CN105304877A - Sulfur-series anode material, preparation method thereof and battery - Google Patents
Sulfur-series anode material, preparation method thereof and battery Download PDFInfo
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- CN105304877A CN105304877A CN201510759906.6A CN201510759906A CN105304877A CN 105304877 A CN105304877 A CN 105304877A CN 201510759906 A CN201510759906 A CN 201510759906A CN 105304877 A CN105304877 A CN 105304877A
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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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- 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 sulfur-series anode material. The chemical formula is as indicated by formula (I) S<1-x>M<x> or formula (II) S<1-x>M<x>/C, wherein x is greater than 0 and less than 1; M is one or more of Se, Te, I, P, Bi and Sn. Compared with an existing sulfur anode material, the sulfur-series anode material can be used for effectively solving the problem that in the circulation process, an intermediate product of the sulfur anode material is dissolved, and excellent electrochemical performance is obtained. Meanwhile, the material can be applied to electrolyte of a conventional lithium ion battery, and the compatibility problem of a complete battery assembled with the material and other high-performance lithium ion battery electrode materials is further solved.
Description
Technical field
The present invention relates to field of material technology, particularly relate to a kind of sulphur system positive electrode and preparation method thereof and a kind of battery.
Background technology
Lithium ion battery is a kind of secondary rechargeable battery, and main dependence lithium ion between a positive electrode and a negative electrode movement carrys out work.In charge and discharge process, Li
+come and go between two electrodes and embed and deintercalation: during charging, Li
+from positive pole deintercalation, embed negative pole through electrolyte, negative pole is in rich lithium state; Then contrary during electric discharge.Due to its volumetric specific energy and specific energy high, can to fill and pollution-free, to be widely used in the modern number such as mobile phone, notebook computer code product.
But, at present owing to being subject to the restriction of traditional positive electrode specific capacity and energy density, as LiCoO
2, LiMn
2o
4, LiFePO
4all 200mAhg is less than Deng material specific capacity
-1, make the energy density of business-like lithium rechargeable battery be only 150-200Whkg
-1, be difficult to be promoted further, cannot have met the demand of growing high accumulation power supply.Therefore, the new type lithium ion battery electrode material researching and developing high-energy-density is particularly important.
Elemental sulfur positive electrode theoretical specific capacity is 1672mAhg
-1, be more than the octuple of traditional positive electrode, take elemental sulfur as positive electrode, lithium-sulfur cell that lithium metal forms for negative material, its energy density can reach 2600Whkg
-1, therefore, lithium-sulfur cell becomes the high-energy battery system of new generation that researcher competitively researches and develops.But the practical application of lithium-sulfur cell is still faced with a lot of problem, as sulphur and discharging product lithium sulfide poorly conductive, in charge and discharge process, there is the change in volume etc. of 79%.Wherein, the polysulfide produced in cyclic process is soluble in electrolyte, and then causes effect of shuttling back and forth, and causes the problems such as active electrode material runs off, coulombic efficiency is low, is the main factor of restriction lithium-sulfur cell performance.Therefore, improve sulphur positive electrode storage lithium performance, suppress the dissolving of polysulfide intermediate, the dissolving especially on traditional lithium-ion battery electrolyte is matter of utmost importance urgently to be resolved hurrily.
Traditional method mainly utilizes the various base materials such as material with carbon element to carry out confinement to sulphur, to improve sulphur positive electrode storage lithium performance.If Canadian Nazar seminar is using having the ordered mesopore carbon CMK-3 of Based on Dual-Aperture as base material, when sulphur load capacity is 70wt%, circulate under 0.168mAhg-1 current density 20 circles, specific capacity remains on 1000mAhg-1 (document 1, Nat.Mater., 2009,8,500-506).But this method can only slow down instead of avoid the course of dissolution of polysulfide, can not tackle the problem at its root.
On the other hand, there is stronger chemically interactive material as substrate by adopting between sulphur positive electrode, the dissolving of polysulfide and effect of shuttling back and forth can be reduced largely, and then improve the cyclical stability of battery.Such as N doping is carried out to porous carbon materials, the electronegativity of carbon material surface can be improved, increase the Li that commute is molten
2s
xabsorption, the Wang Donghai seminar of Pennsylvania State University and the Zhang Qiang seminar of Peking University all confirm and carry out to porous carbon substrate storage lithium performance (document 2, Angew.Chem., 2015,127, the 4399-4403 that N doping can improve sulphur positive pole; Document 3, AdvancedMaterials, 2014,26,6100-6105).
At present, how improving the chemical property of sulphur positive electrode further, is this area problem demanding prompt solution.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of sulphur system positive electrode and preparation method thereof and a kind of battery.
The invention provides a kind of sulphur system positive electrode, chemical formula is such as formula shown in (I) or formula (II):
S
1-xM
x(I)；
S
1-xM
x/C(Ⅱ)；
Wherein, 0<x<1;
M be in Se, Te, I, P, Bi, Sn any one or multiple.
Preferably, in described positive electrode, the molar content of S is greater than 90%.
Present invention also offers the preparation method of a kind of above-mentioned sulphur system positive electrode, comprising:
Sulphur powder is mixed with M, carbon substrate, under air-proof condition, melts reaction altogether, obtain sulphur system positive electrode;
Described M be in selenium powder, antimony powder, iodine, red phosphorus, bismuth, tin any one or multiple;
The addition of described carbon substrate is 0% ~ 80% of raw material gross mass.
Preferably, described carbon substrate be in Graphene, porous carbon materials, carbon nano-tube and CMK-3 any one or multiple.
Preferably, the mol ratio of described sulphur powder and M is (70:30) ~ (99.6:0.4).
Preferably, the mol ratio of described sulphur powder and M is (9 ~ 99): 1.
Preferably, described temperature of melting reaction is altogether 60 DEG C ~ 500 DEG C, and the time is 30min ~ 120h.
Preferably, ball milling mixing is mixed into described in.
Present invention also offers a kind of battery, the sulphur system positive electrode prepared with above-mentioned sulphur system positive electrode or above-mentioned preparation method is for positive electrode.
The invention provides a kind of sulphur system positive electrode, chemical formula is such as formula shown in (I) or formula (II): S
1-xm
x(I); S
1-xm
x/ C (II); Wherein, 0<x<1; M be in Se, Te, I, P, Bi, Sn any one or multiple.Compared with existing sulphur positive electrode, material provided by the invention effectively can solve sulfur electrode material problem such as intermediate product dissolving in cyclic process, obtains excellent chemical property.Simultaneously the type material can be applicable in the electrolyte of traditional lithium-ion battery, further solves the compatibility issue that this material and other high performance lithium ion battery electrode materials assemble full battery.Wherein, the S for preparing of the present invention
1-xm
x/ C material, during for lithium battery anode, demonstrates the specific capacity far above business anode material of lithium battery and energy density.Meanwhile, this material also can further be applied in sode cell.Experimental result shows, S prepared by the present invention
1-xse
x/ C material, is applied in lithium-sulfur cell, and under normal ester class electrolyte, its lithium storage content up to 1050mAh/g, and can have long circulation life, and after circulation 500 circle, capacity remains on 953mAh/g.
Present invention also offers the preparation method of a kind of above-mentioned sulphur system positive electrode, comprising: sulphur powder is mixed with M, carbon substrate, under air-proof condition, melt reaction altogether, obtain sulphur system positive electrode; Described M be in selenium powder, antimony powder, iodine, red phosphorus, bismuth, tin any one or multiple; The addition of described carbon substrate is 0% ~ 80% of raw material gross mass.The present invention directly adopts elemental sulfur to be raw material, and melt reaction altogether, raw material is cheaply easy to get, and greatly reduces reaction cost, has universality widely simultaneously, and required temperature is lower, preparation flow environmental protection, and productive rate is high, is beneficial to amplify to produce; The common thawing that simultaneously can realize one or more elements is closed.
Accompanying drawing explanation
Fig. 1 is S prepared by the embodiment of the present invention 1
1-xse
x/ C (x=0.1) material x-ray diffraction spectrogram at different temperatures;
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 2
1-xse
x(x=0.1) material x-ray diffraction spectrogram at different temperatures;
Fig. 5 is S prepared by the embodiment of the present invention 3
1-xse
x/ C (x=0.2) material is at the x-ray diffraction spectrogram of 260 DEG C;
Fig. 6 is the S that embodiment 9 obtains
1-xse
xthe lithium-sulfur cell charging and discharging curve figure of/C (x=0.1) material;
Fig. 7 is the S that embodiment 9 obtains
1-xse
xthe lithium-sulfur cell electrochemical cycle stability figure of/C (x=0.1) material;
Fig. 8 is the S that embodiment 9 obtains
1-xse
xthe lithium-sulfur cell electrochemistry high rate performance figure of/C (x=0.1) material;
Fig. 9 is the S that embodiment 9 obtains
1-xse
xthe sodium-sulphur battery electrochemical cycle stability figure of/C (x=0.1) material;
Figure 10 is the S that embodiment 9 obtains
1-xse
xthe sodium-sulphur battery electrochemistry high rate performance figure of/C (x=0.1) material;
Figure 11 is the S that embodiment 9 obtains
1-xp
x-yi
ythe lithium-sulfur cell charging and discharging curve figure of/CMK-3 (x=0.07, y=0.02) material;
Figure 12 is the S that embodiment 9 obtains
1-xp
x-yi
ythe lithium-sulfur cell electrochemical cycle stability figure of/CMK-3 (x=0.07, y=0.02) material;
Figure 13 is the S that embodiment 9 obtains
1-xbi
xthe lithium-sulfur cell charging and discharging curve figure of/C (x=0.03) material;
Figure 14 is the S that embodiment 9 obtains
1-xbi
xthe lithium-sulfur cell electrochemical cycle stability figure of/C (x=0.03) material.
Embodiment
The invention provides a kind of sulphur system positive electrode, chemical formula is such as formula shown in (I) or formula (II): S
1-xm
x(I); S
1-xm
x/ C (II); Wherein, 0<x<1; M be in Se, Te, I, P, Bi, Sn any one or multiple.
Compared with existing sulphur positive electrode, material provided by the invention effectively can solve sulfur electrode material problem such as intermediate product dissolving in cyclic process, obtains excellent chemical property.Simultaneously the type material can be applicable in the electrolyte of traditional lithium-ion battery, further solves the compatibility issue that this material and other high performance lithium ion battery electrode materials assemble full battery.S prepared by the present invention
1-xm
x/ C material, during for lithium battery anode, demonstrates the specific capacity far above business anode material of lithium battery and energy density.Meanwhile, this material also can further be applied in sode cell.Experimental result shows, S prepared by the present invention
1-xse
x/ C material, is applied in lithium-sulfur cell, and under normal ester class electrolyte, its lithium storage content up to 1050mAh/g, and can have long circulation life, and after circulation 500 circle, capacity remains on 953mAh/g.
As preferably, in positive electrode of the present invention, the molar content of S is greater than 90%.In the present invention, the molar content of described S refers to the mol ratio of S and S in material, M total amount.
Positive electrode provided by the invention, except Se element, also introduce P, I, Te, Bi, Sn element, wherein, P, I and Te have lower toxicity, to environment facies to close friend, simultaneously, P has lower molecular mass, can effectively reduce hetero-atom and introduce the impact reduced material energy densities; The introducing of I can improve voltage platform.
Present invention also offers the preparation method of a kind of above-mentioned sulphur system positive electrode, comprising:
Sulphur powder is mixed with M, carbon substrate, under air-proof condition, melts reaction altogether, obtain sulphur system positive electrode;
Described M be in selenium powder, antimony powder, iodine, red phosphorus, bismuth, tin any one or multiple;
The addition of described carbon substrate is 0% ~ 80% of raw material gross mass, is more preferably 0% ~ 70% of raw material gross mass, and in some embodiments of the invention, the addition of described carbon substrate is 40% ~ 70% of raw material gross mass.
Wherein, the mol ratio of described sulphur powder and M is preferably (70:30) ~ (99.6:0.4), is more preferably (9 ~ 99): 1.
In the present invention, described carbon substrate be preferably in Graphene, porous carbon materials, carbon nano-tube and CMK-3 any one or multiple.
The present invention there is no particular determination to above-mentioned sulphur powder, selenium powder, antimony powder, iodine, red phosphorus, bismuth, tin and Graphene, porous carbon materials, carbon nano-tube and CMK-3, common commercially available.Wherein, porous carbon materials can also adopt transition metal complex thermal decomposition to prepare.
First, mixed with M, carbon substrate by sulphur powder, described mixing can be hybrid mode well known to those skilled in the art, in some specific embodiment, be ball milling mixing, preferably add deionized water wet ball grinding, the time of described ball milling is preferably 1h ~ 72h, is more preferably 5h ~ 24h.
Material seal after ball milling, in reactor, melts reaction altogether.In the present invention, described temperature of melting reaction is altogether preferably 60 DEG C ~ 500 DEG C, is more preferably 150 DEG C ~ 400 DEG C; Time is preferably 30min ~ 120h, is more preferably 5h ~ 24h.
In some embodiments of the invention, described reaction is carried out in autoclave.
S prepared by the present invention
1-xm
x/ C product is mainly used in electrochemical energy storage aspect, the product prepared is made lithium battery pole slice, as positive electrode, lithium-sulfur cell can be assembled into lithium plate electrode, also can be assembled into sodium-sulphur battery with sodium plate electrode, the negative material of business such as graphite cathode etc. can be adopted further to carry out the assembling of full battery.When this material is used for lithium sulfur battery anode material, in the ester class electrolyte of business, show higher lithium storage content, high coulombic efficiency and long cyclical stability.
Present invention also offers a kind of battery, the sulphur system positive electrode prepared with above-mentioned sulphur system positive electrode or above-mentioned preparation method is for positive electrode.
The present invention is preferred, and described battery is lithium-sulfur cell or sodium-sulphur battery.
In order to further illustrate the present invention, below in conjunction with embodiment, sulphur system provided by the invention positive electrode and preparation method thereof and a kind of battery are described in detail.
Embodiment 1 take porous carbon materials as substrate, preparation S
1-xse
x/ C (x=0.1) material.
Get 5 grams of sulphur powder, 1.2 grams of selenium powders and 4 grams of porous carbons, after wet ball grinding 24h mixes, be sealed in the reactor of 10mL, under being placed in electrical crucible, in 220 DEG C, reacting 10h, then naturally cool to room temperature; S can be obtained after driving still
1-xse
x/ C (x=0.1) material.
Adopt X light powder diffraction instrument to the S of preparation
1-xse
x/ C (x=0.1) material carries out X light diffracting analysis, and Fig. 1 is S prepared by the embodiment of the present invention 1
1-xse
x/ C (x=0.1) material x-ray diffraction spectrogram at different temperatures.As seen from Figure 1, in x-ray diffraction spectra, 2 θ only have apparent amorphous diffraction maximum bag within the scope of 10 ~ 80 °, prove that this material is the structure of amorphous phase.
Adopt ESEM and transmission electron microscope to detect material structure, the results are shown in Figure 2 and Fig. 3, wherein, Fig. 2 is the scanning electron microscope (SEM) photograph of the embodiment of the present invention 1, and Fig. 3 is the transmission electron microscope picture of the embodiment of the present invention 1, from Fig. 2 and Fig. 3, and S prepared by the present invention
1-xse
x/ C (x=0.1) material is the nano-porous structure that size is about 30nm, and hole is evenly distributed in several nanometer (<10nm) scope.
Adopt atomic absorption spectrum to analyze material component, the mol ratio of sulfur content and Se content that result shows this material is about 9:1, and namely the molar content of S is 90%.
Embodiment 2
Get 5 grams of sulphur powder and 1.2 grams of selenium powders, after wet ball grinding 24h mixes, be sealed in the reactor of 10mL, under being placed in electrical crucible, in 200 DEG C, reacting 10h, then naturally cool to room temperature; S can be obtained after driving still
1-xse
x(x=0.1) material.
Adopt X light powder diffraction instrument to the S of preparation
1-xse
x(x=0.1) material carries out X light diffracting analysis, and the results are shown in Figure 4, Fig. 4 is S prepared by the embodiment of the present invention 2
1-xse
x(x=0.1) material x-ray diffraction spectrogram at different temperatures.As seen from Figure 4, after temperature is greater than 110 DEG C, the XRD of product corresponds to the structure of similar monoclinic phase sulphur.
Adopt ESEM and transmission electron microscope to detect material structure, result shows, S prepared by the present invention
1-xse
x(x=0.1) material is the nano-porous structure that size is about 200nm, and hole is evenly distributed in several nanometer (<10nm) scope.
Adopt atomic absorption spectrum to analyze material component, the mol ratio of sulfur content and Se content that result shows this material is about 9:1.
Embodiment 3
Get 5 grams of sulphur powder and 2.4 grams of selenium powders, 6 grams of porous carbons, after wet ball grinding 24h mixes, be sealed in the reactor of 10mL, under being placed in electrical crucible, in 200 DEG C, reacting 10h, then naturally cool to room temperature; S can be obtained after driving still
1-xse
x/ C (x=0.2) material.
Adopt X light powder diffraction instrument to the S of preparation
1-xse
x/ C (x=0.2) material carries out X light diffracting analysis, and the results are shown in Figure 5, Fig. 5 is S prepared by the embodiment of the present invention 3
1-xse
x/ C (x=0.2) material x-ray diffraction spectrogram at different temperatures.As seen from Figure 5, this material is noncrystalline structure.
Adopt ESEM and transmission electron microscope to detect material structure, result shows, S prepared by the present invention
1-xse
x/ C (x=0.2) material is the nano-porous structure that size is about 30nm, and hole is evenly distributed in several nanometer (<10nm) scope.
Adopt atomic absorption spectrum to analyze material component, the mol ratio of sulfur content and Se content that result shows this material is about 4:1.
Embodiment 4
Get 5 grams of sulphur powder and 1.9 grams of antimony powders, 4 grams of porous carbons, after wet ball grinding 24h mixes, be sealed in the reactor of 10mL, under being placed in electrical crucible, in 300 DEG C, reacting 10h, then naturally cool to room temperature; S can be obtained after driving still
1-xte
x/ C (x=0.1) material.
Adopt X light powder diffraction instrument to the S of preparation
1-xte
x/ C (x=0.1) material carries out X light diffracting analysis, and result shows, this material is noncrystalline structure.
Adopt ESEM and transmission electron microscope to detect material structure, result shows, S prepared by the present invention
1-xte
x/ C (x=0.1) material is the nano-porous structure that size is about 30nm, and hole is evenly distributed in several nanometer (<10nm) scope.
Adopt atomic absorption spectrum to analyze material component, the mol ratio of sulfur content and antimony content that result shows this material is about 9:1.
Embodiment 5
Get 5 grams of sulphur powder, 0.6 gram of selenium powder, 0.95 gram of antimony powder, 4 grams of porous carbons, after wet ball grinding 24h mixes, be sealed in the reactor of 10mL, under being placed in electrical crucible, in 350 DEG C, reacting 10h, then naturally cool to room temperature; S can be obtained after driving still
1-xse
x-yte
y/ C (x=0.1, y=0.05) material.
Adopt X light powder diffraction instrument to the S of preparation
1-xse
x-yte
y/ C (x=0.1, y=0.05) material carries out X light diffracting analysis, and result shows, this material is noncrystalline structure.
Adopt ESEM and transmission electron microscope to detect material structure, result shows, S prepared by the present invention
1-xse
x-yte
y/ C (x=0.1, y=0.05) material is the nano-porous structure that size is about 30nm, and hole is evenly distributed in several nanometer (<10nm) scope.
Adopt atomic absorption spectrum to analyze material component, result shows the sulfur content of this material and selenium, the mol ratio of antimony total content is about 9:1.
Embodiment 6
Get 5 grams of sulphur powder, 1.2 grams of selenium powders and 1 gram of Graphene mixing, adopt aqueous dispersion to the slurry of 100mg/mL, after wet ball grinding 24h mixes, be sealed in the reactor of 10mL, under being placed in electrical crucible, reacting 10h, then naturally cool to room temperature in 200 DEG C; S can be obtained after driving still
1-xse
x/ G (x=0.1) material.
Adopt X light powder diffraction instrument to the S of preparation
1-xse
x/ G (x=0.1) material carries out X light diffracting analysis, and result shows, this material is noncrystalline structure.
Adopt ESEM and transmission electron microscope to detect material structure, result shows, S prepared by the present invention
1-xse
x/ G (x=0.1) material is the nano-porous structure that size is about 50nm, and hole is evenly distributed in several nanometer (<10nm) scope.
Adopt atomic absorption spectrum to analyze material component, the mol ratio of sulfur content and Se content that result shows this material is about 9:1.
Embodiment 7
Get 5 grams of sulphur powder, 0.25 gram of red phosphorus powder, 0.41 gram of iodine and 1 gram of CMK-3 mixing, after wet ball grinding 24h mixes, be sealed in the reactor of 10mL, under being placed in electrical crucible, reacting 10h, then naturally cool to room temperature in 280 DEG C; S can be obtained after driving still
1-xp
x-yi
y/ CMK-3 (x=0.07, y=0.02) material.
Adopt X light powder diffraction instrument to the S of preparation
1-xp
x-yi
y/ CMK-3 (x=0.07, y=0.02) material carries out X light diffracting analysis, and result shows, this material is noncrystalline structure.
Adopt ESEM and transmission electron microscope to detect material structure, result shows, S prepared by the present invention
1-xp
x-yi
y/ CMK-3 (x=0.07, y=0.02) material is the nano-porous structure that size is about 40nm, and hole is evenly distributed in several nanometer (<10nm) scope.
Adopt atomic absorption spectrum to analyze material component, result shows the sulfur content of this material and phosphorus, the mol ratio of iodine total content is about 93:7.
Embodiment 8
Get 5 grams of sulphur powder, 1 gram of bismuth meal and 4 grams of porous carbon mixing, after wet ball grinding 24h mixes, be sealed in the reactor of 10mL, under being placed in electrical crucible, reacting 10h, then naturally cool to room temperature in 280 DEG C; S can be obtained after driving still
1-xbi
x/ C (x=0.03) material.
Adopt X light powder diffraction instrument to the S of preparation
1-xbi
x/ C (x=0.03) material carries out X light diffracting analysis, and result shows, except Bi
2s
3diffraction maximum outside there is no other peaks.
Adopt ESEM and transmission electron microscope to detect material structure, result shows, S prepared by the present invention
1-xbi
x/ C (x=0.03) material is the nano-porous structure that size is about 40nm, and hole is evenly distributed in several nanometer (<10nm) scope.
Embodiment 9
Respectively by S prepared by embodiment 1
1-xse
x/ C (x=0.1) material, S prepared by embodiment 7
1-xp
x-yi
y/ CMK-3, executes S prepared by example 8
1-xbi
xcR2016 type button-type battery electrode sheet made by/C material, the sulphur system positive electrode that electrode slice adopts the corresponding embodiment of 70wt% to prepare, the sodium alginate of 10wt%, 20% conductive black, water mix, the substrate of electrode film is metal aluminum foil.
Adopt lithium sheet to be to electrode, polyolefin porous membrane (Celgard2500) is barrier film, with LiPF
6ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio 1:1) as electrolyte, in the glove box of argon gas atmosphere, dress up CR2016 lithium-sulfur cell.
Adopt sodium sheet to be to electrode, polyolefin porous membrane (Celgard2500) is barrier film, with NaPF
6ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio 1:1) as electrolyte, in the glove box of argon gas atmosphere, dress up CR2016 sodium-sulphur battery.
To S
1-xse
xthe lithium-sulfur cell that/C (x=0.1) assembles and sodium-sulphur battery carry out chemical property detection, and the results of property of lithium-sulfur cell is shown in Fig. 6 ~ Fig. 8, and Fig. 6 is that the lithium-sulfur cell of embodiment 9 preparation is at 0.2Ag
-1charging and discharging curve figure under current density, wherein, curve a is the charging and discharging curve figure of first lap, curve b is the charging and discharging curve figure of the second circle, curve c be the 3rd circle charging and discharging curve figure, curve d be the 4th circle charging and discharging curve figure, curve e be the 5th circle charging and discharging curve figure; Fig. 7 is that the lithium-sulfur cell of embodiment 9 preparation is at 0.5Ag
-1under current density, electrochemical cycle stability figure, Fig. 8 are the electrochemistry high rate performance figure of lithium-sulfur cell prepared by embodiment 9, and as seen from Figure 6, current density is 0.2Ag
-1time, the first circle coulombic efficiency of lithium-sulfur cell is 55%, and coulombic efficiency remains on more than 99.5% subsequently.In the figure 7, pass through at 0.2Ag
-1after pre-circulation under low current density, lithium-sulfur cell is at 0.5Ag
-1circulate under current density after 500 circles, reversible specific capacity still can remain on 953mAhg
-1, show excellent cyclical stability.In the high rate performance test of Fig. 8, the lithium-sulfur cell of assembling is at 20Ag
-1under current density, specific capacity still has 572mAhg
-1, show that it has excellent high rate performance.
S
1-xse
xthe performance of the sodium-sulphur battery that/C (x=0.1) assembles as shown in figs. 9-10.Fig. 9 is that the sodium-sulphur battery of assembling is at 0.2Ag
-1cycle performance under current density, first circle coulombic efficiency is about 52%, and after circulation 150 circle, reversible specific capacity remains on 937mAhg
-1.In the high rate performance test of Figure 10, the sodium-sulphur battery of assembling is at 20Ag
-1under current density, specific capacity still has 328mAhg
-1, show that it has good high rate performance.
S
1-xp
x-yi
ythe performance of the lithium-sulfur cell of/CMK-3C assembling as depicted in figs. 11-12.Wherein, Figure 11 is the S that embodiment 9 obtains
1-xp
x-yi
ythe lithium-sulfur cell charging and discharging curve figure of/CMK-3 (x=0.07, y=0.02) material, curve 1 is the first charge-discharge curve of this battery, curve 2, and 3 correspond respectively to second time, for the third time charging and discharging curve; Figure 12 is that the lithium-sulfur cell of assembling is at 0.2Ag
-1electrochemical cycle stability figure under current density, as seen from Figure 12, first circle coulombic efficiency is about 63%, and after circulation 350 circle, reversible specific capacity remains on 837mAhg
-1.
S
1-xbi
xthe performance of the lithium-sulfur cell of/C assembling as illustrated in figs. 13-14.Wherein, Figure 13 is the S that embodiment 9 obtains
1-xbi
xthe lithium-sulfur cell charging and discharging curve figure of/C (x=0.03) material, curve 1 is the first charge-discharge curve of this battery, curve 2, and 3 correspond respectively to second time, for the third time charging and discharging curve; Figure 14 is that the lithium-sulfur cell of assembling is at 0.2Ag
-1electrochemical cycle stability figure under current density, as seen from Figure 14, first circle coulombic efficiency is about 72%, and after circulation 300 circle, reversible specific capacity remains on 885mAhg
-1.
As can be seen from the above-described embodiment, the battery adopting sulphur system provided by the invention positive electrode to prepare, has excellent chemical property.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection range of the claims in the present invention.
Claims (9)
1. a sulphur system positive electrode, chemical formula is such as formula shown in (I) or formula (II):
S
1-xM
x(I)；
S
1-xM
x/C(Ⅱ)；
Wherein, 0<x<1;
M be in Se, Te, I, P, Bi, Sn any one or multiple.
2. sulphur system according to claim 1 positive electrode, is characterized in that, in described positive electrode, the molar content of S is greater than 90%.
3. a preparation method for the sulphur system positive electrode described in any one of claim 1 or 2, comprising:
Sulphur powder is mixed with M, carbon substrate, under air-proof condition, melts reaction altogether, obtain sulphur system positive electrode;
Described M be in selenium powder, antimony powder, iodine, red phosphorus, bismuth, tin any one or multiple;
The addition of described carbon substrate is 0% ~ 80% of raw material gross mass.
4. preparation method according to claim 3, is characterized in that, described carbon substrate be in Graphene, porous carbon materials, carbon nano-tube and CMK-3 any one or multiple.
5. preparation method according to claim 3, is characterized in that, the mol ratio of described sulphur powder and M is (70:30) ~ (99.6:0.4).
6. preparation method according to claim 5, is characterized in that, the mol ratio of described sulphur powder and M is (9 ~ 99): 1.
7. preparation method according to claim 3, is characterized in that, described temperature of melting reaction is altogether 60 DEG C ~ 500 DEG C, and the time is 30min ~ 120h.
8. preparation method according to claim 3, is characterized in that, described in be mixed into ball milling mixing.
9. a battery, the sulphur system positive electrode prepared with the preparation method described in the sulphur system positive electrode described in any one in claim 1 ~ 2 or any one in claim 3 ~ 9 is for positive electrode.
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Cited By (6)
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| CN108539178A (en) * | 2018-04-25 | 2018-09-14 | 广东工业大学 | Ion battery novel phosphorus and sulphur selenium composite negative pole material and preparation method thereof |
| CN108539196A (en) * | 2018-05-15 | 2018-09-14 | 华中科技大学 | A kind of high-performance sulfur-based composite anode material and preparation method thereof |
| CN109390572A (en) * | 2018-10-12 | 2019-02-26 | 大连海事大学 | A kind of phosphorus sulphur/carbon composite and its preparation and application |
| CN109411737A (en) * | 2018-12-06 | 2019-03-01 | 中国地质大学（北京） | A kind of polarity sulfide-sulphur/porous carbon composite anode material and preparation method thereof with three-dimensional structure |
| CN109888254A (en) * | 2019-03-29 | 2019-06-14 | 华中科技大学 | A kind of zinc-base cell positive material based on aqueous solution, its preparation and application |
| CN108328589B (en) * | 2018-01-11 | 2021-07-20 | 三峡大学 | PSe negative electrode material with high coulombic efficiency for the first time and preparation method thereof |
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| CN108328589B (en) * | 2018-01-11 | 2021-07-20 | 三峡大学 | PSe negative electrode material with high coulombic efficiency for the first time and preparation method thereof |
| CN108539178A (en) * | 2018-04-25 | 2018-09-14 | 广东工业大学 | Ion battery novel phosphorus and sulphur selenium composite negative pole material and preparation method thereof |
| CN108539178B (en) * | 2018-04-25 | 2020-11-13 | 广东工业大学 | Novel phosphorus-sulfur-selenium composite negative electrode material for ion battery and preparation method thereof |
| CN108539196A (en) * | 2018-05-15 | 2018-09-14 | 华中科技大学 | A kind of high-performance sulfur-based composite anode material and preparation method thereof |
| CN108539196B (en) * | 2018-05-15 | 2020-12-29 | 华中科技大学 | High-performance sulfur-based composite cathode material and preparation method thereof |
| CN109390572A (en) * | 2018-10-12 | 2019-02-26 | 大连海事大学 | A kind of phosphorus sulphur/carbon composite and its preparation and application |
| CN109411737A (en) * | 2018-12-06 | 2019-03-01 | 中国地质大学（北京） | A kind of polarity sulfide-sulphur/porous carbon composite anode material and preparation method thereof with three-dimensional structure |
| CN109411737B (en) * | 2018-12-06 | 2021-07-09 | 中国地质大学（北京） | Polar sulfide-sulfur/porous carbon composite positive electrode material with three-dimensional structure and preparation method thereof |
| CN109888254A (en) * | 2019-03-29 | 2019-06-14 | 华中科技大学 | A kind of zinc-base cell positive material based on aqueous solution, its preparation and application |
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