CN110148717A - A kind of N doping graphene oxide/manganese sulfide carries sulphur composite material and preparation method and application - Google Patents
A kind of N doping graphene oxide/manganese sulfide carries sulphur composite material and preparation method and application Download PDFInfo
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- CN110148717A CN110148717A CN201910351525.2A CN201910351525A CN110148717A CN 110148717 A CN110148717 A CN 110148717A CN 201910351525 A CN201910351525 A CN 201910351525A CN 110148717 A CN110148717 A CN 110148717A
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- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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Abstract
The invention discloses the preparation methods that a kind of N doping graphene oxide/manganese sulfide carries sulphur composite material, include the following steps: the preparation of (1) N doping graphene oxide/vulcanization manganese material: graphene oxide powder is dissolved in aqueous solution and is dispersed, sequentially add thiocarbamide and four acetate hydrate manganese, stirring is transferred to water heating kettle to after being completely dissolved, successively toasted, cooling, be centrifugally separating to obtain N doping graphene oxide/vulcanization manganese material；(2) N doping graphene oxide/manganese sulfide composite material preparation of sulphur is carried: by N doping graphene oxide/vulcanization manganese material and sublimed sulfur mixed grinding, it is transferred to water heating kettle fusion, Baking out obtains carrying N doping graphene oxide/manganese sulfide composite material of sulphur.The present invention is by simple hydro-thermal method and melts mixed thermal method, and lithium sulfur battery anode material obtained has high specific surface area, specific capacity and carries sulfur content, excellent cycle performance and high rate performance, excellent combination property.
Description
Technical field
Sulphur is carried the present invention relates to lithium-sulfur cell technical field more particularly to a kind of N doping graphene oxide/manganese sulfide to answer
Condensation material and its preparation method and application.
Background technique
Lithium-sulfur cell is a kind of lithium battery of the lithium metal as cathode using element sulphur as anode.Elemental sulfur is on ground
Rich reserves in ball have the characteristics that cheap, environmental-friendly.Using sulphur as the lithium-sulfur cell of positive electrode, material
Theoretical specific capacity and battery theory specific energy are higher, still, lithium-sulfur cell there are the shortcomings that it is also very obvious, be mainly reflected in
Anode, due to shuttle effect, active material constantly loses during cycle charge-discharge, so that the performance of positive electrode is from theory
Level disparity is larger, reduces the electric conductivity of electrode, shortens the battery electrode service life, meanwhile, existing lithium-sulfur cell prepares work
Skill is complicated, and manufacturing cost is higher, is not suitable for batch production.
Therefore, inventor is dedicated to designing a kind of N doping graphene oxide/manganese sulfide and carries sulphur composite material and its preparation
Methods and applications are to solve the above problems.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, it is an object of the invention to: a kind of N doping oxygen is provided
Graphite alkene/manganese sulfide carries the preparation method of sulphur composite material, and the preparation method is by simple hydro-thermal method, by graphite oxide
Alkene, transition metal vulcanization manganese introducing sulphur are positive and compound therewith, and the NGM/S composite material of preparation has high specific surface area, shape
The advantages that looks are easily controllable, and preparation process is simple reduces manufacturing cost.
It is another object of the present invention to: a kind of N doping graphene oxide/manganese sulfide load sulphur composite material is provided, it should
Composite material has high specific capacity and carries sulfur content, and excellent cycle performance and high rate performance, excellent combination property can be used for lithium
Sulphur cell positive electrode extends the service life of lithium-sulfur cell.
A further object of the invention is: providing a kind of N doping graphene oxide/manganese sulfide and carries sulphur composite material
Using the N doping rGO-MnS/S composite material of the load sulphur of production can be used as the positive electrode of lithium-sulfur cell.
The purpose of the invention is achieved by the following technical solution:
A kind of N doping graphene oxide/manganese sulfide carries the preparation method of sulphur composite material, includes the following steps:
(1) hydro-thermal method prepares N doping rGO-MnS material: graphene oxide powder is dissolved in aqueous solution and is dispersed,
Sequentially add thiocarbamide and four acetate hydrate manganese, stirring is transferred to water heating kettle to after being completely dissolved, it is successively toasted, cooling, from
The isolated N doping rGO-MnS material of the heart；
(2) melt the N doping rGO-MnS/S composite material that mixed thermal method preparation carries sulphur: by N doping rGO-MnS material with
Sublimed sulfur mixed grinding, is transferred to water heating kettle fusion, and Baking out obtains carrying the N doping rGO-MnS/S composite material of sulphur；
The fundamental reaction principle of this programme is: thiocarbamide (NH2CSNH2) and four acetate hydrate manganese (Mn (CH3COO)2·4H2O)
Ion exchange occurs in aqueous solution to react to obtain product manganese sulfide, in the displacement reaction process, thiocarbamide (NH2CSNH2) is sulphur
Source provides sulphion, four acetate hydrate manganese (Mn (CH3COO)2·4H2O) it is manganese source, manganese ion, graphene oxide (GO) is provided
It is intended only as the hydrothermal growth carrier of transition metal vulcanization manganese, subsequent also to need hydro-thermal composite sulfuration manganese, the two acts synergistically on
Lithium-sulfur cell.
Preferably, in the step (1), graphene oxide quality is 45-55mg, and the volume of aqueous solution is 27-33mL, sulphur
The molal weight ratio of urea and four acetate hydrate manganese is 2:1, and baking temperature is 160-200 DEG C, baking time 18-22h.
Preferably, the step 1 specifically: the graphene oxide powder of load weighted 45-55mg is dissolved in 27-33mL
Deionized water solution in, carry out the dispersion of graphene oxide in the solution using ultrasonoscope, after 0.9-1.1h, successively
The thiocarbamide of 1.8-2.2mmol and the four acetate hydrate manganese of 0.9-1.1mmol, mole matter of thiocarbamide and four acetate hydrate manganese is added
Amount carries out magnetic agitation to being completely dissolved, continues that mixed solution is transferred to water heating kettle liner after stirring 27-33min than being 2:1
In, it is put into baking oven after water heating kettle is tightened, adjusts the temperature to 160-200 DEG C and keep 18-22h, passed through after water heating kettle is cooling
The isolated N doping rGO-MnS material of centrifuge high speed rotation.
Preferably, in the step (1), graphene oxide powder is prepared by Hummer ' s method, the graphene oxide powder
Ultrasonic Pulverization 0.9-1.1h need to be passed through.
Preferably, in the step (2), the mass ratio of N doping rGO-MnS material and sublimed sulfur is 1:4, baking temperature
It is 140-170 DEG C, baking time 10-14h.
Preferably, the step 2 specifically: weigh the sublimed sulfur and N doping that mass ratio is 4:1 using electronic balance
RGO-MnS material is put into agate mortar and is sufficiently mixed grinding, mixed material is put into water heating kettle, is heated in an oven
To 140-170 DEG C, so that sulphur is sufficiently merged with N doping rGO-MnS material, temperature stops heating after stablizing holding 10-14h, takes
Sample obtains N doping rGO-MnS/S composite material out.
Preferably, in the step (1), the N doping rGO-MnS material is carrier material, the N doping rGO-
After MnS material carries sulphur, MnS therein is not intended as active material contribution capacity, but plays the more vulcanizations of absorption as close sulphur component
The effect of object.
Preferably, in the step (2), N doping rGO-MnS material needs to be passed through nitrogen deoxygenation, deoxygenation when merging with sulphur
Time is 9-11min.
Another object of the present invention is achieved through the following technical solutions: a kind of N doping graphene oxide/manganese sulfide load
Sulphur composite material, the N doping graphene oxide/manganese sulfide carry sulphur composite material and are made according to above-mentioned preparation method.
A further object of the invention is achieved through the following technical solutions: a kind of N doping graphene oxide/manganese sulfide load
The application of sulphur composite material, the N doping graphene oxide/manganese sulfide carry the anode that sulphur composite material is applied to lithium-sulfur cell
In, which is 1.7-2.8V.
The beneficial effects of the present invention are: the preparation method of composite material of the present invention is mixed by simple hydro-thermal method and melting
Manufacturing cost is effectively reduced without complicated preparation flow in thermal method, and lithium sulfur battery anode material pattern obtained is easily controllable,
With high specific surface area, specific capacity and carry sulfur content, excellent cycle performance and high rate performance, excellent combination property.
The present invention is prepared for N doping rGO-MnS composite material (NGM) using graphene as substrate, by hydro-thermal method, as
Lithium-sulphur cell positive electrode carrier material, after which carries sulphur, though transient metal Mn S therein not as active material,
But plays the role of adsorbing polysulfide, do not influence lithium-sulfur cell charging/discharging voltage not only, also there is characteristic of semiconductor, effectively mention
High electrode electric conductivity extends the service life of lithium-sulfur cell.
Detailed description of the invention
Fig. 1 is that the SEM figure (a) of N doping rGO-MnS material (NGM) of the present invention and the SEM amplified under certain multiple scheme
(b)；
Fig. 2 is the SEM figure (c) for the N doping rGO-MnS/S composite material (NGM/S) that the present invention carries sulphur；
Fig. 3 is the EDS energy spectrum diagram (d) of N doping rGO-MnS material (NGM) of the present invention；
Fig. 4 is that the present invention carries the N doping rGO-MnS/S composite material (NGM/S) of sulphur and the XRD comparison diagram of standard substance；
Fig. 5 is the Raman figure for the N doping rGO-MnS/S composite material (NGM/S) that the present invention carries sulphur；
Fig. 6 is the full spectrogram (a) of XPS for the N doping rGO-MnS/S composite material (NGM/S) that the present invention carries sulphur, N1S spectrogram
(b), S2p spectrogram (c) and Mn2p spectrogram (d)；
Fig. 7 is that the present invention carries 200 of the N doping rGO-MnS/S composite material (NGM/S) of sulphur under 0.5C current density
It encloses cyclic curve (a)；
Fig. 8 is lithium-sulfur cell charging and discharging curve figure (b) of the present invention；
Fig. 9 is the high rate performance figure for the N doping rGO-MnS/S composite material (NGM/S) that the present invention carries sulphur.
Specific embodiment
Below with reference to examples and drawings 1-9, embodiments of the present invention are specifically illustrated, attached drawing is only for reference and explanation makes
With not constituting the limitation to the invention patent protection scope.
Embodiment 1
A kind of N doping graphene oxide/manganese sulfide carries the preparation method of sulphur composite material, includes the following steps:
(1) hydro-thermal method prepares N doping rGO-MnS material (NGM): graphene oxide (GO) powder is by Hummer ' s legal system
Standby, which need to be by Ultrasonic Pulverization 0.9h, by graphene oxide (GO) powder of load weighted 45mg
It is dissolved in the deionized water solution of 27mL, carries out the dispersion of graphene oxide (GO) in the solution using ultrasonoscope, pass through
After 0.9h, the thiocarbamide (NH2CSNH2) of 1.8mmol and the four acetate hydrate manganese (Mn (CH of 0.9mmol are sequentially added3COO)2·
4H2O), it is ensured that thiocarbamide (NH2CSNH2) and four acetate hydrate manganese (Mn (CH3COO)2·4H2O molal weight ratio) is 2:1, into
Row magnetic agitation to being completely dissolved continues that mixed solution is transferred in the water heating kettle liner of 100mL volume after stirring 27min,
It is put into baking oven after water heating kettle is tightened, adjusts the temperature to 160 DEG C and keeps 22h, through centrifuge high speed after water heating kettle is cooling
Rotating separation obtains N doping rGO-MnS material (NGM)；
(2) it melts the N doping rGO-MnS/S composite material (NGM/S) that mixed thermal method preparation carries sulphur: being claimed using electronic balance
Taking mass ratio is the sublimed sulfur and N doping rGO-MnS material (NGM) of 4:1, is put into agate mortar and is sufficiently mixed grinding, will mix
Material afterwards is put into small water heating kettle, is heated to 140 DEG C in an oven so that sulphur sufficiently with N doping rGO-MnS material (NGM)
Fusion, N doping rGO-MnS material (NGM) need to be passed through nitrogen deoxygenation with sulphur when merging, the deoxygenation time is 9min, small water heating kettle
Middle temperature stops heating after stablizing holding 14h, takes out the N doping rGO-MnS/S composite material (NGM/S) that sample obtains carrying sulphur.
A kind of N doping graphene oxide/manganese sulfide load sulphur composite material, the N doping graphene oxide/manganese sulfide carry
Sulphur composite material is above-mentioned N doping rGO-MnS/S composite material (NGM/S), is made according to above-mentioned preparation method.
A kind of N doping graphene oxide/manganese sulfide carries the application of sulphur composite material, the N doping graphene oxide/sulphur
Change manganese and carry sulphur composite material applied in the anode of lithium-sulfur cell, which is 1.7V.
Embodiment 2
The present embodiment and above-described embodiment 1 the difference is that: it is multiple that a kind of N doping graphene oxide/manganese sulfide carries sulphur
The preparation method of condensation material, includes the following steps:
(1) hydro-thermal method prepares N doping rGO-MnS material (NGM): graphene oxide (GO) powder is by Hummer ' s legal system
Standby, which need to be molten by graphene oxide (GO) powder of load weighted 50mg by Ultrasonic Pulverization 1h
Solution carries out the dispersion of graphene oxide (GO) using ultrasonoscope, by 1h in the deionized water solution of 30mL in the solution
Afterwards, the thiocarbamide (NH2CSNH2) of 2mmol and the four acetate hydrate manganese (Mn (CH of 1mmol are sequentially added3COO)2·4H2), O really
Protect thiocarbamide (NH2CSNH2) and four acetate hydrate manganese (Mn (CH3COO)2·4H2O molal weight ratio) is 2:1, carries out magnetic force and stirs
It mixes and continues that mixed solution is transferred in the water heating kettle liner of 100mL volume after stirring 30min to being completely dissolved, by water heating kettle
It is put into baking oven after tightening, adjusts the temperature to 180 DEG C and keeps 20h, separated after water heating kettle is cooling through centrifuge high speed rotation
Obtain N doping rGO-MnS material (NGM)；
(2) it melts the N doping rGO-MnS/S composite material (NGM/S) that mixed thermal method preparation carries sulphur: being claimed using electronic balance
Taking mass ratio is the sublimed sulfur and N doping rGO-MnS material (NGM) of 4:1, is put into agate mortar and is sufficiently mixed grinding, will mix
Material afterwards is put into small water heating kettle, is heated to 155 DEG C in an oven so that sulphur sufficiently with N doping rGO-MnS material (NGM)
Fusion, N doping rGO-MnS material (NGM) need to be passed through nitrogen deoxygenation with sulphur when merging, the deoxygenation time is 10min, small hydro-thermal
Temperature stops heating after stablizing holding 12h in kettle, takes out the N doping rGO-MnS/S composite material (NGM/ that sample obtains carrying sulphur
S)。
A kind of N doping graphene oxide/manganese sulfide carries the application of sulphur composite material, the N doping graphene oxide/sulphur
Change manganese and carry sulphur composite material applied in the anode of lithium-sulfur cell, which is 2.25V.
Embodiment 3
The present embodiment and above-described embodiment 1 the difference is that: it is multiple that a kind of N doping graphene oxide/manganese sulfide carries sulphur
The preparation method of condensation material, includes the following steps:
(1) hydro-thermal method prepares N doping rGO-MnS material (NGM): graphene oxide (GO) powder is by Hummer ' s legal system
Standby, which need to be by Ultrasonic Pulverization 1.1h, by graphene oxide (GO) powder of load weighted 55mg
It is dissolved in the deionized water solution of 33mL, carries out the dispersion of graphene oxide (GO) in the solution using ultrasonoscope, pass through
After 1.1h, the thiocarbamide (NH2CSNH2) of 2.2mmol and the four acetate hydrate manganese (Mn (CH of 1.1mmol are sequentially added3COO)2·
4H2O), it is ensured that thiocarbamide (NH2CSNH2) and four acetate hydrate manganese (Mn (CH3COO)2·4H2O molal weight ratio) is 2:1, into
Row magnetic agitation to being completely dissolved continues that mixed solution is transferred in the water heating kettle liner of 100mL volume after stirring 33min,
It is put into baking oven after water heating kettle is tightened, adjusts the temperature to 200 DEG C and keeps 18h, through centrifuge high speed after water heating kettle is cooling
Rotating separation obtains N doping rGO-MnS material (NGM)；
(2) it melts the N doping rGO-MnS/S composite material (NGM/S) that mixed thermal method preparation carries sulphur: being claimed using electronic balance
Taking mass ratio is the sublimed sulfur and N doping rGO-MnS material (NGM) of 4:1, is put into agate mortar and is sufficiently mixed grinding, will mix
Material afterwards is put into small water heating kettle, is heated to 170 DEG C in an oven so that sulphur sufficiently with N doping rGO-MnS material (NGM)
Fusion, N doping rGO-MnS material (NGM) need to be passed through nitrogen deoxygenation with sulphur when merging, the deoxygenation time is 11min, small hydro-thermal
Temperature stops heating after stablizing holding 10h in kettle, takes out the N doping rGO-MnS/S composite material (NGM/ that sample obtains carrying sulphur
S)。
A kind of N doping graphene oxide/manganese sulfide carries the application of sulphur composite material, the N doping graphene oxide/sulphur
Change manganese and carry sulphur composite material applied in the anode of lithium-sulfur cell, which is 2.8V.
The fundamental reaction principle of step (1) of the present invention is: thiocarbamide (NH2CSNH2) and four acetate hydrate manganese (Mn
(CH3COO)2·4H2O ion exchange) occurs in aqueous solution to react to obtain product manganese sulfide, in the displacement reaction process, thiocarbamide
(NH2CSNH2) it is sulphur source, sulphion, four acetate hydrate manganese (Mn (CH is provided3COO)2·4H2O) it is manganese source, manganese ion is provided,
Graphene oxide (GO) is intended only as the hydrothermal growth carrier of transition metal vulcanization manganese, subsequent also to need hydro-thermal composite sulfuration manganese,
The two acts synergistically on lithium-sulfur cell, thiocarbamide (NH2CSNH2) and four acetate hydrate manganese (Mn (CH3COO)2·4H2It O) is all synthesis
Raw material can theoretically be replaced with other raw materials, and still, the pattern and performance that different sulphur sources and manganese source can be final to product are all
It can have an impact.
NGM is the abbreviation of product N doping rGO-MnS material english abbreviation in the present invention, and Chinese is interpreted as the oxygen of N doping
Graphite alkene/manganese sulfide compound, NGM/S are the abbreviation for carrying the N doping rGO-MnS/S composite material english abbreviation of sulphur, Chinese
Graphene oxide/the manganese sulfide for being interpreted as N doping carries sulfur compound, and N represents nitrogen, and G represents graphene, and M represents manganese sulfide, S generation
Table sulphur.
Comparison diagram 1 and Fig. 2 scheme according to the sample SEM before and after load sulphur, determine N doping rGO-MnS material (NGM) and carry sulphur
N doping rGO-MnS/S composite material (NGM/S) pattern, due to carry sulphur N doping rGO-MnS/S composite material (NGM/
S) there is high specific surface area, pattern is easily controllable, convenient for batch production.
Fig. 4 is compared by the XRD of the N doping rGO-MnS/S composite material (NGM/S) and standard substance S that carry sulphur, is shown
Final sample, which carries in the N doping rGO-MnS/S composite material (NGM/S) of sulphur, the presence of S, and in the sample sulphur crystalline form simultaneously
It has not been changed.
Distribution of the Fig. 5 for the graphitization and defect of confirmatory sample, it was demonstrated that defect is more in sample, is easy to compound.
Referring to Fig. 7 and Fig. 8, for positive electrode when current density is 0.5C, capacity still possesses 701.7mAh after 200 circle of circulation
G-1, the capacity are equivalent to the 77.3% of highest point.
It can be seen that under the high current density of 2C from the high rate performance of Fig. 9, the positive electrode of lithium-sulfur cell still has
The reversible specific capacity of 360mAh g-1.
N doping rGO-MnS material (NGM) in the present invention is lithium-sulphur cell positive electrode carrier material, graphene oxide (GO)
Only play auxiliary substrate, after the N doping rGO-MnS material (NGM) carries sulphur, MnS therein is not intended as active material
Capacity is contributed, but plays the role of adsorbing polysulfide as close sulphur component, MnS has the advantages that first in the present invention, gathers around
There is very strong close chalcogen, it is strong for the suction-operated of polysulfide；Second, the voltage platform of lithiation is low, will not and lithium
The response voltage section of sulphur battery charging and discharging, which coincides, to be impacted；Third has metal or semimetal characteristic, improves conductive
Property.
The present invention is prepared for N doping rGO-MnS composite material (NGM) using graphene as substrate, by hydro-thermal method, as
Lithium-sulphur cell positive electrode carrier material, after which carries sulphur, though transient metal Mn S therein not as active material,
But plays the role of adsorbing polysulfide, will not coincide and impact with the response voltage section of lithium-sulfur cell charge and discharge, also
With characteristic of semiconductor, electrode conductivuty is effectively improved, extends the service life of lithium-sulfur cell.
The preparation method of composite material of the present invention is by simple hydro-thermal method and melts mixed thermal method, without complicated preparation stream
Manufacturing cost is effectively reduced in journey, and lithium sulfur battery anode material pattern obtained is easily controllable, has high specific surface area, specific volume
Amount and load sulfur content, excellent cycle performance and high rate performance, excellent combination property.
Above disclosed is only presently preferred embodiments of the present invention, cannot limit rights protection model of the invention with this
It encloses, therefore according to equivalent variations made by scope of the present invention patent, is still within the scope of the present invention.
Claims (10)
1. the preparation method that a kind of N doping graphene oxide/manganese sulfide carries sulphur composite material, which is characterized in that including walking as follows
It is rapid:
(1) hydro-thermal method prepares N doping rGO-MnS material: graphene oxide powder being dissolved in aqueous solution and dispersed, successively
Thiocarbamide and four acetate hydrate manganese are added, stirring is transferred to water heating kettle to after being completely dissolved, successively toasted, cooling, centrifugation point
From obtaining N doping rGO-MnS material；
(2) the N doping rGO-MnS/S composite material that mixed thermal method preparation carries sulphur is melted: by N doping rGO-MnS material and distillation
Sulphur mixed grinding, is transferred to water heating kettle fusion, and Baking out obtains carrying the N doping rGO-MnS/S composite material of sulphur.
2. N doping graphene oxide as described in claim 1/manganese sulfide carries the preparation method of sulphur composite material, feature exists
In in the step (1), graphene oxide quality is 45-55mg, and the volume of aqueous solution is 27-33mL, thiocarbamide and four hydration second
The molal weight ratio of sour manganese is 2:1, and baking temperature is 160-200 DEG C, baking time 18-22h.
3. N doping graphene oxide as described in claim 1/manganese sulfide carries the preparation method of sulphur composite material, feature exists
In the step 1 specifically: the deionization that the graphene oxide powder of load weighted 45-55mg is dissolved in 27-33mL is water-soluble
In liquid, the dispersion of graphene oxide is carried out in the solution using ultrasonoscope, after 0.9-1.1h, sequentially add 1.8-
The molal weight ratio of the thiocarbamide of 2.2mmol and the four acetate hydrate manganese of 0.9-1.1mmol, thiocarbamide and four acetate hydrate manganese is 2:
1, magnetic agitation is carried out to being completely dissolved, and continues that mixed solution is transferred in water heating kettle liner after stirring 27-33min, by water
Hot kettle is put into baking oven after tightening, and is adjusted the temperature to 160-200 DEG C and is kept 18-22h, through centrifuge height after water heating kettle is cooling
Fast rotating separation obtains N doping rGO-MnS material.
4. N doping graphene oxide as described in claim 1/manganese sulfide carries the preparation method of sulphur composite material, feature exists
In in the step (1), graphene oxide powder is prepared by Hummer ' s method, which need to pass through ultrasonic powder
Broken 0.9-1.1h.
5. N doping graphene oxide as described in claim 1/manganese sulfide carries the preparation method of sulphur composite material, feature exists
In, in the step (2), the mass ratio of N doping rGO-MnS material and sublimed sulfur is 1:4, and baking temperature is 140-170 DEG C,
Baking time is 10-14h.
6. N doping graphene oxide as described in claim 1/manganese sulfide carries the preparation method of sulphur composite material, feature exists
In the step 2 specifically: weigh the sublimed sulfur and N doping rGO-MnS material that mass ratio is 4:1 using electronic balance, put
Enter agate mortar and be sufficiently mixed grinding, mixed material is put into water heating kettle, is heated to 140-170 DEG C in an oven, is made
It obtains sulphur sufficiently to merge with N doping rGO-MnS material, temperature stops heating after stablizing holding 10-14h, and taking-up sample obtains nitrogen and mixes
Miscellaneous rGO-MnS/S composite material.
7. N doping graphene oxide as described in claim 1/manganese sulfide carries the preparation method of sulphur composite material, feature exists
In, in the step (1), the N doping rGO-MnS material is carrier material, after the N doping rGO-MnS material carries sulphur,
MnS therein is not intended as active material contribution capacity, but plays the role of adsorbing polysulfide as close sulphur component.
8. N doping graphene oxide as described in claim 1/manganese sulfide carries the preparation method of sulphur composite material, feature exists
In in the step (2), N doping rGO-MnS material needs to be passed through nitrogen deoxygenation with sulphur when merging, and the deoxygenation time is 9-
11min。
9. a kind of N doping graphene oxide/manganese sulfide carries sulphur composite material, which is characterized in that the N doping graphite oxide
Alkene/manganese sulfide carries sulphur composite material preparation method according to claim 1-8 and is made.
10. a kind of N doping graphene oxide/manganese sulfide as claimed in claim 9 carries the application of sulphur composite material, feature
It is, the N doping graphene oxide/manganese sulfide carries sulphur composite material and is applied in the anode of lithium-sulfur cell, the lithium-sulfur cell
Charging/discharging voltage section is 1.7-2.8V.
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