CN106159234A - Manganese dioxide carbon coated sulfur composite and preparation method thereof, lithium-sulfur cell - Google Patents

Manganese dioxide carbon coated sulfur composite and preparation method thereof, lithium-sulfur cell Download PDF

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CN106159234A
CN106159234A CN201610727950.3A CN201610727950A CN106159234A CN 106159234 A CN106159234 A CN 106159234A CN 201610727950 A CN201610727950 A CN 201610727950A CN 106159234 A CN106159234 A CN 106159234A
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sulfur
carbon
sulfur composite
solution
manganese dioxide
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CN106159234B (en
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施志聪
王诚文
刘军
柯曦
刘丽英
黄宗雄
尚永亮
刘斌
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Guangdong University of Technology
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Guangdong University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 the preparation method of a kind of manganese dioxide carbon coated sulfur composite, including: S1) carbon sulfur composite, surfactant are mixed with manganous salt in water, obtain mixed solution；S2) in mixed solution, add oxidizing agent solution, reaction, obtain manganese dioxide carbon coated sulfur composite.Compared with prior art, the present invention by first allow surfactant-dispersed in the surface of carbon sulfur composite, then by surfactant and Mn2+Between chemical action make Mn2+It is scattered in the surface of carbon sulfur composite uniformly, so that the MnO generated2Directly it is coated on the surface of carbon sulfur composite, sulfur and contacting of electrolyte can be reduced and reduce sulfur component and dissolve in the electrolytic solution；MnO2Also there is a chemical action to make sulfur be more difficult to dissolve in the electrolytic solution to sulfur；The method is also highly suitable for being applied on the high carbon sulfur composite carrying sulfur content, can preferably improve charging and discharging capacity and the cycle performance of its material.

Description

Manganese dioxide carbon coated sulfur composite and preparation method thereof, lithium-sulfur cell
Technical field
The invention belongs to lithium-sulfur cell technical field, particularly relate to a kind of manganese dioxide carbon coated sulfur composite and system thereof Preparation Method, lithium-sulfur cell.
Background technology
Secondary lithium-sulfur battery is to study hotter a kind of novel energy-storing system in the last few years, and to have reserves rich because of it for elemental sulfur Richness, cheap, environmental friendliness, it has higher theoretical specific capacity (1675mAhg compared with lithium rechargeable battery-1) and Higher theoretical specific energy (2600WhKg-1) etc. advantage, thus become company in one's power of Ge great Research Center study hotspot problem it One, and great sizable application value.
But, the intermediate product high-valence state polysulfide that sulfur electrode generates in electric discharge and charging process is soluble in electrolysis Liquid, causes the loss of elemental sulfur.Additionally, lithium-sulfur cell there is also shuttle effect, self discharge effect, battery in charge and discharge process Serious polarization, volumetric expansion, the dissolving of negative pole lithium form the problem such as SEI film and Li dendrite.In recent years, by home and abroad Research understands, electrode material adds the material with excellent electric conductivity and absorption property, can further increase The chemical property of sulfur, prepares the positive electrode of lithium-sulfur cell, so can improve sulfur for example with porous carbon materials cladding sulfur Electric conductivity, can reduce the loss contacting to avoid active component with electrolyte during sulfur is scattered in the hole of porous carbon simultaneously, Thus reach to improve the cycle performance of lithium-sulfur cell.But, this type of method still suffers from amount of activated component and electrolyte contacts, Its porous carbon surface of sulfur carbon composite of high capacity sulfur is certain to remain substantial amounts of active component sulfur simultaneously, still can make part Sulfur dissolves in the electrolytic solution, thus active component cannot play the effect of protection and the abundant profit to active substance completely With.
Summary of the invention
In view of this, the technical problem to be solved is to provide a kind of manganese dioxide carbon coated sulfur composite And preparation method thereof, lithium-sulfur cell, manganese dioxide carbon coated sulfur composite prepared by the method has preferable discharge and recharge ratio Capacity and cycle performance.
The invention provides the preparation method of a kind of manganese dioxide carbon coated sulfur composite, including:
S1) carbon sulfur composite, surfactant are mixed with manganous salt in water, obtain mixed solution；
S2) in mixed solution, add oxidizing agent solution, reaction, obtain manganese dioxide carbon coated sulfur composite.
Preferably, described carbon sulfur composite is prepared in accordance with the following methods:
Being mixed with Sublimed Sulfur by porous carbon, heating is reacted, and obtains carbon sulfur composite.
Preferably, described porous carbon selected from CMK, single wall CNT, many walls CNT, Graphene, CNF activated carbon, fullerene with One or more in MOFs；Described porous carbon is 1:(1～4 with the mass ratio of Sublimed Sulfur).
Preferably, including:
S1) carbon sulfur composite is dispersed in surfactant solution, mixes with manganous salt solution the most again, obtain Mixed solution；
S2) in mixed solution, add oxidizing agent solution, reaction, obtain manganese dioxide carbon coated sulfur composite.
Preferably, described surfactant is selected from polyvinylpyrrolidone, poly(ethylene oxide), octyl phenyl polyoxyethylene ether With in cetyl trimethylammonium bromide one or more；Described manganous salt is selected from MnSO4、MnCl2With Mn (CH3COO)2In One or more；Oxidant in described oxidizing agent solution is selected from potassium permanganate, potassium ferrate and the one in potassium dichromate Or it is multiple.
Preferably, the mass concentration of described surfactant solution is 0.25%～6%；Described manganous salt solution dense Degree is 1～50mmol/L；The concentration of described oxidizing agent solution is 0.1～50mmol/L；Described carbon sulfur composite is lived with surface The mass volume ratio of property agent solution is (0.25～1) g:(20～200) ml.
Preferably, described step S1) in mixing time be 3～10h；Described step S2) in reaction temperature be 10 DEG C ～60 DEG C；The time of reaction is 10～60min.
Preferably, the speed of the addition of described oxidizing agent solution is 5～20ml/min.
Present invention also offers a kind of manganese dioxide carbon coated sulfur composite, be made up of kernel and shell, described kernel For carbon sulfur composite, described shell is manganese dioxide.
Present invention also offers a kind of lithium-sulfur cell, including manganese dioxide carbon coated sulfur composite.
The invention provides the preparation method of a kind of manganese dioxide carbon coated sulfur composite, including: S1) carbon sulfur is combined Material, surfactant mix in water with manganous salt, obtain mixed solution；S2) in mixed solution, oxidant is added molten Liquid, reaction, obtain manganese dioxide carbon coated sulfur composite.Compared with prior art, the present invention is by first allowing surfactant It is scattered in the surface of carbon sulfur composite, then by surfactant and Mn2+Between chemical action make Mn2+Uniform dispersion In the surface of carbon sulfur composite, finally by dropping oxidizing agent solution and Mn2+Reaction makes the MnO of generation2Directly it is coated on carbon The surface of sulfur composite.First, so can reduce sulfur and contacting of electrolyte and reduce sulfur component and dissolve in the electrolytic solution； Secondly, MnO2Also there is a chemical action to make sulfur be more difficult to dissolve in the electrolytic solution to sulfur；Finally, the method is also highly suitable for answering Carry the carbon sulfur composite of sulfur content for height, can preferably improve charging and discharging capacity and the cycle performance of its material.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the carbon sulfur composite CMK-3@S obtained in the embodiment of the present invention 1；
Fig. 2 is carbon sulfur composite CMK-3@S and MnO obtained in the embodiment of the present invention 12The TGA of@CMK-3/S material Curve chart；
Fig. 3 is the MnO obtained in the embodiment of the present invention 12The stereoscan photograph of@CMK-3/S material；
Fig. 4 is the MnO obtained in the embodiment of the present invention 12@CMK-3/S material first charge-discharge under 0.1C multiplying power is bent Line chart；
Fig. 5 is the MnO obtained in the embodiment of the present invention 12@CMK-3/S and CMK-3@S cycle performance under 0.1C multiplying power Figure；
Fig. 6 is the stereoscan photograph of the carbon sulfur composite CNT@S obtained in the embodiment of the present invention 2；
Fig. 7 is the MnO obtained in the embodiment of the present invention 22The stereoscan photograph of@CNT/S material；
Fig. 8 is the MnO obtained in the embodiment of the present invention 22@CNT/S first charge-discharge curve chart under 0.1C multiplying power.
Detailed description of the invention
The invention provides the preparation method of a kind of manganese dioxide carbon coated sulfur composite, including: S1) carbon sulfur is combined Material, surfactant mix in water with manganous salt, obtain mixed solution；S2) in mixed solution, oxidant is added molten Liquid, reaction, obtain manganese dioxide carbon coated sulfur composite.
Wherein, the source of all raw materials is not particularly limited by the present invention, for commercially available or self-control.
In the present invention, described carbon sulfur composite preferably follows the steps below preparation: by porous carbon and Sublimed Sulfur Mixing, heating is reacted, and obtains carbon sulfur composite.
Wherein, the porous carbon that described porous carbon is well known to those skilled in the art, there is no special restriction, the present invention In be preferably one or more in CMK, single wall CNT, many walls CNT, Graphene, CNF, activated carbon, fullerene and MOFs.
Porous carbon is mixed with Sublimed Sulfur, is preferably 1:(1～4 according to mass ratio) ratio mixing, more preferably 1: (1.5～4), are further preferably 1:(2～4), be further preferably 1:(3～4), most preferably 1:4；Described mixing is preferably to grind and mixes Close；The time of described mixing is preferably 1～3h, more preferably 1～2h.
After mixing, heating is reacted；The temperature that described heating carries out reacting is preferably 120 DEG C～180 DEG C, more preferably 130 DEG C～170 DEG C, be further preferably 140 DEG C～160 DEG C, is further preferably 150 DEG C～160 DEG C, most preferably 155 DEG C；Described reaction Time be preferably 8～16h, more preferably 10～14h, then elect 11～13h as, most preferably 12h.
After reaction terminates, preferably reactant is cooled down, then carry out ball milling, obtain carbon sulfur composite；Turning of described ball milling Speed is preferably 100～1000r/min, and more preferably 100～800r/min, be further preferably 100～600r/min, most preferably 200～400r/min；The time of described ball milling is preferably 1～20h, and more preferably 5～15h, be further preferably 8～12h, most preferably It is 8～9h.
Then carbon sulfur composite, surfactant are mixed in water with manganous salt；Wherein, described surfactant The surfactant being well known to those skilled in the art, there is no special restriction, is preferably polyvinyl pyrrole in the present invention Alkanone (PVP), poly(ethylene oxide) (PEO), octyl phenyl polyoxyethylene ether (TX-100) and cetyl trimethylammonium bromide (CTAB) in one or more；The manganous salt that described manganous salt is well known to those skilled in the art, it is special to there is no Limit, the present invention is preferably MnSO4、MnCl2With Mn (CH3COO)2In one or more.
According to the present invention, carbon sulfur composite is the most first dispersed in surfactant solution by this step；Described surface The mass concentration of activator solution is preferably 0.25%～6%, and more preferably 0.5%～6%, be further preferably 1%～5%, It is preferably 2%～4%；In some embodiments that the present invention provides, the mass concentration of described surfactant solution is preferably 2%；In other embodiments that the present invention provides, the mass concentration of described surfactant solution is preferably 4%；Described carbon Sulfur composite is preferably (0.25～1) g:(20～200 with the mass volume ratio of surfactant solution) ml, more preferably (0.25～1) g:(20～150) ml, be further preferably (0.25～1) g:(20～100) ml, it is further preferably (0.25～1) g:(40 ～80) ml, most preferably (0.25～1) g:(40～60) ml；In some embodiments that the present invention provides, described carbon sulfur is combined Material is preferably 0.25g:40ml with the mass volume ratio of surfactant solution；In other embodiments that the present invention provides In, described carbon sulfur composite is preferably 1g:40ml with the mass volume ratio of surfactant solution.
Mix with manganous salt solution the most again, obtain mixed solution；The concentration of described manganous salt solution be preferably 1～ 50mmol/L, more preferably 3～40mmol/L, be further preferably 5～30mmol/L, is further preferably 5～25mmol/L, most preferably 10～25mmol/L；In some embodiments that the present invention provides, the concentration of described manganous salt solution is preferably 11.4mmol/ L；In some embodiments that the present invention provides, the concentration of described manganous salt solution is preferably 23.7mmol/L；In the present invention In other embodiments provided, the concentration of described manganous salt solution is preferably 3.5mmol/L；Described carbon sulfur composite with The mass volume ratio of manganous salt solution is preferably (0.25～1) g:(5～50) ml, more preferably (0.25～1) g:(5～40) Ml, is further preferably (0.25～1) g:(10～30) ml, most preferably (0.25～1) g:(10～20) ml；There is provided in the present invention In some embodiments, described carbon sulfur composite is preferably 0.25g:10ml with the mass volume ratio of manganous salt solution；At this In other embodiments that invention provides, the mass volume ratio of described carbon sulfur composite and manganous salt solution is preferably 1g: 10ml；The time of described mixing is preferably 3～10h, and more preferably 4～8h, be further preferably 4～7h, most preferably 5～6h；? In some embodiments that the present invention provides, the time of described mixing is preferably 5h.
Oxidizing agent solution is added in mixed solution；The oxidant that described oxidizing agent solution is well known to those skilled in the art Solution, there is no special restriction, is preferably potassium permanganate, potassium ferrate and the one or many in potassium dichromate in the present invention The aqueous solution planted；The concentration of described oxidizing agent solution is preferably 0.1～50mmol/L, more preferably 0.6～40mmol/L, more excellent Elect 0.6～30mmol/L as, be further preferably 0.6～20mmol/L, be further preferably 0.6～10mmol/L, be further preferably 0.6～ 5mmol/L, most preferably 0.6～4mmol/L；In some embodiments that the present invention provides, the concentration of described oxidizing agent solution It is preferably 0.6mmol/L；In some embodiments that the present invention provides, the concentration of described oxidizing agent solution is preferably 1.8mmol/ L；In other embodiments that the present invention provides, the concentration of described oxidizing agent solution is preferably 3.2mmol/L；Described oxidant Oxidant in solution is preferably (2～20) with the mol ratio of divalent manganesetion in manganous salt: 1, more preferably (4～15): 1, it is further preferably (6～10): 1；In some embodiments that the present invention provides, the oxidant in described oxidizing agent solution and bivalence In manganese salt, the mol ratio of divalent manganesetion is preferably 7.89: 1；In some embodiments that the present invention provides, described oxidant is molten Oxidant in liquid is preferably 6.75: 1 with the mol ratio of divalent manganesetion in manganous salt；In other realities that the present invention provides Executing in example, the oxidant in described oxidizing agent solution is preferably 8.57: 1 with the mol ratio of divalent manganesetion in manganous salt.
In the present invention, described oxidizing agent solution is preferably added dropwise in mixed solution；The addition speed of described oxidizing agent solution Degree is preferably 5～20ml/min, and more preferably 5～15ml/min, be further preferably 8～12ml/min, most preferably 10ml/min.
After adding oxidizing agent solution, react；The temperature of described reaction is preferably 10 DEG C～60 DEG C, more preferably 20 DEG C ～50 DEG C, it is further preferably 30 DEG C～40 DEG C；The time of described reaction is preferably 10～60min, more preferably 20～50min, then It is preferably 20～40min, most preferably 20～30min.
After having reacted, preferably filter, wash, after drying, obtain manganese dioxide carbon coated sulfur composite；Described dry Temperature be preferably 50 DEG C～80 DEG C, more preferably 60 DEG C～70 DEG C, be further preferably 60 DEG C～65 DEG C, most preferably 65 DEG C；Institute Stating the dry time is preferably 10～20h, and more preferably 10～18h, be further preferably 12～16h, most preferably 12～14h.
The present invention by first allow surfactant-dispersed in the surface of carbon sulfur composite, then by surfactant with Mn2+Between chemical action make Mn2+It is scattered in the surface of carbon sulfur composite uniformly, finally by dropping oxidizing agent solution With Mn2+Reaction makes the MnO of generation2Directly it is coated on the surface of carbon sulfur composite.First, sulfur and electrolyte can so be reduced Contact and reduce sulfur component dissolve in the electrolytic solution；Secondly, MnO2Also there is a chemical action to make sulfur be more difficult to dissolve to sulfur In the electrolytic solution；Finally, the method is also highly suitable for being applied on the high carbon sulfur composite carrying sulfur content, can preferably improve it The charging and discharging capacity of material and cycle performance.
Present invention also offers manganese dioxide carbon coated sulfur composite prepared by a kind of said method, by kernel and shell Composition, described kernel is carbon sulfur composite, and described shell is manganese dioxide；The thickness of described shell is preferably 10～50nm, More preferably 20～40nm, it is further preferably 20～30nm.
The present invention, with manganese dioxide carbon coated sulfur composite, so can reduce sulfur and reduce sulfur with contacting of electrolyte Component is dissolved in the electrolytic solution；MnO2Also there is a chemical action to make sulfur be more difficult to dissolve in the electrolytic solution to sulfur；The method is also It is highly suitable to be applied on the high carbon sulfur composite carrying sulfur content, can preferably improve charging and discharging capacity and the circulation of its material Performance.
Present invention also offers a kind of lithium-sulfur cell, the manganese dioxide carbon coated sulfur composite wood prepared including said method Material；Described manganese dioxide carbon coated sulfur composite is positive electrode.
Technical scheme below in conjunction with the embodiment of the present invention is clearly and completely described, it is clear that described enforcement Example is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, this area is common The every other embodiment that technical staff is obtained under not making creative work premise, broadly falls into the model of present invention protection Enclose.
Embodiment 1
1.1 weigh 4g Sublimed Sulfur and 1g CMK-3 mixed grinding 1.5h in mortar, and compound is being loaded on polytetrafluoroethyl-ne Alkene reaction still is put in 155 DEG C of heating 12h in vacuum drying oven, is then added in planetary ball mill carry out ball milling after cooling, turns Speed, at 300r/min ball milling 8h, i.e. can get carbon sulfur composite CMK-3 S.
1.2 weigh 250mgCMK-3@S joins in 40ml 2%PVP aqueous solution, magnetic agitation 5h, then to mixed solution The MnSO of middle addition 10ml 11.4mmol/L4Solution magnetic agitation 30min, finally by the 50ml1.8mmol/L's that configured KMnO4Solution drips in mixed liquor in 5min uniformly, is stirred for 25min after dripping off；Solution after having reacted filters, Washing i.e. obtains the manganese dioxide carbon coated i.e. MnO of sulfur composite2@CMK-3/S material, then by gained MnO2@CMK-3/S material First being put in 60 DEG C of dry 12h in air dry oven, then be placed in 60 DEG C of dry 12h in vacuum drying oven, the thickness of clad is 25nm。
1.3 by 1.2 MnO prepared2@CMK-3/S material is pressed with conductive black Super-P, binding agent (Kynoar) Mass ratio according to 8:1:1 mixes, and adds appropriate additive N-Methyl pyrrolidone (NMP), is then coated uniformly on aluminium foil collection On fluid and vacuum dried, roll-in, is prepared as positive plate；Using lithium sheet is negative plate, the LiCF of 0.5mol/L3SO3Coordinate 0.5mol/L LiNO3Mixed solution (DME:DOL=1:1 (V/V)) be electrolyte, barrier film select model be Celgard The microporous polypropylene membrane of 2400, is assembled into CR2016 simulated battery.
Utilize scanning electron microscope that the carbon sulfur composite CMK-3@S obtained in 1.1 is analyzed, obtain its scanning Electromicroscopic photograph, as shown in Figure 1.The surface of carbon sulfur composite CMK-3@S there is also the component sulfur of part as shown in Figure 1, thus Surface ratio is rougher.
To the MnO obtained in the carbon sulfur composite CMK-3@S and 1.2 obtained in 1.12@CMK-3/S material carries out thermogravimetric Analyze, obtain its TGA curve chart, as shown in Figure 2.MnO as shown in Figure 22The load sulfur content of@CMK-3/S and CMK-3@S is respectively 80% and 72%, all there is higher load sulfur content.
Utilize the scanning electron microscope MnO to obtaining in 1.22@CMK-3/S material is analyzed, and obtains its scanning electricity Mirror photo, as shown in Figure 3.The Surface coating of CMK-3/S lepidiod MnO as shown in Figure 32, sulfur component is completely by MnO2Wrapped Cover.
The CR2016 simulated battery obtained in 1.3 is carried out Electrochemical Detection, obtains MnO2@CMK-3/S is in 0.1C multiplying power Under first charge-discharge curve chart, as shown in Figure 4, its first discharge specific capacity reaches 1083mAh/g as shown in Figure 4；Obtain MnO2@CMK-3/S and CMK-3@S cycle performance figure under 0.1C multiplying power, can obtain CMK-3@S surface as it is shown in figure 5, compare Cladding MnO2Its first discharge specific capacity is increased to 1083mAh/g by 956mAh/g afterwards, and MnO after circulating 100 times2@CMK- The capacity of the battery of 3/S material still also has 589mAh/g, far above the capacity of the battery 365mAh/g of CMK-3@S material, and Coulombic efficiency is all close to 100%, it can be seen that MnO2The initial capacity of@CMK-3/S material and cycle performance are obtained for substantially Raising.
Embodiment 2
2.1 weigh 3g Sublimed Sulfur and 2gCNT mixed grinding 1.5h in mortar, anti-compound is loaded on politef Answering and be put in 155 DEG C of heating 12h in vacuum drying oven in still, be then added in planetary ball mill carry out ball milling after cooling, rotating speed exists 300r/min ball milling 8h, i.e. can get carbon sulfur composite CNT S.
2.2 weigh the CNT@S obtained in 1g 2.1 joins in 40ml2%PVP aqueous solution, magnetic agitation 5h, then to mixed Close the MnSO adding 10ml23.7mmol/L in solution4Solution magnetic agitation 30min, the 50ml3.2mmol/ that finally will configure The KMnO of L4Solution drips in mixed liquor in 5min uniformly, is stirred for 25min after dripping off.Solution mistake after having reacted Filter, washing i.e. obtain the manganese dioxide carbon coated i.e. MnO of sulfur composite2@CNT/S material, then by the MnO of gained2@CNT/S material First being put in 60 DEG C of dry 12h in air dry oven, then be placed in 60 DEG C of dry 12h in vacuum drying oven, the thickness of clad is 20nm。
2.3 MnO that will prepare in 2.22@CNT/S material is pressed with conductive black Super-P, binding agent (Kynoar) Mass ratio according to 8:1:1 mixes, and adds appropriate additive N-Methyl pyrrolidone (NMP), is then coated uniformly on aluminium foil collection On fluid and vacuum dried, roll-in, is prepared as positive plate；Using lithium sheet is negative plate, the LiCF of 0.5mol/L3SO3Coordinate 0.5mol/L LiNO3Mixed solution (DME:DOL=1:1 (V/V)) be electrolyte, barrier film select model be Celgard The microporous polypropylene membrane of 2400, is assembled into CR2016 simulated battery.
Utilize scanning electron microscope that the carbon sulfur composite CNT@S obtained in 2.1 is analyzed, obtain its scanning electricity Mirror photo, as shown in Figure 6.During sulfur component is evenly distributed on the carbon pipe of CNT as shown in Figure 6.
Utilize the scanning electron microscope MnO to obtaining in 2.22@CNT/S material is analyzed, and obtains its scanning electron microscope Photo, as shown in Figure 7.CMK-3/S is uniformly by MnO as shown in Figure 72It is coated with.
The CR2016 simulated battery obtained in 2.3 is carried out Electrochemical Detection, obtains MnO2@CNT/S is under 0.1C multiplying power First charge-discharge curve chart, as shown in Figure 8, its first discharge specific capacity reaches 1239mAh/g as shown in Figure 8, has higher Initial discharge capacity.
Embodiment 3
3.1 weigh 4g Sublimed Sulfur and 1g CMK-3 mixed grinding 1.5h in mortar, and compound is being loaded on polytetrafluoroethyl-ne Alkene reaction still is put in 155 DEG C of heating 12h in vacuum drying oven, is then added in planetary ball mill carry out ball milling after cooling, turns Speed, at 300r/min ball milling 8h, i.e. can get carbon sulfur composite CMK-3 S.
3.2 weigh the CMK-3@S obtained in 250mg 3.1 joins in 40ml 2%PVP aqueous solution, magnetic agitation 5h, The MnSO of 10ml 3.5mmol/L is added again in mixed solution4Solution magnetic agitation 30min, 50 ml that finally will configure The KMnO of 0.6mmol/L4Solution drips in mixed liquor in 5min uniformly, is stirred for 25min after dripping off.After having reacted Solution filter, washing i.e. obtain the manganese dioxide carbon coated i.e. MnO of sulfur composite2@CMK-3/S material, then by gained MnO2@CMK-3/S material is first put in 60 DEG C of dry 12h in air dry oven, then is placed in 60 DEG C of dry 12h in vacuum drying oven.
3.3 MnO that will prepare in 3.22@CMK-3/S material and conductive black Super-P, binding agent (Kynoar) Mix according to the mass ratio of 8:1:1, add appropriate additive N-Methyl pyrrolidone (NMP), be then coated uniformly on aluminium foil On collector and vacuum dried, roll-in, is prepared as positive plate；Using lithium sheet is negative plate, the LiCF of 0.5mol/L3SO3Join Close 0.5mol/L LiNO3Mixed solution (DME:DOL=1:1 (V/V)) be electrolyte, barrier film select model be Celgard The microporous polypropylene membrane of 2400, is assembled into CR2016 simulated battery.
Embodiment 4
4.1 weigh 4g Sublimed Sulfur and 1g CMK-3 mixed grinding 1.5h in mortar, and compound is being loaded on polytetrafluoroethyl-ne Alkene reaction still is put in 155 DEG C of heating 12h in vacuum drying oven, is then added in planetary ball mill carry out ball milling after cooling, turns Speed, at 300r/min ball milling 8h, i.e. can get carbon sulfur composite CMK-3 S.
4.2 weigh the CMK-3@S obtained in 250mg 4.1 joins in 40ml 4%PVP aqueous solution, magnetic agitation 5h, The MnSO of 10ml 11.4mmol/L is added again in mixed solution4Solution magnetic agitation 30min, finally will configure The KMnO of 50ml1.8mmol/L4Solution drips in mixed liquor in 5min uniformly, is stirred for 25min after dripping off.Will reaction Solution after complete filters, washing i.e. obtains the manganese dioxide carbon coated i.e. MnO of sulfur composite2@CMK-3/S material, then by gained MnO2@CMK-3/S material is first put in 60 DEG C of dry 12h in air dry oven, then is placed in vacuum drying oven 60 DEG C and is dried 12h。
4.3 MnO that will prepare in 4.22@CMK-3/S material and conductive black Super-P, binding agent (Kynoar) Mix according to the mass ratio of 8:1:1, add appropriate additive N-Methyl pyrrolidone (NMP), be then coated uniformly on aluminium foil On collector and vacuum dried, roll-in, is prepared as positive plate；Using lithium sheet is negative plate, the LiCF of 0.5mol/L3SO3Join Close 0.5mol/L LiNO3Mixed solution (DME:DOL=1:1 (V/V)) be electrolyte, barrier film select model be Celgard The microporous polypropylene membrane of 2400, is assembled into CR2016 simulated battery.
Embodiment 5
5.1 weigh 4g Sublimed Sulfur and 1g CMK-3 mixed grinding 1.5h in mortar, and compound is being loaded on polytetrafluoroethyl-ne Alkene reaction still is put in 155 DEG C of heating 12h in vacuum drying oven, is then added in planetary ball mill carry out ball milling after cooling, turns Speed, at 300r/min ball milling 8h, i.e. can get carbon sulfur composite CMK-3 S.
5.2 weigh the CMK-3@S obtained in 250mg 5.1 joins in 40ml4%PVP aqueous solution, magnetic agitation 5h, then The MnSO of 10ml3.5mmol/L is added in mixed solution4Solution magnetic agitation 30min, finally will configure The KMnO of 50ml0.6mmol/L4Solution drips in mixed liquor in 5min uniformly, is stirred for 25min after dripping off.Will reaction Solution after complete filters, washing i.e. obtains the manganese dioxide carbon coated i.e. MnO of sulfur composite2@CMK-3/S material, then by gained MnO2@CMK-3/S material is first put in 60 DEG C of dry 12h in air dry oven, then is placed in vacuum drying oven 60 DEG C and is dried 12h。
5.3 MnO that will prepare in 5.22@CMK-3/S material and conductive black Super-P, binding agent (Kynoar) Mix according to the mass ratio of 8:1:1, add appropriate additive N-Methyl pyrrolidone (NMP), be then coated uniformly on aluminium foil On collector and vacuum dried, roll-in, is prepared as positive plate；Using lithium sheet is negative plate, the LiCF of 0.5mol/L3SO3Join Close 0.5mol/L LiNO3Mixed solution (DME:DOL=1:1 (V/V)) be electrolyte, barrier film select model be Celgard The microporous polypropylene membrane of 2400, is assembled into CR2016 simulated battery.
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It is right to it should be pointed out that, For those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention is carried out Some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.

Claims (10)

1. the preparation method of a manganese dioxide carbon coated sulfur composite, it is characterised in that including:
S1) carbon sulfur composite, surfactant are mixed with manganous salt in water, obtain mixed solution；
S2) in mixed solution, add oxidizing agent solution, reaction, obtain manganese dioxide carbon coated sulfur composite.
Preparation method the most according to claim 1, it is characterised in that described carbon sulfur composite is made in accordance with the following methods Standby:
Being mixed with Sublimed Sulfur by porous carbon, heating is reacted, and obtains carbon sulfur composite.
Preparation method the most according to claim 2, it is characterised in that described porous carbon is selected from CMK, single wall CNT, Duo Bi CNT, Graphene, CNF, activated carbon, fullerene and one or more in MOFs；Described porous carbon with the mass ratio of Sublimed Sulfur is 1:(1～4).
Preparation method the most according to claim 1, it is characterised in that including:
S1) carbon sulfur composite is dispersed in surfactant solution, mixes with manganous salt solution the most again, mixed Solution；
S2) in mixed solution, add oxidizing agent solution, reaction, obtain manganese dioxide carbon coated sulfur composite.
Preparation method the most according to claim 4, it is characterised in that described surfactant is selected from polyvinylpyrrolidine In ketone, poly(ethylene oxide), octyl phenyl polyoxyethylene ether and cetyl trimethylammonium bromide one or more；Described bivalent manganese Salt is selected from MnSO4、MnCl2With Mn (CH3COO)2In one or more；Oxidant in described oxidizing agent solution is selected from Gao Meng Acid potassium, potassium ferrate and one or more in potassium dichromate.
Preparation method the most according to claim 4, it is characterised in that the mass concentration of described surfactant solution is 0.25%～6%；The concentration of described manganous salt solution is 1～50mmol/L；The concentration of described oxidizing agent solution be 0.1～ 50mmol/L；Described carbon sulfur composite is (0.25～1) g:(20～200 with the mass volume ratio of surfactant solution) ml。
Preparation method the most according to claim 4, it is characterised in that described step S1) in mixing time be 3～10h； Described step S2) in reaction temperature be 10 DEG C～60 DEG C；The time of reaction is 10～60min.
Preparation method the most according to claim 4, it is characterised in that the speed of the addition of described oxidizing agent solution be 5～ 20ml/min。
9. a manganese dioxide carbon coated sulfur composite, it is characterised in that being made up of kernel and shell, described kernel is carbon sulfur Composite, described shell is manganese dioxide.
10. a lithium-sulfur cell, it is characterised in that include the manganese dioxide carbon coated prepared by claim 1～8 any one Manganese dioxide carbon coated sulfur composite described in sulfur composite or claim 9.
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CN106992291A (en) * 2017-04-19 2017-07-28 扬州大学 Manganese dioxide modification core shell structure-hollow microporous carbon ball coats the preparation method of nanometer sulfur molecule
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CN112038635A (en) * 2020-08-04 2020-12-04 湘潭大学 Lithium-sulfur battery graphene-loaded cementite particle composite positive electrode material and preparation method thereof
CN112968173A (en) * 2021-02-01 2021-06-15 江苏华富储能新技术股份有限公司 Porous carbon-coated sulfur vacancy composite electrode material, preparation method thereof and circular electrode adopting material
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