CN105304877B - Sulphur system positive electrode and preparation method thereof and a kind of battery - Google Patents
Sulphur system positive electrode and preparation method thereof and a kind of battery Download PDFInfo
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- CN105304877B CN105304877B CN201510759906.6A CN201510759906A CN105304877B CN 105304877 B CN105304877 B CN 105304877B CN 201510759906 A CN201510759906 A CN 201510759906A CN 105304877 B CN105304877 B CN 105304877B
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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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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 provides a kind of sulphur system positive electrode, shown in chemical formula such as formula (I) or formula (II)：S1‑xMx(I)；S1‑xMx/C(Ⅱ)；Wherein, 0<x<1；M is any one or more in Se, Te, I, P, Bi, Sn.Compared with existing sulphur positive electrode, material provided by the invention can effectively solve the problem that sulfur electrode material the problems such as intermediate product dissolving, has obtained excellent chemical property in cyclic process.The type material can be suitably used in the electrolyte of traditional lithium-ion battery simultaneously, further solve the compatibility issue that the material assembles full battery with other high performance lithium ion battery electrode materials.
Description
Technical field
The present invention relates to field of material technology, more particularly to a kind of sulphur system positive electrode and preparation method thereof and a kind of electricity
Pond.
Background technology
Lithium ion battery is a kind of secondary rechargeable battery, and relying primarily on lithium ion, movement carrys out work between a positive electrode and a negative electrode
Make.In charge and discharge process, Li+Insertion and deintercalation are come and gone between two electrodes：During charging, Li+From positive pole deintercalation, by electricity
Matter insertion negative pole is solved, negative pole is in rich lithium state；It is then opposite during electric discharge., can because its energy density per unit volume and specific energy are high
Fill and pollution-free, be widely used to the modern digital product such as mobile phone, notebook computer.
However, at present due to being limited by traditional positive electrode specific capacity and energy density, such as LiCoO2,LiMn2O4,
LiFePO4200mAh g are respectively less than Deng material specific capacity-1So that the energy density of commercialized lithium rechargeable battery is only
150-200Wh kg-1, it is difficult to further lifted, the demand of growing high accumulation power supply can not have been met.Therefore, grind
The new type lithium ion battery electrode material for sending out high-energy-density is particularly important.
Elemental sulfur positive electrode theoretical specific capacity is 1672mAh g-1, be traditional positive electrode it is octuple more than, with simple substance
The lithium-sulfur cell that sulphur is positive electrode, lithium metal is negative material composition, its energy density can reach 2600Wh kg-1, therefore,
Lithium-sulfur cell becomes the high-energy battery system of new generation that researcher competitively researches and develops.However, the practical application of lithium-sulfur cell still face
Face many problems, such as sulphur and discharging product lithium sulfide poorly conductive, there are 79% Volume Changes etc. in charge and discharge process.Its
In, caused polysulfide is soluble in electrolyte in cyclic process, and then triggers shuttle effect, causes active electrode material stream
Lose, the problem such as coulombic efficiency is low, be the main factor for limiting lithium-sulfur cell performance.Therefore, sulphur positive electrode storage lithium is improved
Can, suppress the dissolving of polysulfide intermediate, the especially dissolving on traditional lithium-ion battery electrolyte is urgently to be resolved hurrily
Matter of utmost importance.
Traditional method mainly carries out confinement using the various base materials such as carbon material to sulphur, to improve sulphur positive electrode
Store up lithium performance.If Canadian Nazar seminars are using the ordered mesopore carbon CMK-3 with Based on Dual-Aperture as base material, born in sulphur
20 circles are circulated when carrying capacity is 70wt%, under 0.168mA h g-1 current densities, specific capacity is maintained at 1000mA h g-1 (documents
1, Nat.Mater., 2009,8,500-506).But this method can only slow down rather than avoid the course of dissolution of polysulfide,
It can not tackle the problem at its root.
On the other hand, by using between sulphur positive electrode have stronger chemically interactive material as base
Bottom, dissolving and the shuttle effect of polysulfide can be largely reduced, and then improve the cyclical stability of battery.Such as to more
Hole carbon material carries out N doping, can improve the electronegativity of carbon material surface, increase to readily soluble Li2SxAbsorption, guest sunset method Buddhist nun
The Wang Donghai seminar of sub- state university and the Zhang Qiang seminars of Peking University confirm carries out N doping to porous carbon substrate
The storage lithium performance (document 2, Angew.Chem., 2015,127,4399-4403 of sulphur positive pole can be improved；Document 3, Advanced
Materials,2014,26,6100-6105)。
At present, the chemical property of sulphur positive electrode how is further improved, is this area urgent problem to be solved.
The content of the invention
In view of this, the technical problem to be solved in the present invention be to provide a kind of sulphur system positive electrode and preparation method thereof with
A kind of and battery.
The invention provides a kind of sulphur system positive electrode, shown in chemical formula such as formula (I) or formula (II)：
S1-xMx(I)；
S1-xMx/C(Ⅱ)；
Wherein, 0<x<1；
M is any one or more in Se, Te, I, P, Bi, Sn.
Preferably, in the positive electrode, S molar content is more than 90%.
Present invention also offers a kind of preparation method of above-mentioned sulphur system positive electrode, including：
Sulphur powder is mixed with M, carbon substrate, under air-proof condition, co-melting reaction, obtains sulphur system positive electrode；
The M is any one or more in selenium powder, antimony powder, iodine, red phosphorus, bismuth, tin；
The addition of the carbon substrate is the 0%~80% of raw material gross mass.
Preferably, the carbon substrate is any one in graphene, porous carbon materials, CNT and CMK-3 or more
Kind.
Preferably, the sulphur powder and M mol ratio are (70:30)~(99.6:0.4).
Preferably, the sulphur powder and M mol ratio are (9~99)：1.
Preferably, the temperature of the co-melting reaction is 60 DEG C~500 DEG C, and the time is 30min~120h.
Preferably, it is described to be mixed into ball milling mixing.
Present invention also offers a kind of battery, the sulphur system positive pole prepared with above-mentioned sulphur system positive electrode or above-mentioned preparation method
Material is positive electrode.
The invention provides a kind of sulphur system positive electrode, shown in chemical formula such as formula (I) or formula (II)：S1-xMx(I)；S1-xMx/
C(Ⅱ)；Wherein, 0<x<1；M is any one or more in Se, Te, I, P, Bi, Sn.Compared with existing sulphur positive electrode,
Material provided by the invention can effectively solve the problem that sulfur electrode material the problems such as intermediate product dissolving, has obtained excellent in cyclic process
Good chemical property.The type material can be suitably used in the electrolyte of traditional lithium-ion battery simultaneously, further solve
The material assembles the compatibility issue of full battery with other high performance lithium ion battery electrode materials.Wherein, prepared by the present invention
S1-xMx/ C-material, during for lithium battery anode, show close far above the specific capacity and energy of business anode material of lithium battery
Degree.Meanwhile the material further can also be applied in sode cell.Test result indicates that S prepared by the present invention1-xSex/ C materials
Material, applied in lithium-sulfur cell, under common esters electrolyte, its lithium storage content may be up to 1050mAh/g, and have long circulating
In the life-span, capacity is maintained at 953mAh/g after circulation 500 is enclosed.
Present invention also offers a kind of preparation method of above-mentioned sulphur system positive electrode, including：Sulphur powder and M, carbon substrate are mixed
Close, under air-proof condition, co-melting reaction, obtain sulphur system positive electrode；The M is in selenium powder, antimony powder, iodine, red phosphorus, bismuth, tin
Any one or more；The addition of the carbon substrate is the 0%~80% of raw material gross mass.The present invention directly uses elemental sulfur
For raw material, co-melting reaction is carried out, raw material is cheap and easily-available, greatly reduces reaction cost, while has extensive universality, required
Temperature it is relatively low, preparation flow environmental protection, yield is high, is produced beneficial to amplification；Being total to for one or more kinds of elements can be realized simultaneously
Melt and close.
Brief description of the drawings
Fig. 1 is S prepared by the embodiment of the present invention 11-xSexThe x-ray diffraction spectrum of/C (x=0.1) material at different temperatures
Figure；
Fig. 2 is the scanning electron microscope (SEM) photograph of the embodiment of the present invention 1；
Fig. 3 is the transmission electron microscope picture of the embodiment of the present invention 1；
Fig. 4 is S prepared by the embodiment of the present invention 21-xSex(x=0.1) the x-ray diffraction spectrum of material at different temperatures
Figure；
Fig. 5 is S prepared by the embodiment of the present invention 31-xSexX-ray diffraction spectrogram of/C (x=0.2) materials at 260 DEG C；
Fig. 6 is the S that embodiment 9 obtains1-xSexThe lithium-sulfur cell charging and discharging curve figure of/C (x=0.1) material；
Fig. 7 is the S that embodiment 9 obtains1-xSexThe lithium-sulfur cell electrochemical cycle stability figure of/C (x=0.1) material；
Fig. 8 is the S that embodiment 9 obtains1-xSexThe lithium-sulfur cell electrochemistry high rate performance figure of/C (x=0.1) material；
Fig. 9 is the S that embodiment 9 obtains1-xSexThe sodium-sulphur battery electrochemical cycle stability figure of/C (x=0.1) material；
Figure 10 is the S that embodiment 9 obtains1-xSexThe sodium-sulphur battery electrochemistry high rate performance figure of/C (x=0.1) material；
Figure 11 is the S that embodiment 9 obtains1-xPx-yIyThe lithium-sulfur cell charge and discharge of/CMK-3 (x=0.07, y=0.02) material
Electric curve map；
Figure 12 is the S that embodiment 9 obtains1-xPx-yIyThe lithium-sulfur cell electrification of/CMK-3 (x=0.07, y=0.02) material
Learn stable circulation figure；
Figure 13 is the S that embodiment 9 obtains1-xBixThe lithium-sulfur cell charging and discharging curve figure of/C (x=0.03) material；
Figure 14 is the S that embodiment 9 obtains1-xBixThe lithium-sulfur cell electrochemical cycle stability figure of/C (x=0.03) material.
Embodiment
The invention provides a kind of sulphur system positive electrode, shown in chemical formula such as formula (I) or formula (II)：S1-xMx(I)；S1-xMx/
C(Ⅱ)；Wherein, 0<x<1；M is any one or more in Se, Te, I, P, Bi, Sn.
Compared with existing sulphur positive electrode, material provided by the invention can effectively solve the problem that sulfur electrode material is being circulated throughout
The problems such as intermediate product dissolves in journey, has obtained excellent chemical property.Simultaneously the type material can be suitably used for conventional lithium from
In the electrolyte of sub- battery, further solve the material and other high performance full electricity of lithium ion battery electrode material assembling
The compatibility issue in pond.S prepared by the present invention1-xMx/ C-material, during for lithium battery anode, show far above business lithium electricity
The specific capacity and energy density of pond positive electrode.Meanwhile the material further can also be applied in sode cell.Experimental result table
Bright, prepared by present invention S1-xSex/ C-material, applied in lithium-sulfur cell, under common esters electrolyte, its lithium storage content can
Up to 1050mAh/g, and there is long circulation life, capacity is maintained at 953mAh/g after the circle of circulation 500.
Preferably, in positive electrode of the present invention, S molar content is more than 90%.In the present invention, the S's rubs
Your content refers to S and the mol ratio of S, M total amount in material.
Positive electrode provided by the invention, in addition to Se elements, P, I, Te, Bi, Sn element are also introduced, wherein, P, I and Te
All there is lower toxicity, it is relatively friendly to environment, meanwhile, P has relatively low molecular mass, can effectively reduce hetero atom
Introduce the influence reduced to material energy densities；I introducing can improve voltage platform.
Present invention also offers a kind of preparation method of above-mentioned sulphur system positive electrode, including：
Sulphur powder is mixed with M, carbon substrate, under air-proof condition, co-melting reaction, obtains sulphur system positive electrode；
The M is any one or more in selenium powder, antimony powder, iodine, red phosphorus, bismuth, tin；
The addition of the carbon substrate be raw material gross mass 0%~80%, more preferably the 0% of raw material gross mass~
70%, in some embodiments of the invention, the addition of the carbon substrate is the 40%~70% of raw material gross mass.
Wherein, the sulphur powder and M mol ratio are preferably (70:30)~(99.6:0.4), more preferably (9~99)：1.
In the present invention, the carbon substrate is preferably any one in graphene, porous carbon materials, CNT and CMK-3
Kind is a variety of.
The present invention is to above-mentioned sulphur powder, selenium powder, antimony powder, iodine, red phosphorus, bismuth, tin and graphene, porous carbon materials, carbon nanometer
Pipe and CMK-3 are simultaneously not particularly limited, common commercially available.Wherein, porous carbon materials can also use transition metal complex heat
Decomposition is prepared.
First, sulphur powder being mixed with M, carbon substrate, the mixing can be hybrid mode well known to those skilled in the art,
Be ball milling mixing in some specific embodiments, preferably plus deionized water wet ball grinding, time of the ball milling be preferably 1h~
72h, more preferably 5h~24h.
Material after ball milling is sealed in reactor, carries out co-melting reaction.In the present invention, the temperature of the co-melting reaction is excellent
Elect 60 DEG C~500 DEG C, more preferably 150 DEG C~400 DEG C as；Time is preferably 30min~120h, more preferably 5h~24h.
In some embodiments of the invention, the reaction is carried out in autoclave.
S prepared by the present invention1-xMxIn terms of/C products are mainly used in electrochemical energy storage, the product system that will be prepared
Into lithium battery pole slice, as positive electrode, can also can be assembled into lithium piece electrode assembling into lithium-sulfur cell with sodium plate electrode
Sodium-sulphur battery, it can further use the assembling of the full batteries of carry out such as the negative material such as graphite cathode of business.When the material is used
When lithium sulfur battery anode material, shown in the esters electrolyte of business higher lithium storage content, high coulombic efficiency and
Long cyclical stability.
Present invention also offers a kind of battery, the sulphur system positive pole prepared with above-mentioned sulphur system positive electrode or above-mentioned preparation method
Material is positive electrode.
Currently preferred, the battery is lithium-sulfur cell or sodium-sulphur battery.
In order to further illustrate the present invention, with reference to embodiment to sulphur system provided by the invention positive electrode and its preparation
Method and a kind of battery are described in detail.
Embodiment 1 prepares S using porous carbon materials as substrate1-xSex/ C (x=0.1) material.
5 grams of sulphur powders, 1.2 grams of selenium powders and 4 grams of porous carbons are taken, after wet ball grinding 24h mixing, are sealed in 10mL reaction
In kettle, it is placed under electrical crucible, 10h is reacted in 220 DEG C, then naturally cools to room temperature；S can be obtained after driving kettle1- xSex/ C (x=0.1) material.
S using X light powder diffraction instrument to preparation1-xSex/ C (x=0.1) material carries out X light diffracting analysis, and Fig. 1 is this
S prepared by inventive embodiments 11-xSexThe x-ray diffraction spectrogram of/C (x=0.1) material at different temperatures.It can be seen by Fig. 1
Go out, 2 θ only have high-visible amorphous diffraction maximum bag in the range of 10~80 ° in x-ray diffraction spectra, it was demonstrated that the material is amorphous
The structure of phase.
Material structure is detected using ESEM and transmission electron microscope, as a result sees Fig. 2 and Fig. 3, wherein, Fig. 2 is this
The scanning electron microscope (SEM) photograph of inventive embodiments 1, Fig. 3 are the transmission electron microscope pictures of the embodiment of the present invention 1, from Fig. 2 and Fig. 3, the present invention
The S of preparation1-xSex/ C (x=0.1) material be size about 30nm nano-porous structure, hole be evenly distributed on several nanometers (<
In the range of 10nm).
Material component is analyzed using atomic absorption spectrum, as a result shows the sulfur content of the material and rubbing for Se content
That ratio about 9:1, i.e. S molar content is 90%.
Embodiment 2
5 grams of sulphur powders and 1.2 grams of selenium powders are taken, after wet ball grinding 24h mixing, is sealed in 10mL reactor, is placed in electricity
Hinder under crucible furnace, 10h is reacted in 200 DEG C, then naturally cools to room temperature；S can be obtained after driving kettle1-xSex(x=0.1) material
Material.
S using X light powder diffraction instrument to preparation1-xSex(x=0.1) material carries out X light diffracting analysis, as a result sees Fig. 4,
Fig. 4 is S prepared by the embodiment of the present invention 21-xSex(x=0.1) the x-ray diffraction spectrogram of material at different temperatures.Can by Fig. 4
To find out, after temperature is more than 110 DEG C, the XRD of product corresponds to the structure of similar monoclinic phase sulphur.
Material structure is detected using ESEM and transmission electron microscope, the results showed that, S prepared by the present invention1-xSex
(x=0.1) material be size about 200nm nano-porous structure, hole be evenly distributed on several nanometers (<In the range of 10nm).
Material component is analyzed using atomic absorption spectrum, as a result shows the sulfur content of the material and rubbing for Se content
That ratio about 9:1.
Embodiment 3
5 grams of sulphur powders and 2.4 grams of selenium powders, 6 grams of porous carbons are taken, after wet ball grinding 24h mixing, are sealed in 10mL reactor
It is interior, it is placed under electrical crucible, 10h is reacted in 200 DEG C, then naturally cools to room temperature；S can be obtained after driving kettle1-xSex/
C (x=0.2) material.
S using X light powder diffraction instrument to preparation1-xSex/ C (x=0.2) material carries out X light diffracting analysis, as a result sees figure
5, Fig. 5 be S prepared by the embodiment of the present invention 31-xSexThe x-ray diffraction spectrogram of/C (x=0.2) material at different temperatures.By
It is noncrystalline structure that Fig. 5, which can be seen that the material,.
Material structure is detected using ESEM and transmission electron microscope, the results showed that, S prepared by the present invention1-xSex/
C (x=0.2) material be size about 30nm nano-porous structure, hole be evenly distributed on several nanometers (<In the range of 10nm).
Material component is analyzed using atomic absorption spectrum, as a result shows the sulfur content of the material and rubbing for Se content
That ratio about 4:1.
Embodiment 4
5 grams of sulphur powders and 1.9 grams of antimony powders, 4 grams of porous carbons are taken, after wet ball grinding 24h mixing, are sealed in 10mL reactor
It is interior, it is placed under electrical crucible, 10h is reacted in 300 DEG C, then naturally cools to room temperature；S can be obtained after driving kettle1-xTex/
C (x=0.1) material.
S using X light powder diffraction instrument to preparation1-xTex/ C (x=0.1) material carries out X light diffracting analysis, as a result table
Bright, the material is noncrystalline structure.
Material structure is detected using ESEM and transmission electron microscope, the results showed that, S prepared by the present invention1-xTex/
C (x=0.1) material be size about 30nm nano-porous structure, hole be evenly distributed on several nanometers (<In the range of 10nm).
Material component is analyzed using atomic absorption spectrum, as a result shows the sulfur content of the material and rubbing for antimony content
That ratio about 9:1.
Embodiment 5
5 grams of sulphur powders, 0.6 gram of selenium powder, 0.95 gram of antimony powder, 4 grams of porous carbons are taken, after wet ball grinding 24h mixing, are sealed in
In 10mL reactor, it is placed under electrical crucible, 10h is reacted in 350 DEG C, then naturally cools to room temperature；Open after kettle i.e.
S can be obtained1-xSex-yTey/ C (x=0.1, y=0.05) material.
S using X light powder diffraction instrument to preparation1-xSex-yTey/ C (x=0.1, y=0.05) material carries out X-ray diffraction
Analysis, the results showed that, the material is noncrystalline structure.
Material structure is detected using ESEM and transmission electron microscope, the results showed that, S prepared by the present invention1-xSex- yTey/ C (x=0.1, y=0.05) material be size about 30nm nano-porous structure, hole be evenly distributed on several nanometers (<
In the range of 10nm).
Material component is analyzed using atomic absorption spectrum, the sulfur content and selenium, antimony for as a result showing the material always contain
The mol ratio of amount is about 9:1.
Embodiment 6
5 grams of sulphur powders, 1.2 grams of selenium powders and 1 gram of graphene mixing are taken, 100mg/mL slurry is dissipated to using moisture, through wet
After method ball milling 24h mixing, it is sealed in 10mL reactor, is placed under electrical crucible, 10h is reacted in 200 DEG C, then certainly
So it is cooled to room temperature；S can be obtained after driving kettle1-xSex/ G (x=0.1) material.
S using X light powder diffraction instrument to preparation1-xSex/ G (x=0.1) material carries out X light diffracting analysis, as a result table
Bright, the material is noncrystalline structure.
Material structure is detected using ESEM and transmission electron microscope, the results showed that, S prepared by the present invention1-xSex/
G (x=0.1) material be size about 50nm nano-porous structure, hole be evenly distributed on several nanometers (<In the range of 10nm).
Material component is analyzed using atomic absorption spectrum, as a result shows the sulfur content of the material and rubbing for Se content
That ratio about 9:1.
Embodiment 7
5 grams of sulphur powders, 0.25 gram of red phosphorus powder, 0.41 gram of iodine and 1 gram of CMK-3 mixing are taken, is mixed through wet ball grinding 24h
Afterwards, it is sealed in 10mL reactor, is placed under electrical crucible, 10h is reacted in 280 DEG C, then naturally cools to room temperature；
S can be obtained after driving kettle1-xPx-yIy/ CMK-3 (x=0.07, y=0.02) material.
S using X light powder diffraction instrument to preparation1-xPx-yIy/ CMK-3 (x=0.07, y=0.02) material carries out X-ray and spread out
Penetrate analysis, the results showed that, the material is noncrystalline structure.
Material structure is detected using ESEM and transmission electron microscope, the results showed that, S prepared by the present invention1-xPx- yIy/ CMK-3 (x=0.07, y=0.02) material is size about 40nm nano-porous structure, and hole is evenly distributed on several nanometers
(<In the range of 10nm).
Material component is analyzed using atomic absorption spectrum, the sulfur content and phosphorus, iodine for as a result showing the material always contain
The mol ratio of amount is about 93:7.
Embodiment 8
5 grams of sulphur powders, 1 gram of bismuth meal and 4 grams of porous carbon mixing are taken, after wet ball grinding 24h mixing, are sealed in the anti-of 10mL
Answer in kettle, be placed under electrical crucible, 10h is reacted in 280 DEG C, then naturally cools to room temperature；S can be obtained after driving kettle1- xBix/ C (x=0.03) material.
S using X light powder diffraction instrument to preparation1-xBix/ C (x=0.03) material carries out X light diffracting analysis, as a result table
It is bright, except Bi2S3Diffraction maximum outside without other peaks.
Material structure is detected using ESEM and transmission electron microscope, the results showed that, S prepared by the present invention1-xBix/
C (x=0.03) material be size about 40nm nano-porous structure, hole be evenly distributed on several nanometers (<In the range of 10nm).
Embodiment 9
The S respectively prepared by embodiment 11-xSex/ C (x=0.1) material, S prepared by embodiment 71-xPx-yIy/ CMK-3, is applied
S prepared by example 81-xBixCR2016 type button-type battery electrode pieces are made in/C-material, and electrode slice uses 70wt% corresponding embodiment
Sulphur system positive electrode, 10wt% sodium alginate, 20% conductive black, the water of preparation mix, and the substrate of electrode film is
Metal aluminum foil.
Lithium piece is used as to electrode, polyolefin porous membrane (Celgard 2500) is barrier film, with LiPF6Ethylene carbonate
And dimethyl carbonate (DMC) (volume ratio 1 (EC):1) mixed solution is dressed up as electrolyte in the glove box of argon gas atmosphere
CR2016 lithium-sulfur cells.
Sodium piece is used as to electrode, polyolefin porous membrane (Celgard 2500) is barrier film, with NaPF6Ethylene carbonate
And dimethyl carbonate (DMC) (volume ratio 1 (EC):1) mixed solution is dressed up as electrolyte in the glove box of argon gas atmosphere
CR2016 sodium-sulphur batteries.
To S1-xSexThe lithium-sulfur cell and sodium-sulphur battery of/C (x=0.1) assemblings carry out chemical property detection, lithium-sulfur cell
Results of property see Fig. 6~Fig. 8, Fig. 6 be embodiment 9 prepare lithium-sulfur cell in 0.2A g-1Discharge and recharge under current density is bent
Line chart, wherein, curve a is the charging and discharging curve figure of first lap, and curve b is the charging and discharging curve figure of the second circle, and curve c is the 3rd
The charging and discharging curve figure of circle, curve d are the charging and discharging curve figure of the 4th circle, and curve e is the charging and discharging curve figure of the 5th circle；Fig. 7
Be embodiment 9 prepare lithium-sulfur cell in 0.5A g-1Electrochemical cycle stability figure under current density, Fig. 8 are prepared by embodiment 9
The electrochemistry high rate performance figure of lithium-sulfur cell, as seen from Figure 6, current density are 0.2A g-1When, the first circle storehouse of lithium-sulfur cell
Human relations efficiency is 55%, and subsequent coulombic efficiency is maintained at more than 99.5%.In the figure 7, by 0.2A g-1Under low current density
After pre- circulation, lithium-sulfur cell is in 0.5A g-1Under current density after the circle of circulation 500, reversible specific capacity remains to be maintained at 953mAh g-1, show excellent cyclical stability.In Fig. 8 high rate performance test, the lithium-sulfur cell of assembling is in 20A g-1Electric current is close
Under degree, specific capacity still has 572mAh g-1, show that it has excellent high rate performance.
S1-xSexThe performance of the sodium-sulphur battery of/C (x=0.1) assemblings is as shown in figs. 9-10.Fig. 9 is the sodium-sulphur battery of assembling
In 0.2A g-1Cycle performance under current density, first circle coulombic efficiency are about 52%, and after the circle of circulation 150, reversible specific capacity is kept
In 937mAh g-1.In Figure 10 high rate performance test, the sodium-sulphur battery of assembling is in 20A g-1Under current density, specific capacity is still
There are 328mAh g-1, show that it has preferable high rate performance.
S1-xPx-yIyThe performance of the lithium-sulfur cell of/CMK-3C assemblings is as depicted in figs. 11-12.Wherein, Figure 11 is that embodiment 9 obtains
The S arrived1-xPx-yIyThe lithium-sulfur cell charging and discharging curve figure of/CMK-3 (x=0.07, y=0.02) material, curve 1 are the battery
First charge-discharge curve, curve 2,3 correspond respectively to second, third time charging and discharging curve；Figure 12 is the lithium-sulfur cell of assembling
In 0.2A g-1Electrochemical cycle stability figure under current density, as seen from Figure 12, first circle coulombic efficiency is about 63%, circulation 350
After circle, reversible specific capacity is maintained at 837mAh g-1。
S1-xBixThe performance of the lithium-sulfur cell of/C assemblings is as illustrated in figs. 13-14.Wherein, Figure 13 is the S that embodiment 9 obtains1- xBixThe lithium-sulfur cell charging and discharging curve figure of/C (x=0.03) material, curve 1 be the battery first charge-discharge curve, curve 2,
3 correspond respectively to second, third time charging and discharging curve；Figure 14 is the lithium-sulfur cell of assembling in 0.2A g-1Under current density
Electrochemical cycle stability figure, as seen from Figure 14, first circle coulombic efficiency are about 72%, and after the circle of circulation 300, reversible specific capacity is maintained at
885mAh g-1。
As can be seen from the above-described embodiment, the battery prepared using sulphur system provided by the invention positive electrode, have excellent
Chemical property.
The explanation of above example is only intended to help the method and its core concept for understanding the present invention.It should be pointed out that pair
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (8)
1. shown in a kind of sulphur system positive electrode, chemical formula such as formula (I) or formula (II)：
S1-xMx(I)；
S1-xMx/C(Ⅱ)；
Wherein, 0<x<1；
M is any one or more in Te, I, P, Bi, Sn；
In the positive electrode, S molar content is more than 90%；The molar content of the S refers to rubbing for S and S, M total amount in material
That ratio.
2. a kind of preparation method of the sulphur system positive electrode described in claim 1, including：
Sulphur powder is mixed with M, carbon substrate, under air-proof condition, co-melting reaction, obtains sulphur system positive electrode；
The M is any one or more in antimony powder, iodine, red phosphorus, bismuth, tin；
The addition of the carbon substrate is the 0%~80% of raw material gross mass.
3. preparation method according to claim 2, it is characterised in that the carbon substrate is graphene, porous carbon materials, carbon
Any one or more in nanotube and CMK-3.
4. preparation method according to claim 2, it is characterised in that the sulphur powder and M mol ratio are (70:30)~
(99.6:0.4)。
5. preparation method according to claim 4, it is characterised in that the sulphur powder and M mol ratio are (9~99)：1.
6. preparation method according to claim 2, it is characterised in that the temperature of the co-melting reaction is 60 DEG C~500 DEG C,
Time is 30min~120h.
7. preparation method according to claim 2, it is characterised in that described to be mixed into ball milling mixing.
A kind of 8. battery, with the system described in any one of the sulphur system positive electrode described in claim 1 or claim 2~7
Sulphur system positive electrode prepared by Preparation Method is positive electrode.
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