CN103746095B - Carbon-sulfur composite positive pole material and preparation method thereof - Google Patents

Carbon-sulfur composite positive pole material and preparation method thereof Download PDF

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Publication number
CN103746095B
CN103746095B CN201310696559.8A CN201310696559A CN103746095B CN 103746095 B CN103746095 B CN 103746095B CN 201310696559 A CN201310696559 A CN 201310696559A CN 103746095 B CN103746095 B CN 103746095B
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sulfur
carbon
positive pole
composite positive
activated carbon
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CN103746095A (en
Inventor
梁兴华
曾帅波
刘于斯
史琳
叶超超
刘天骄
华晓鸣
宋清清
刘浩
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Guangxi University of Science and Technology
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Guangxi University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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 discloses a carbon-sulfur composite positive pole material which comprises activated carbon and sulfur. The material is characterized in that the sulfur is filled in pores of the activated carbon, and Al2O3 can be coated on the surface of the carbon-sulfur composite positive pole material. The composite positive pole material can be used for positive poles of lithium-sulfur batteries, can improve the cyclic charging-discharging property when the simple substance sulfur is used as the positive pole, reduces the generation of the lithium-sulfur polymers, and avoids the lithium-sulfur irreversible reaction.

Description

A kind of carbon sulfur composite positive pole and preparation method thereof
Technical field
The invention belongs to lithium-sulfur cell field, relate to a kind of carbon sulfur composite positive pole for lithium-sulfur cell and preparation method thereof.
Background technology
The electrochmical power source performance that it is used is had higher requirement by the development of portable electronic commnication device, especially can require more and more higher to the ratio of battery.One as lithium ion battery, the theoretical specific capacity of lithium/sulfur battery is 1675 mAh/g, and the elemental sulfur as positive electrode has the advantages such as abundance, low price, environmentally friendly, battery security is good, and therefore lithium-sulfur cell is considered as the most potential battery system that the next generation is provided that high specific energy.But owing to elemental sulfur is typical electronics and ion insulator, the many polysulfides of intermediate that reduction process produces are soluble in organic liquid electrolyte, partly soluble many polysulfides are diffused into and reach lithium metal anode surface and occur with it self discharge to react, and accelerate the corrosion of lithium, generate unordered Li2S2And Li2S is part irreversible reaction, and it is low poor with cycle performance of battery that this series of problem results in electrode active material utilization rate.Prior art has used organic sulfur compound or sulfur compound PDDTB, PDTDA, PABTH, FeS2Replace elemental sulfur to solve the problems referred to above with CuS, but the theoretical specific capacity of this compounds is less than the 30% of elemental sulfur, thus limit the application of this kind of material.
Summary of the invention
Present invention aim to address that existing elemental sulfur is as the problem of cycle performance of battery difference during positive electrode, it is provided that a kind of carbon sulfur composite positive pole and preparation method thereof.
It is as follows that the present invention realizes the technical scheme that above-mentioned purpose used:
A kind of carbon sulfur composite positive pole, including activated carbon and sulfur, its feature is, described sulfur is filled in the duct of described activated carbon.
Further, the Surface coating of described carbon sulfur composite positive pole has Al2O3。
The preparation method of above-mentioned carbon sulfur composite positive pole, mixes with sulfur including by activated carbon, under an inert atmosphere, is incubated 3～20 hours in 120～300 DEG C, obtains described carbon sulfur composite positive pole.
Further, described activated carbon is 1:(0.5～2 with the mass ratio of sulfur).
The preparation method of above-mentioned carbon sulfur composite positive pole, including: activated carbon is mixed with sulfur, under an inert atmosphere, is incubated 3～20 hours in 120～300 DEG C；Again the mixture obtained after insulation is joined in the cotton-shaped liquid of aluminium hydroxide, filter, be dried, roasting, obtain described carbon sulfur composite positive pole.
Further, described activated carbon is 1:(0.5～2 with the mass ratio of sulfur).
Further, the cotton-shaped liquid of described aluminium hydroxide is to be obtained to 7～8 by the pH value of regulation aluminum sulfate aqueous solution.Preferably with the pH value of ammonia regulation aluminum sulfate aqueous solution.
Further, the temperature of described roasting is 250～350 DEG C, time 4～10 hours.
Accompanying drawing explanation
Fig. 1 is the XRD figure of material.
Fig. 2 is the Electronic Speculum figure of C/S composite described in embodiment 1.
Fig. 3 is the Electronic Speculum figure of C/S composite described in embodiment 2.
Fig. 4 is the charge and discharge cycles figure of C/S composite described in embodiment 1.
Fig. 5 is the charge and discharge cycles figure of C/S composite described in embodiment 2.
Detailed description of the invention
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in further details.
Embodiment 1
Activated carbon (analytical pure) and elemental sulfur (analytical pure) are pressed the mass ratio of 1:1 grinding in ball grinder uniformly after, put in vacuum drying oven, pour argon about 20min, with the air inside getting rid of, it is to avoid under high temperature, sulfur is oxidized.Then under the nitrogen atmosphere of flowing, activated carbon and elemental sulfur mixture are heated to about 155 DEG C, keep 10 hours at this temperature, the most again temperature is increased to about 250 degree, keeps 3h at this temperature, obtain black product, i.e. C/S composite.
Embodiment 2
Aluminum sulfate is dissolved in deionized water in the ratio of 1g:16ml, it is sufficiently stirred for, after being completely dissolved, dropping ammonia, regulation pH value is to 7.5, becoming cloudy solution, black product embodiment 1 prepared joins cloudy solution mixing by n (Al): n (C)=3:200, after stirring, after filtration, it is washed with deionized again, is dried 10h in an oven at 100 DEG C, then is placed in chamber type electric resistance furnace, in air atmosphere, the ramp of 3 DEG C/min is to 300 DEG C, constant temperature calcining 7h, furnace cooling, obtain being coated with Al2O3C/S composite.
The sign of battery performance: the composite of gained is weighed according to mass ratio 80:10 with polyvinylidene fluoride (PVDF), being modulated into uniform pulpous state with N-Methyl pyrrolidone for solvent, carry out drying tabletting after coating, positive plate is made in cut-parts, lithium sheet is as negative plate, the LiPF of 1mol/L6EC/DNC(ethylene carbonate/butylene, volume 1:1) as electrolyte, barrier film Celgard2300, be assembled into button cell.
Fig. 1 is elemental sulfur (A), activated carbon (B), Al2O3The XRD figure of the carbon sulfur composite of (C) (D) afterwards before cladding, as seen from Figure 1, elemental sulfur exists with amorphous state in the composite, and composite is 23 at 2 γ0Diffraction maximum relatively activated carbon during neighbouring position reduces, show to exist between elemental sulfur and activated carbon to interact, and illustrate that sulfur is the state of high degree of dispersion in activated carbon, this is due in heating process, the sulfur steam under melted elemental sulfur and high temperature under the higher surface force of activated carbon and the strongest adsorptivity dispersed filler in the duct of activated carbon.
Fig. 2 is the Electronic Speculum figure of embodiment 1 gained carbon sulfur composite, and Fig. 3 is that embodiment 2 is coated with Al2O3The Electronic Speculum figure of rear carbon sulfur composite.It can be seen that before and after Bao Fu, the pattern of C/S has obvious difference.Al2O3 C/S primary particle before cladding is less, and grain corner is clearly demarcated, combines loosely each other； Al2O3C/S primary particle after cladding is grown up, and grain corner gradually obscures, and combines tightr each other.This shows Al2O3Being coated with the primary particle to C/S and have obvious the Surface Modification Effect, reunite to creating cladding between granule and granule, make each coated particle become individual, outer layer is by Al2O3Protection, serves and the effect of Li spaced-apart, which reduces the generation of lithium sulfur polymer, and the irreversible reaction of lithium sulfur also can reduce.
Fig. 4 is the charge and discharge cycles figure of embodiment 1 gained carbon sulfur composite, and Fig. 5 is that embodiment 2 is coated with Al2O3The charge and discharge cycles figure of rear carbon sulfur composite.It can be seen that uncoated Al2O3C/S composite initial capacity be 850mAh/g, the 20th time circulate time, capability retention 82.3%.Cladding Al2O3After C/S composite initial capacity be 900mAh/g, the 20th time circulation capability retention still have 93.04%.Visible, after elemental sulfur is compound with activated carbon, the cycle performance of battery of material can be improved, be coated with Al2O3After the cycle performance of C/S composite can be made preferably to be improved, and attenuation amplitude is less.

Claims (4)

1. a carbon sulfur composite positive pole, including activated carbon and sulfur, it is characterised in that described sulfur is filled in the duct of described activated carbon, and the Surface coating of described carbon sulfur composite positive pole has Al2O3；By being mixed with sulfur by activated carbon, under an inert atmosphere, it is incubated 3～20 hours in 120～300 DEG C；The mixture obtained after being incubated again is according to n(Al): n (C)=3:200 joins in the cotton-shaped liquid of aluminium hydroxide, filters, and is dried, roasting, obtains described carbon sulfur composite positive pole；Described activated carbon is 1:1 with the mass ratio of sulfur.
2. the preparation method of carbon sulfur composite positive pole described in claim 1, it is characterised in that including: mixed with sulfur by activated carbon, under an inert atmosphere, is incubated 3～20 hours in 120～300 DEG C；The mixture obtained after being incubated again is according to n(Al): n (C)=3:200 joins in the cotton-shaped liquid of aluminium hydroxide, filters, and is dried, roasting, obtains described carbon sulfur composite positive pole；Described activated carbon is 1:1 with the mass ratio of sulfur.
The preparation method of carbon sulfur composite positive pole the most according to claim 2, it is characterised in that the cotton-shaped liquid of described aluminium hydroxide is to be obtained to 7～8 by the pH value of regulation aluminum sulfate aqueous solution.
The preparation method of carbon sulfur composite positive pole the most according to claim 2, it is characterised in that the temperature of described roasting is 250～350 DEG C, time 4～10 hours.
CN201310696559.8A 2013-12-18 2013-12-18 Carbon-sulfur composite positive pole material and preparation method thereof Expired - Fee Related CN103746095B (en)

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Publication number Priority date Publication date Assignee Title
CN105118972B (en) * 2015-07-06 2017-05-17 浙江大学 Metal hydroxide coated carbon and sulfur lithium-sulfur battery positive electrode material, and preparation method and application thereof
CN106129352A (en) * 2016-07-04 2016-11-16 吉林大学 A kind of method and application being improved sulfur charge and discharge cycles ability by dopen Nano aluminium sesquioxide
CN114604892A (en) * 2022-03-24 2022-06-10 广东技术师范大学 Preparation method of double-doped hollow sphere material and application of double-doped hollow sphere material in lithium-sulfur battery

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CN102280614B (en) * 2011-07-07 2013-08-28 天津大学 Preparation method of sulfur positive electrode of lithium sulfur battery
CN103050669B (en) * 2011-10-17 2015-04-08 中国科学院大连化学物理研究所 Carbon-sulphur composite used for cathode material of lithium sulphur battery as well as preparation method and application thereof
CN103178247B (en) * 2013-03-22 2015-04-29 中南大学 Sulfur/carbon composite material and preparation method thereof

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