperature, foamed nickel supported Zinc oxide nano sheet is made.
It is that 2mol/L D/Ws are put into polytetrafluoroethylene (PTFE) high pressure hydro-thermal tank by 80ml molar concentrations, and puts in advance
Enter foamed nickel supported Zinc oxide nano sheet (substrate).Hydro-thermal tank is sealed in autoclave, in an oven 240 DEG C of conditions
Lower hydro-thermal reaction 6 hours.25 DEG C of room temperature is cooled to after reaction completely, places after cleaning three times with deionized water and is dried in baking oven.
Calcined 3 hours under the conditions of 800 DEG C in argon gas afterwards, naturally cool to 25 DEG C of room temperature, foamed nickel supported carbon nanosheet is made
With the composite of Nano carbon balls.
The carbon disulfide saturated solution of sulfur-bearing is uniformly added dropwise and is crosslinked in foamed nickel supported carbon nanosheet and Nano carbon balls
Composite substrate (i.e. foamed nickel supported carbon nanosheet and the composite of Nano carbon balls) on, sulphur unit area load capacity is
5mg/cm2.Above-mentioned electrode is positioned in polytetrafluoroethylene (PTFE) high pressure hydro-thermal tank, is sealed in autoclave, in an oven 165
Heated 6 hours under the conditions of DEG C, the foamed nickel supported compound lithium sulfur battery anode material of nano flower Spherical Carbon sulphur is made.
Performance test
Three-dimensional manometer flower ball-shaped carbon sulphur composite foamed nickel supported made of above-described embodiment 1~3 is prepared into lithium
Sulphur cell positive electrode, lithium metal test battery performance as negative pole in two electrode systems.Lithium ion battery is assembled into 2025 types,
Microporous polypropylene membrane (Cellgard 2400) is used as barrier film, using volume ratio 1:1 1,3- dioxolanes (DOL) and second two
Diethylene glycol dimethyl ether (DME) is used as solvent.Added in electrolyte double (fluoroform) the sulfonamide lithium salts (LiTFSI) of 1mol/L with
1.0wt.% LiNO3.The lithium ion battery assembles completion in the dry glove box full of argon gas.The lithium-ion electric assembled
Pond carries out constant current charge-discharge test after placing 48h, and charging/discharging voltage is 1.7V~2.8V.Lithium ion battery is in 25 ± 1 DEG C of environment
Charge-discharge performance, Reversible lithium insertion capacity and the high-rate characteristics of middle circulation measurement anode.
By in embodiment 1 be assembled into lithium ion battery after, carry out various electrochemical property tests.As seen from Figure 5, lithium
Ion battery has 1300mAh/g discharge capacity first, its discharge capacity after 200 circulations under current density 0.5C
Still there is 1046mAh/g, coulombic efficiency maintains more than 97%, shows excellent capability retention and cyclical stability.
Fig. 6 show the high rate performance figure of positive electrode manufactured in the present embodiment, and the material shows very excellent high rate performance,
Capacity respectively reaches 1300,1136,1038,960,880 and 699mAh/g under 0.5C, 1C, 1.5C, 2.0C, 3.0C, 10C.Work as electricity
Stream from 10C return to 0.5C suddenly when, battery capacity returns to 975mAh/g.
By in embodiment 2 be assembled into lithium ion battery after, carry out various electrochemical property tests.The lithium ion battery exists
There is 1247mAh/g discharge capacity first, its discharge capacity still has after 200 circulations under current density 0.5C
1003mAh/g, coulombic efficiency maintain more than 97%, show excellent capability retention and cyclical stability.From this reality
Apply example preparation positive electrode high rate performance figure in find out, the material shows very excellent high rate performance, 0.5C, 1C,
Capacity respectively reaches 1247,1100,1001,912,879 and 682mAh/g under 1.5C, 2.0C, 3.0C, 10C.When electric current is from 10C
When returning to 0.5C suddenly, battery capacity returns to 940mAh/g.
By in embodiment 3 be assembled into lithium ion battery after, carry out various electrochemical property tests.Lithium ion battery is in electricity
There is 1198mAh/g discharge capacity first, its discharge capacity still has after 200 circulations under current density 0.5C
985mAh/g, coulombic efficiency maintain more than 97%, show excellent capability retention and cyclical stability.From this implementation
Example prepare positive electrode high rate performance figure in find out, the material shows very excellent high rate performance, 0.5C, 1C,
Capacity respectively reaches 1198,1036,979,913,863 and 651mAh/g under 1.5C, 2.0C, 3.0C, 10C.When electric current is dashed forward from 10C
When so returning to 0.5C, battery capacity returns to 902mAh/g.
A kind of foamed nickel supported compound lithium sulfur battery anode material of three-dimensional manometer flower ball-shaped carbon sulphur in embodiment 1~3
Its maximum discharge capacity in difference under current density is as shown in table 1 after being assembled into lithium ion battery：
Table 1
Claims (6)
1. a kind of foamed nickel supported compound lithium sulfur battery anode material of nano flower Spherical Carbon sulphur, it is characterised in that including foam
Nickel substrate, it is arranged in nickel foam substrate and the carbon nanosheet of composite crosslinking and Nano carbon balls and is filled in carbon nanosheet and carbon
Sulphur on nanosphere；
The described foamed nickel supported compound lithium sulfur battery anode material of nano flower Spherical Carbon sulphur is prepared according to following steps：
1) it is zinc nitrate hexahydrate, urea and ammonium fluoride is soluble in water, it is well mixed, uniform solution is formed, then by nickel foam
Substrate is immersed in uniform solution, carries out first time hydro-thermal reaction, and first time hydrothermal temperature is 90~150 DEG C, first time water
The thermal response time is 6~9 hours, and first time hydro-thermal reaction product is scrubbed, dries, after heat treatment, obtains foamed nickel supported
Zinc oxide nano sheet；
2) using foamed nickel supported Zinc oxide nano sheet prepared by step 1) as template is sacrificed, D/W is dipped in,
Second of hydro-thermal reaction is carried out, second of hydrothermal temperature is 180~240 DEG C, and second of the hydro-thermal reaction time is 3~6 small
When, second of hydro-thermal reaction product is scrubbed, dries, after heat treatment, and foamed nickel supported carbon nanosheet and Nano carbon balls is made
Composite；
3) the carbon disulfide saturated solution of sulfur-bearing is uniformly added dropwise to the foamed nickel supported carbon nanosheet and carbon prepared in step 2)
On the composite of nanosphere, 1~5mg/cm of unit area sulphur load quality2, reacted 3~6 hours at 155~165 DEG C, through anti-
Ying Hou, obtain foamed nickel supported nano flower Spherical Carbon sulphur composite positive pole.
2. the foamed nickel supported compound lithium sulfur battery anode material of nano flower Spherical Carbon sulphur according to claim 1, it is special
Sign is that the thickness of described carbon nanosheet is 10~50nm, a diameter of 100~800nm of described Nano carbon balls.
3. the foamed nickel supported compound lithium sulfur battery anode material of nano flower Spherical Carbon sulphur according to claim 1, it is special
Sign is, in step 1), the mass ratio of described zinc nitrate hexahydrate, urea and ammonium fluoride is 0.6-1.8：0.6-1.8：
0.15-0.45。
4. the foamed nickel supported compound lithium sulfur battery anode material of nano flower Spherical Carbon sulphur according to claim 1, it is special
Sign is, in step 1), the condition of described heat treatment is：It is heat-treated 1~3 hour through 500~800 DEG C in argon gas.
5. the foamed nickel supported compound lithium sulfur battery anode material of nano flower Spherical Carbon sulphur according to claim 1, it is special
Sign is, in step 2), the concentration of described D/W is 0.1~2mol/L.
6. the foamed nickel supported compound lithium sulfur battery anode material of nano flower Spherical Carbon sulphur according to claim 1, it is special
Sign is, in step 2), the condition of described heat treatment is：It is heat-treated 1~3 hour through 500~800 DEG C in argon gas.
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| CN108232115B (en) * | 2018-01-26 | 2020-12-15 | 南开大学 | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery |
| CN109461910B (en) * | 2018-10-19 | 2021-04-06 | 浙江大学 | Lithium battery positive electrode based on graphene-sulfur composite material and preparation method thereof |
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