CN106374087A - Cathode material for long-circulation lithium-sulfur battery and preparation method thereof - Google Patents
Cathode material for long-circulation lithium-sulfur battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cathode material for a long-circulation lithium-sulfur battery and a preparation method thereof. The cathode material is compounded from the following materials: a three-dimensional metallic oxide or metallic sulfide/carbon composite material and a sulfur-containing material, wherein the three-dimensional metallic oxide or metallic sulfide/carbon composite material is compounded from the following materials: a metallic oxide or metallic sulfide, and a carbon composite material. The carbon composite material is a nanocarbon composite material, with a two-dimensional structure, compounded by a one-dimensional material and a two-dimensional material. The sulfur-containing material is elemental sulfur or a polysulfide containing a -Sm- structure in which m is greater than 2. The cathode material for the long-circulation lithium-sulfur battery prepared in the invention has high conductivity and a three-dimensional space structure, the coulombic efficiency and cycle performance of the lithium-sulfur battery can be improved effectively, and meanwhile the cathode material has excellent rate capability.
Description
Technical field
The present invention relates to a kind of positive electrode of lithium-sulfur cell is and in particular to a kind of long circulating positive material for lithium-sulfur battery
And preparation method thereof.
Background technology
With social fast development, the either civilian city with electric automobile, intelligent grid and energy-accumulating power station as representative
, or the military domain with satellite, unmanned plane etc. as representative all proposes more and more high demand to the energy density of battery.
Lithium-sulfur cell, due to becoming the focus of current research the advantages of with low cost, environmental friendliness, energy density are high, becomes of future generation high
Representative than energy lithium battery.
Lithium-sulfur cell is also there are disadvantages that hamper its industrialized process.Electrical conductivity as positive active material sulfur
Low, discharge and recharge intermediate product is dissolved in electrolyte and forms reaction of shuttling, and positive electrode volumetric expansion in charge and discharge process.More than
Defect leads to that the active utilization rate of cell positive material is low, coulombic efficiency is low and cyclicity is poor.For above shortcoming, Duo Geyan
The person of studying carefully has carried out substantial amounts of research.Most common method be by active substance sulfur be packed into duct enrich, specific surface area larger
The duct of carbon is internal to improve material electric conductivity, the purpose of suppression polysulfide dissolving thus reaching.As linda f. nazar becomes
Work(is prepared for sulfur/cmk-3 composite (nat. mater., 2009,8,500)；Wang Weikun etc. is by the Os Sus domestica of sulfur and carbonization
Carbon is combined (energy environ. sci., 2011,4,736 740) etc..The studies above improves lithium sulfur to a certain extent
The specific discharge capacity of battery, coulombic efficiency and cycle life.But, because carbon material surface is polarity, to nonpolar many sulfur
The adsorptivity of compound is weaker, and only limits many sulfur by the physical absorption in material duct and shuttle, therefore lead to coulombic efficiency relatively low,
Cycle performance is undesirable.
At present, research report points out that metal sulfide and metal-oxide have significant chemisorbed and make to many lithium sulfides
With the cycle performance of lithium-sulfur cell can be significantly improved.But the electrical conductivity of conventional oxide material is typically relatively low, therefore exists
The high rate performance of electrode can be affected to a certain extent.Therefore, there is the composite sulfur positive pole material of excellent cycle performance and high rate performance
The regulation and control preparation of material or a very big challenge.
Content of the invention
It is an object of the invention to provide a kind of long circulating positive material for lithium-sulfur battery and preparation method thereof, this positive electrode
There is high conductivity, excellent cycle performance, coulombic efficiency and high rate performance, this positive electrode is as lithium-sulfur cell just
Pole, can significantly improve the performance of lithium-sulfur cell.
In order to achieve the above object, the invention provides a kind of long circulating positive material for lithium-sulfur battery, this positive electrode
By following Material cladding: three-dimensional metal oxide or metal sulfide/carbon composite, sulphurous materials.
Wherein, described three-dimensional metal oxide or metal sulfide/carbon composite are by following Material cladding: metal oxygen
Compound or metal sulfide, carbon composite.
Wherein, described carbon composite is the nanometer with two-dimensional structure of one-dimensional material with carbon element and Two-dimensional Carbon Material cladding
Carbon composite.
Wherein, described sulphurous materials are elemental sulfur or contain-sm-, the polysulfide of m ＞ 2 structure.
Wherein, in described positive electrode, the mass percent of described sulphurous materials is 70%～90%, described gold
Belonging to oxide or the mass percent of metal sulfide is 5%～20%, and the mass percent of described one-dimensional material with carbon element is 0.5%
～5%, the mass percent of described two-dimentional material with carbon element is 0.1%～5%.
Described one-dimensional material with carbon element is SWCN, multi-walled carbon nano-tubes, vapour deposition carbon fiber, biomass carbonization
In carbon fiber, the carbon fiber of polymer carbonization any one or two or more.
Described two-dimentional material with carbon element is N doping graphene oxide, N doping reduced graphene, nitrogen-doped graphene, nitrogen are mixed
In miscellaneous nanometer carbon plate any one or two or more.
Described metal-oxide is manganese dioxide, calcium oxide, titanium oxide, magnesium oxide, lanthana, aluminium oxide, oxidation
In cerium any one or two or more.
Described metal sulfide is cobalt sulfide or zinc sulfide.
Described elemental sulfur is crystallization sulfur, colloid sulfur or no in crystalline state sulfur any one or two or more.
Described crystallization sulfur is Sublimed Sulfur or crystallite sulfur.
Present invention also offers the preparation method of described long circulating positive material for lithium-sulfur battery, this preparation method bag
Contain:
The first step: by the surface etch chemistry of strong oxidizer, the nano surface carrying out one-dimensional material with carbon element is peeled off；
Second step: material, two-dimentional material with carbon element and metal-oxide that above-mentioned stripping is obtained or metal sulfide are combined, and are had
There are the carbon composite/metal-oxide of three dimensional structure or the composite of metal sulfide；
3rd step: will there is the carbon composite/metal-oxide of three dimensional structure or the composite of metal sulfide and sulfur-bearing
Material is combined, and obtains thering is the sulfur/carbon composite/metal-oxide of three dimensional structure or the composite wood of metal sulfide
Material.
Wherein, compound method in described second step is in in-situ compositing, chemical precipitation method or ULTRASONIC COMPLEX method
Kind or two or more be used in combination；
Wherein, compound method in described 3rd step is the in-situ solution sedimentation method, melts composite algorithm, Vacuum Heat composite algorithm or solvent
One of exchange process or two or more united method.
Strong oxidizer described in the first step is the mixed acid of concentrated nitric acid and concentrated sulphuric acid.
Described one-dimensional material with carbon element is 1:10 ~ 100 with the mass ratio of strong oxidizer.
Long circulating positive material for lithium-sulfur battery that the present invention provides and preparation method thereof, solves the lithium sulfur of prior art
Battery conductance rate is low, the problem of cycle performance difference, has the advantage that
The positive electrode of the present invention has 3-D nano, structure, and the CNT within positioned at nanostructured constitutes conductive mesh
Network, not only increases the electrical conductivity of electrode, also contributes to improve the mechanical performance of electrode；In the positive electrode of the present invention
The specific surface area of metal-oxide or metal sulfide is larger, is the deposition space that active substance sulfur provides abundance, this metal
Oxide or metal sulfide and two-dimentional material with carbon element are respectively provided with good polysulfide chemisorbed function, can suppress and vulcanize
The shuttle reaction of lithium, effectively increases coulombic efficiency and the cycle performance of lithium-sulfur cell；Three wieners of the positive electrode of the present invention
Rice structure is conducive to the transmission of ion and electronics, improves the electro-chemical activity of electrode, the cycle performance of positive electrode, coulomb effect
Rate and high rate performance are significantly increased.
Brief description
Fig. 1 is a kind of schematic diagram of the preparation method of long circulating positive material for lithium-sulfur battery of the present invention.
Fig. 2 is the composite of the sulfur/manganese dioxide/graphene oxide/CNT of embodiments of the invention 1 preparation
(mno2/ go/cnts-s) and preparation process in manganese dioxide/graphene oxide/CNT composite (mno2/go/
Cnts (a is mno under projection electron microscope to sem image)2The image of/go/cnts, b is under a scanning electron microscope
mno2The image of/go/cnts, c is mno under projection electron microscope2The image of/go/cnts-s, d is in scanning electron microscopy
Mno under mirror2The image of/go/cnts-s).
Fig. 3 is the composite of the sulfur/manganese dioxide/graphene oxide/CNT of embodiments of the invention 1 preparation
(mno2/ go/cnts-s) cycle performance curve with comparative example 1 and comparative example 2.
Specific embodiment
Below in conjunction with drawings and Examples, technical scheme is described further.
A kind of long circulating positive material for lithium-sulfur battery that the present invention provides, this positive electrode is by following Material cladding: three
Dimension metal-oxide or metal sulfide/carbon composite, sulphurous materials.
Wherein, three-dimensional metal oxide or metal sulfide/carbon composite are by following Material cladding: metal-oxide or
Metal sulfide, carbon composite.
Wherein, carbon composite is the Nano Carbon with two-dimensional structure of one-dimensional material with carbon element and Two-dimensional Carbon Material cladding
Material.
In this positive electrode, the mass percent of sulphurous materials is 70%～90%, metal-oxide or metal sulfide
Mass percent be 5%～20%, the mass percent of one-dimensional material with carbon element is 0.5%～5%, the mass percent of two-dimentional material with carbon element
For 0.1%～5%.
One-dimensional material with carbon element is SWCN, multi-walled carbon nano-tubes, vapour deposition carbon fiber, biomass carbonization carbon are fine
Dimension, in the carbon fiber of polymer carbonization any one or two or more.
Two-dimentional material with carbon element is N doping graphene oxide, N doping reduced graphene, nitrogen-doped graphene, nitrogen-doped nanometer
In carbon plate any one or two or more.
Wherein, metal-oxide is manganese dioxide, calcium oxide, titanium oxide, magnesium oxide, lanthana, aluminium oxide, cerium oxide
In any one or two or more.Metal sulfide is cobalt sulfide or zinc sulfide.This polysulfide has chemisorbed function,
Can be with many lithium sulfide (li2sx, x ＞ 2) and with chemical bonds, suppress its dissolving.
Wherein, for elemental sulfur or containing-s in sulphurous materialsm-, the polysulfide of m ＞ 2 structure.Elemental sulfur is crystallization sulfur, glue
In body sulfur or no crystalline state sulfur any one or two or more.
Above-mentioned crystallization sulfur is Sublimed Sulfur or crystallite sulfur.
Long circulating positive material for lithium-sulfur battery as the positive pole of battery, lithium metal, lithium alloy, is mixed the carbon of lithium, mixes lithium
One or more of silicon-carbon or graphite, as the negative pole of battery, have the pp/pe(polypropylene, polyethylene of MULTILAYER COMPOSITE), glass
One or more of glass fibre diaphragm, coated separator are as the barrier film of battery, liquid organic electrolyte, colloidal polymer electrolysis
One or more of matter, solid polymer electrolyte as the electrolyte of battery, by above-mentioned positive pole, negative pole, barrier film and electricity
Solution matter constitutes lithium-sulfur cell.
Present invention also offers the preparation method of this long circulating positive material for lithium-sulfur battery, concrete preparation method comprises:
The first step: by the surface etch chemistry of strong oxidizer, the nano surface carrying out one-dimensional material with carbon element (cnts) is peeled off, one-dimensional
Material with carbon element is 1:10 ~ 100 with the mass ratio of strong oxidizer, and strong oxidizer is the mixed acid of concentrated nitric acid and concentrated sulphuric acid；
Second step: material, two-dimentional material with carbon element and metal-oxide that above-mentioned stripping is obtained or metal sulfide are combined, and are had
There are the carbon composite/metal-oxide of three dimensional structure or the composite (mno of metal sulfide2/ go/cnts), as Fig. 1 institute
That shows prepares schematic diagram, prepares mno by cnts2/go/cnts；
3rd step: will there is the carbon composite/metal-oxide of three dimensional structure or the composite of metal sulfide and sulfur-bearing
Material is combined, and obtains thering is the sulfur/carbon composite/metal-oxide of three dimensional structure or the composite of metal sulfide
(mno2/ go/cnts-s), as shown in Figure 1 prepares schematic diagram, by mno2/ go/cnts prepares mno2/go/cnts-s.
The method that above-mentioned second step is combined is one of in-situ compositing, chemical precipitation method or ULTRASONIC COMPLEX method or two kinds
More than it is used in combination.
In-situ compositing: refer to using nano carbon composite material as reactant and carrier, by chemical reaction by metal oxygen
Compound or metal sulfide growth in situ are in nanometer carbon surface.
Chemical precipitation method: refer to, using nano carbon composite material as carrier, prepare by chemical precipitation method in the liquid phase
Metal-oxide or metal sulfide be deposited directly to the surface of nano-sized carbon.
ULTRASONIC COMPLEX method: refer to mix nano carbon composite material with metal-oxide or metal sulfide, then super
Under the auxiliary of sound wave, metal-oxide or sulfide are compound on nano-carbon material.
The method that above-mentioned 3rd step is combined is the in-situ solution sedimentation method, melting composite algorithm, Vacuum Heat composite algorithm or solvent are handed over
Change one of method or two or more united method.
The in-situ solution sedimentation method: refer to using chemical reaction in-situ preparation sulfur, and the carbon composite/gold in three dimensional structure
Belong to oxide or sulfide composite material surface deposition, the method is carried out in the solution, and reaction temperature is 0～150 DEG C, during reaction
Between be 1～6h；
Melting composite algorithm: refer to by sulfur liquefaction or gasify using rising high-temperature, in inert gas environment, sulfur and three dimensional structure
Carbon composite/metal-oxide or sulfide composite are combined, and reaction temperature is 100～300 DEG C, and the response time is
1～10h；
Vacuum Heat composite algorithm: refer to be combined in vacuum-tight environmental interior, reaction temperature is 100～400 DEG C, during reaction
Between be 1～10h, vacuum be 0.1～10mmhg；
Solvent exchange method: refer to dissolve in a solvent by sulfur, then add another kind of solvent, carried out using the difference of dissolubility
Compound.
Embodiment 1
There is the first preparation method of the composite of sulfur/manganese dioxide/graphene oxide/CNT of three dimensional structure
(melting composite algorithm).
The first step: take 1g CNT, be scattered in concentrated acid solution (concentrated nitric acid and concentrated sulfuric acid volume are than 1:3), carbon nanometer
Pipe is mass ratio 1:10～preferred 1:50 of 100(with the ratio of concentrated acid), it is changed to magnetic force stirring at normal temperature 1h after ultrasonic disperse 10 min,
Rise high-temperature to 70 DEG C, stir 4h, the nano surface carrying out CNT is peeled off, this step can be used for miscellaneous in removal CNT
Matter, and it is grafted oxygen containing chemical functional group；
Second step: above-mentioned solution temperature is reduced to 0 DEG C, adds 5ml concentrated sulphuric acid and continue stirring 30min, subsequent liter high-temperature to 55
DEG C, and add 3g potassium permanganate continuation stirring 120min, and it is warming up to 90 DEG C and stir 10min, last filtering drying, had
Composite (the mno of the manganese dioxide/graphene oxide/CNT of three dimensional structure2/ go/cnts)；
3rd step: take the composite 1g of above-mentioned manganese dioxide/graphene oxide/CNT, mix all with 10g Sublimed Sulfur
Even, it is placed in tube furnace 300 DEG C of insulation 6h under nitrogen protection, obtain the sulfur/manganese dioxide/graphite oxide with three dimensional structure
Composite (the mno of alkene/CNT2/ go/cnts-s).
Embodiment 2
There is the second preparation method of the composite of sulfur/manganese dioxide/graphene oxide/CNT of three dimensional structure
(solvent exchange method).
The first step and second step are same as Example 1；
3rd step: take the composite 1g of above-mentioned manganese dioxide/graphene oxide/CNT, be scattered in Carbon bisulfide solution
In, add 3g sulphur powder, airtight stirring 2h in above-mentioned dispersion liquid, be subsequently placed in fume hood and stir to curing at 50 DEG C
Carbon volatilizees completely, obtains the composite (mno with the sulfur/manganese dioxide/graphene oxide/CNT of three dimensional structure2/
Go/cnts-s).
Embodiment 3
There is the third preparation method of the composite of sulfur/manganese dioxide/graphene oxide/CNT of three dimensional structure
(the in-situ solution sedimentation method).
The first step and second step are same as Example 1；
3rd step: take the composite 1g of above-mentioned manganese dioxide/graphene oxide/CNT, be scattered in 200ml deionized water
In, ultrasonic 30min, adds many sodium sulfides solution 100ml of 1mol/l in solution, continues stirring 1h, state dispersion then up
It is added dropwise over 1mol/l hydrochloric acid 200ml, filtering drying in liquid, obtain the sulfur/manganese dioxide/graphite oxide with three dimensional structure
Composite (the mno of alkene/CNT2/ go/cnts-s).
Embodiment 4
There is the 4th kind of preparation method of the composite of sulfur/manganese dioxide/graphene oxide/CNT of three dimensional structure
(melting composite algorithm).
The first step is same as Example 1；
Second step: above-mentioned solution temperature is reduced to 0 DEG C, adds 5ml concentrated sulphuric acid and continue stirring 30min, subsequent liter high-temperature to 55
DEG C, and add 3g potassium permanganate continuation stirring 120min, it is warming up to 90 DEG C and stirs 10 min, then add enough hydrogen peroxide,
Filter and dry, obtain the composite of CNT/graphene oxide.Take the compound of 0.5g CNT/graphene oxide
Material, is scattered in the deionized water that 200ml adds p123, adds 3g tetraethyl orthosilicate solution, continues stirring 2h, Ran Houtian
Plus a certain amount of dilute hydrochloric acid be transferred in water heating kettle constant temperature 20 h at 120 DEG C, finally filter and dry, obtain with three-dimensional
Composite (the mno of the silicon dioxide/graphene oxide/CNT of structure2/ go/cnts-s)；
3rd step is same as Example 1.
Comparative example 1
By business-like CNT, graphene oxide and manganese dioxide mechanical mixture according to a certain percentage, take after mix homogeneously
1g mixing material, is mixed homogeneously with 10g Sublimed Sulfur, is placed in tube furnace 300 DEG C of insulation 6h under nitrogen protection, finally gives material
Material mno2/go/cnts-s-2.
Comparative example 2
Take 1g CNT, mix homogeneously with 10g Sublimed Sulfur, be placed in tube furnace 300 DEG C of insulation 6h under nitrogen protection, finally
Obtain material cnts-s.
The composite wood of the sulfur/manganese dioxide/graphene oxide/CNT with three dimensional structure of embodiment 1-4 preparation
Material (mno2/ go/cnts-s) the performance test results:
(1) electron microscope observation structure
Composite to the sulfur/manganese dioxide/graphene oxide/CNT with three dimensional structure of embodiment 1 preparation
(mno2/ go/cnts-s) structure observed, the manganese dioxide/oxidation with three dimensional structure obtaining in its preparation process
Composite (the mno of graphene/carbon nano-tube2/ go/cnts) image under projection electron microscope as shown in a of Fig. 2,
Image under a scanning electron microscope, as shown in the b of Fig. 2, has the sulfur/manganese dioxide/graphene oxide/carbon of three dimensional structure
Composite (the mno of nanotube2/ go/cnts-s) image under projection electron microscope as shown in the c of Fig. 2, in scanning electricity
Image under sub- microscope is as shown in the d of Fig. 2 it can be seen that having obvious 3-D solid structure.
(2) electrochemical property test
Composite (mno by the sulfur/manganese dioxide/graphene oxide/CNT of the present invention2/ go/cnts-s) and contrast
The mno of example 1 preparation2The 2cnts-s of/go/cnts-s-2 and comparative example preparation carries out electrochemical property test, as shown in figure 3,
Composite (the mno of the sulfur/manganese dioxide/graphene oxide/CNT of present invention preparation2/ go/cnts-s) electric discharge ratio
Capacity remains at 1000mah/g after 100 circulations, and apparently higher than comparative example 1 and 2, its coulombic efficiency is about its capacitance
100%, show that the composite of the sulfur/manganese dioxide/graphene oxide/CNT of the present invention has good electrical conductivity, follows
Ring performance.The stable high connductivity network of CNT and Graphene composition is conducive to improving the electronic conductivity of sulfur materials, from
And improve the high rate performance of electrode.
A kind of long circulating positive material for lithium-sulfur battery of present invention preparation, this positive electrode has high electrical conductivity and three
Dimension space structure, this three-D space structure is conducive to the transmission of ion and electronics, can effectively improve the coulomb effect of lithium-sulfur cell
Rate and cycle performance, also have excellent high rate performance simultaneously.
Although present disclosure has been made to be discussed in detail by above preferred embodiment, but it should be appreciated that above-mentioned
Description is not considered as limitation of the present invention.After those skilled in the art have read the above, for the present invention's
Multiple modifications and substitutions all will be apparent from.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. a kind of long circulating positive material for lithium-sulfur battery is it is characterised in that this positive electrode is by following Material cladding: three Vygens
Belong to oxide or metal sulfide/carbon composite, sulphurous materials；
Described three-dimensional metal oxide or metal sulfide/carbon composite are by following Material cladding: metal-oxide or gold
Belong to sulfide, carbon composite；
Described carbon composite is the Nano Carbon material with two-dimensional structure of one-dimensional material with carbon element and Two-dimensional Carbon Material cladding
Material；
Described sulphurous materials are elemental sulfur or contain-sm-, the polysulfide of m ＞ 2 structure；
In described positive electrode, the mass percent of described sulphurous materials is 70%～90%, described metal-oxide
Or the mass percent of metal sulfide is 5%～20%, the mass percent of described one-dimensional material with carbon element is 0.5%～5%, described
Two-dimentional material with carbon element mass percent be 0.1%～5%.
2. long circulating positive material for lithium-sulfur battery according to claim 1 is it is characterised in that described one-dimensional material with carbon element
Fine for the carbon of SWCN, multi-walled carbon nano-tubes, vapour deposition carbon fiber, biomass carbonization carbon fiber, polymer carbonization
In dimension any one or two or more.
3. long circulating positive material for lithium-sulfur battery according to claim 1 is it is characterised in that described two-dimentional material with carbon element
For any one in N doping graphene oxide, N doping reduced graphene, nitrogen-doped graphene, nitrogen-doped nanometer carbon plate or
Two or more.
4. long circulating positive material for lithium-sulfur battery according to claim 1 is it is characterised in that described metal-oxide
For any one in manganese dioxide, calcium oxide, titanium oxide, magnesium oxide, lanthana, aluminium oxide, cerium oxide or two or more.
5. long circulating positive material for lithium-sulfur battery according to claim 1 is it is characterised in that described metal sulfide
For cobalt sulfide or zinc sulfide.
6. long circulating positive material for lithium-sulfur battery according to claim 1 is it is characterised in that described elemental sulfur is knot
Brilliant sulfur, colloid sulfur or no in crystalline state sulfur any one or two or more.
7. long circulating positive material for lithium-sulfur battery according to claim 6 is it is characterised in that described crystallization sulfur is to rise
Magnificent sulfur or crystallite sulfur.
8. the preparation method of long circulating positive material for lithium-sulfur battery according to claim 1 is it is characterised in that this preparation
Method comprises:
The first step: by the surface etch chemistry of strong oxidizer, the nano surface carrying out one-dimensional material with carbon element is peeled off；
Second step: material, two-dimentional material with carbon element and metal-oxide that above-mentioned stripping is obtained or metal sulfide are combined, and are had
There are the carbon composite/metal-oxide of three dimensional structure or the composite of metal sulfide；
3rd step: will there is the carbon composite/metal-oxide of three dimensional structure or the composite of metal sulfide and sulfur-bearing
Material is combined, and obtains thering is the sulfur/carbon composite/metal-oxide of three dimensional structure or the composite wood of metal sulfide
Material；
Wherein, compound method in described second step be one of in-situ compositing, chemical precipitation method or ULTRASONIC COMPLEX method or
Two or more it is used in combination；
Wherein, compound method in described 3rd step is the in-situ solution sedimentation method, melts composite algorithm, Vacuum Heat composite algorithm or solvent
One of exchange process or two or more united method.
9. the preparation method of long circulating positive material for lithium-sulfur battery according to claim 8 is it is characterised in that the first step
Described in strong oxidizer be concentrated nitric acid and concentrated sulphuric acid mixed acid.
10. the preparation method of long circulating positive material for lithium-sulfur battery according to claim 8 is it is characterised in that described
The mass ratio of one-dimensional material with carbon element and strong oxidizer be 1:10 ~ 100.
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| CN106935796A (en) * | 2017-05-16 | 2017-07-07 | 中国科学院青岛生物能源与过程研究所 | A kind of sulphur/sulfide/copper tri compound positive pole and its preparation and the application in magnesium sulphur battery |
| CN106941168A (en) * | 2017-04-19 | 2017-07-11 | 扬州大学 | A kind of column GO@WO3The preparation method of@S composites |
| CN107248571A (en) * | 2017-06-02 | 2017-10-13 | 昆明理工大学 | A kind of S@MgO Graphene electrodes materials and preparation method |
| CN107492639A (en) * | 2017-07-28 | 2017-12-19 | 清华大学 | A kind of lithium-sulfur battery composite anode material and preparation method |
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