CN109360956A - A kind of positive electrode and preparation method thereof, lithium-sulfur cell - Google Patents
A kind of positive electrode and preparation method thereof, lithium-sulfur cell Download PDFInfo
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- CN109360956A CN109360956A CN201811156935.3A CN201811156935A CN109360956A CN 109360956 A CN109360956 A CN 109360956A CN 201811156935 A CN201811156935 A CN 201811156935A CN 109360956 A CN109360956 A CN 109360956A
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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
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of positive electrodes and preparation method thereof, lithium-sulfur cell.Positive electrode disclosed by the invention includes: the C of apertures3N4‑x, wherein 0 < x < 4；And it is carried on C3N4‑xSulphur.The preparation method of positive electrode according to the present invention, comprising steps of S1: by the C of apertures3N4It is mixed with Mg, heating reaction obtains the C of apertures after a certain period of time3N4‑x, wherein 0 < x < 4；S2: in the C of apertures3N4‑xMiddle sulfur loaded, obtains positive electrode.Positive electrode provided by the invention, on the one hand due to C3N4‑xIn contain nitrogen, to more sulphur lithiumation objects have good absorption property；On the other hand, due to C3N4‑xMiddle nitrogen content is with respect to C3N4It is lower, relative to C3N4When improving intrinsic conductivity, therefore the positive electrode being used for lithium-sulfur cell, the cyclical stability of lithium-sulfur cell can be improved.
Description
Technical field
The present invention relates to field of batteries more particularly to a kind of positive electrode and preparation method thereof, lithium-sulfur cell.
Background technique
Lithium ion battery occupies leading position in energy storage, due to the preparation process of its relative maturity and higher steady
It is qualitative to become a part indispensable in the modern life.Since the positive electrode and negative electrode capacity mismatch of lithium ion battery causes
Traditional lithium ion battery theoretical density is limited, to limit its answering in hybrid power electric car and large-scale intelligent power grid
With.The factors such as furthermore at high cost, toxicity is big and dangerous also counteract that its further develops.
Lithium-sulfur cell is as battery of new generation due to causing more and more researchs with preferable theoretical energy density
The concern of person.Further, since the low cost of element sulphur, environmental protection and resource content height make it be more suitable for doing electrode material.But
In cyclic process, the volume deformation rate of sulphur anode is up to 22% in lithium-sulfur cell, may make sulphur anode is internal to generate micro-crack,
Aggravate the capacity attenuation of lithium-sulfur cell.
Currently, the basis material of sulfur loaded generally selects three-dimensional porous carbon material, graphene and its derivative.However it is existing
Basis material in have the following deficiencies: that (1) porosity is low, storage sulphur ability it is weaker, cause the cyclical stability of lithium-sulfur cell compared with
Difference；(2) carbon materials such as three-dimensional porous carbon material, graphene and its derivative, absorption lithium-sulfur cell generate during the charging process
The ability of more sulphur lithiumation objects is weaker, still has more more sulphur lithiumation objects and is dissolved in electrolyte, keeps the circulation of lithium-sulfur cell steady
Qualitative reduction.
Wherein, C is generally used3N4Basis material of this carbon-nitrogen material as sulfur loaded, wherein the N element contained can be with
More sulphur lithiumation objects are adsorbed, but since its nitrogen content is relatively high, leads to the reduction of its intrinsic conductivity, so that lithium-sulfur cell can be reduced
Cyclical stability.
Summary of the invention
(1) technical problems to be solved
In order to solve the above problem of the prior art, the present invention provides a kind of positive electrode and preparation method thereof, the present invention
Positive electrode include apertures C3N4-x, wherein 0 < x < 4；And it is carried on C3N4-xSulphur, due to C3N4-xMiddle nitrogen content drop
It is low, relative to C3N4When improving intrinsic conductivity, therefore the positive electrode being used for lithium-sulfur cell, it is steady that its circulation can be improved
It is qualitative.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include:
According to an aspect of the present invention, a kind of positive electrode is provided, positive electrode includes: the C of apertures3N4-x, wherein 0
<x<4；And
It is carried on the C3N4-xSulphur.
A kind of embodiment of positive electrode according to the present invention, the C of the apertures3N4-xPorosity be 20~30m2/g。
According to another aspect of the present invention, a kind of preparation method of positive electrode is provided, comprising steps of
S1: by the C of apertures3N4It is mixed with Mg, heating reaction obtains the C of apertures after a certain period of time3N4-x, wherein 0 < x < 4；
S2: in the C of the apertures3N4-xMiddle sulfur loaded, obtains positive electrode.
A kind of embodiment of method produced according to the present invention, in step sl, the C of the apertures3N4With the quality of Mg
Than for 3~1.5:1；
Heating temperature is 600~800 DEG C, and the reaction time is 1~5h.
A kind of embodiment of method produced according to the present invention further comprises in step sl with dilute after the reaction was completed
The post-processing operation of acid and deionized water washing；
The diluted acid is the sulfuric acid or hydrochloric acid that concentration is 0.5~1.5mol/L.
A kind of embodiment of method produced according to the present invention, in step s 2, by the C of the apertures3N4-xIt is mixed with S
After heat certain time, positive electrode is obtained after cooling.
A kind of embodiment of method produced according to the present invention, the C of the apertures3N4-xMass ratio with S is 3~1:1；
The heating temperature is 150~155 DEG C, and the reaction time is 5~20h.
A kind of embodiment of method produced according to the present invention, the C of the apertures3N4It is to be mixed by thiocarbamide and ammonium chloride
Heating obtains.
A kind of embodiment of method produced according to the present invention, the mass ratio of the thiocarbamide and the ammonium chloride be 1:1~
2；
The temperature of heating is 500~600 DEG C, and heating time is 1~5h.
According to another aspect of the present invention, a kind of lithium-sulfur cell is provided, comprising: anode, cathode, electrolyte, wherein institute
Stating includes positive electrode of the invention in anode, or
It include the positive electrode that preparation method of the present invention obtains in the anode.
(3) beneficial effect
Positive electrode provided by the invention includes the C of apertures3N4-x, wherein 0 < x < 4；And it is carried on C3N4-xSulphur；One
Aspect is due to C3N4-xIn contain nitrogen, to more sulphur lithiumation objects have good absorption property；On the other hand, due to C3N4-xMiddle nitrogen
Content is with respect to C3N4It is lower, relative to C3N4It, can when improving intrinsic conductivity, therefore the positive electrode being used for lithium-sulfur cell
To improve its cyclical stability.
Preparation method of the invention, uses C3N4It is reacted with magnesium powder, generates C3N4-x, on the one hand due to C3N4-xIn contain nitrogen,
It has good absorption property to more sulphur lithiumation objects；On the other hand due to C3N4-xMiddle nitrogen content is with respect to C3N4It is lower, relative to
C3N4When improving intrinsic conductivity, therefore the positive electrode being used for lithium-sulfur cell, its cyclical stability can be improved.
Preparation method of the invention prepares C using thiocarbamide and ammonium chloride3N4, wherein C is formed after thiocarbamide heat resolve3N4,
And ammonium chloride forms ammonia and HCl since ammonium chloride decomposes as pore-foaming agent, can form porosity is 20~30m2/ g's
C3N4, improve C3N4Porosity, thus improve its store up sulphur ability, further improve the lithium sulphur containing the positive electrode
The cyclical stability of battery.
Preparation method of the invention, raw material is easy to get, is low in cost, reaction condition is mild, easy to operate.
Lithium of the invention has good cyclical stability from battery.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.
The application is described in further detail below in conjunction with specific embodiment, these embodiments should not be understood as limiting
The application range claimed processed.
According to an aspect of the present invention, a kind of positive electrode is provided, positive electrode includes: the C of apertures3N4-x, wherein 0
<x<4；And it is carried on C3N4-xSulphur.
Positive electrode provided by the invention, on the one hand, due to C3N4-xIn contain nitrogen, have to more sulphur lithiumation objects good
Absorption property；On the other hand, due to C3N4-xMiddle nitrogen content is with respect to C3N4It is lower, relative to C3N4Its intrinsic conductivity is improved,
When the positive electrode being therefore used for lithium-sulfur cell, its cyclical stability can be improved.
Wherein, it is carried on C3N4-xIn sulphur, can be and be filled in its hole or be carried on surface.
A kind of embodiment of positive electrode according to the present invention, the C of apertures3N4-xPorosity be 20~30m2/g。
The C of apertures in positive electrode of the invention3N4-xPorosity be 20~30m2/ g, and common C3N4Porosity
Only 9m2/ g or so, therefore the storage sulphur ability of positive electrode of the invention is stronger, using the lithium-ion electric of positive electrode of the present invention
Pond has good cycle performance.
According to another aspect of the present invention, a kind of preparation method of positive electrode is provided, comprising steps of
S1: by the C of apertures3N4It is mixed with Mg, heating reaction obtains the C of apertures after a certain period of time3N4-x, wherein 0 < x < 4；
S2: in the C of apertures3N4-xMiddle sulfur loaded, obtains positive electrode.
Preparation method of the invention, uses C3N4C is generated with Mg reaction3N4-x, on the one hand due to C3N4-xIn contain nitrogen,
There is good absorption property to more sulphur lithiumation objects；On the other hand due to C3N4-xMiddle nitrogen content is with respect to C3N4It is lower, relative to
C3N4When improving intrinsic conductivity, therefore the positive electrode being used for lithium-sulfur cell, its cyclical stability can be improved.
Further, it is preferable that C3N4It is mixed with Mg powder, can mix more evenly, react more thorough.
Wherein, the C of Mg and apertures3N4Shown in the reaction mechanism is as follows:
C3N4+3x/2Mg→C3N4-x+x/2Mg3N2
The C obtained by the reaction3N4-xIn N content, compare C3N4In N content reduce, to improve the sheet of material
Conductivity is levied, the migration rate of the lithium ion of material is improved, further improves the lithium sulphur electricity containing positive electrode of the present invention
The battery capacity and cycle performance in pond.
A kind of embodiment of method produced according to the present invention, in step sl, the C of apertures3N4Mass ratio with Mg is 3
~1.5:1；Heating temperature is 600~800 DEG C, and the reaction time is 1~5h.
The C of apertures in the preparation process in accordance with the present invention3N4Mass ratio with Mg is preferably 3~1.5:1；If magnesium accounting mistake
Height, will lead to that nitrogen content is too low, is unfavorable for the absorption of polysulfide, if magnesium accounting is too low, can make C3N4-xIn nitrogen content compared with
Height is unfavorable for improving the intrinsic conductivity of material；In the range, both it can be made to have the absorption of good polysulfide
Ability, and the intrinsic conductivity for improving material can be improved.It is wherein typical but preferred without limitation: 3:1,2.8:1,2.5:
1,2.3:1,2:1 and 1.5:1.
Heating temperature is preferably 600~800 DEG C, if temperature is greater than 800 DEG C of C that will lead to apertures3N4There is surface to lack
It falls into, if temperature is lower than 600 DEG C, the C of apertures can be hindered3N4With reacting for magnesium powder；Apertures can both be made at 600~800 DEG C
C3N4With magnesium powder occur it is good react, and the C of apertures can be prevented3N4There is surface defect.Wherein, typical but non-limiting
Preferably 600 DEG C of ground, 630 DEG C, 650 DEG C, 670 DEG C, 690 DEG C, 700 DEG C, 710 DEG C, 730 DEG C, 740 DEG C, 750 DEG C, 760 DEG C, 770
DEG C, 780 DEG C, 790 DEG C and 800 DEG C.
In step sl, heating process carries out under inert gas protection, is oxidized to avoid magnesium, influences C3N4-xProduction
It is raw.Inert gas is preferably argon gas, helium, hydrogen and CO2。
A kind of embodiment of method produced according to the present invention further comprises in step sl with dilute after the reaction was completed
The post-processing operation of acid and deionized water washing；Diluted acid is the sulfuric acid or hydrochloric acid that concentration is 0.5~1.5 mol/L.
In post-processing operation, with pickling primarily to the Mg and by-product Mg of removal remnants3N2, remnants are washed with water
Diluted acid, obtain black powder after dry.
A kind of embodiment of method produced according to the present invention, in step s 2, by the C of apertures3N4-xAdd after being mixed with S
Hot certain time obtains positive electrode after cooling.
Preparation method according to the present invention, step S2 are carried out in autoclave, and sulphur is filled to apertures in this step
C3N4-xIn, and/or it is supported on its surface.Wherein cooling is generally down to room temperature, and such as 25 DEG C.
A kind of embodiment of method produced according to the present invention, the C of the apertures3N4-xMass ratio with S is 3~1:1；
The heating temperature is 150~155 DEG C, and the reaction time is 5~20h.
In the preparation process in accordance with the present invention, in step s 2, C3N4-xMass ratio with S is 3~1:1, when sulfur content is low
When 3:1, the amount of sulfur loaded is too low, can reduce the capacity of the lithium-sulfur cell containing it, when sulfur content is higher than 1:1, can make
Its electric conductivity is too poor；When its mass ratio is 3~1:1, both the load capacity of sulphur can be made suitable, and not influence the appearance of lithium-sulfur cell
Amount, nor affects on its electric conductivity.Typical but preferred without limitation 3:1,2.5:1:2:1:1.5:1,1:1.
In the preparation process in accordance with the present invention, in step s 2, preferably 150~155 DEG C of heating temperature, if temperature is higher than
155 DEG C can make sulphur distillation cause load capacity too low, and temperature is lower than 150 DEG C, and sulphur incomplete fusion then hardly enters in duct.Allusion quotation
Type but without limitation preferably 150 DEG C, 151 DEG C, 152 DEG C, 153 DEG C, 154 DEG C and 155 DEG C.
A kind of embodiment of method produced according to the present invention, the C of apertures3N4It is by thiocarbamide and ammonium chloride Hybrid Heating
It obtains.
Preparation method of the invention prepares C using thiocarbamide and ammonium chloride3N4, wherein thiocarbamide, which heats, generates C3N4And SO2With
H2S etc., the ammonium chloride as pore-foaming agent decompose, and form NH3And HCl, since the bubble effect of sal-ammoniac makes C3N4Form macropore
Structure, the C being prepared3N4Porosity can reach 20~30m2/ g, this structure not only can provide storage space for sulphur, from
And improve it and store up sulphur ability, the cyclical stability of the lithium-sulfur cell containing the positive electrode is further increased, furthermore it is also possible to
Tunnel is provided for the infiltration of electrolyte.
In preparation method of the invention, the C of apertures3N4It is to be obtained by thiocarbamide and ammonium chloride Hybrid Heating.
Concrete operation step can be preferred, and first thiocarbamide and ammonium chloride are mixed evenly with deionized water, is dried
White powder is obtained, is in this step only to be uniformly mixed the two, so that the reaction of next step is more evenly.Wherein drying temperature
It is preferred that 50~80 DEG C, dry 4~for 24 hours.Drying temperature is preferably 50~80 DEG C, can not only ammonium chloride be made not decompose, but also can be incited somebody to action
Deionized water removal.Then mixture is heated to the C for generating apertures3N4。
Wherein, preferred 1:1~2 of the mass ratio of thiocarbamide and ammonium chloride；
Preferably 500~600 DEG C of heating temperature, heating time preferably 1~5h.
Preferably 500~600 DEG C of heating temperature, if heating temperature is higher than 600 DEG C, C3N4It can volatilize in synthesis, if warm
Degree is lower than 500 DEG C, then will not generate C3N4.It is typical but without limitation preferably 500 DEG C, 510 DEG C, 520 DEG C, 530 DEG C, 540 DEG C,
550 DEG C, 560 DEG C, 570 DEG C, 580 DEG C and 600 DEG C.In the temperature range, thiocarbamide, which can both decompose, generates C3N4, ammonium chloride can also
NH is generated to decompose3And HCl, and speed ratio is more gentle, so that the macroporous structure generated is more balanced, it is not in suddenly big or suddenly small
Pore structure.
According to another aspect of the present invention, a kind of lithium-sulfur cell is provided, comprising: anode, cathode, electrolyte, wherein institute
Stating includes the positive electrode obtained in positive electrode or anode of the invention including preparation method of the present invention in anode.
Lithium-sulfur cell according to the present invention has good cyclical stability.
In order to preferably explain the present invention, below in conjunction with examples illustrate the present invention, but embodiment only conduct
The description of the invention does not limit protection scope.
Embodiment 1
In the preparation method of the embodiment positive electrode, the C of apertures is prepared first3N4, mixed by thiocarbamide and ammonium chloride
Heating obtains the C of apertures3N4；The mass ratio of thiocarbamide and ammonium chloride is 1:1；The temperature of heating is 500~600 DEG C, and heating time is
1~5h.
Then step S1 is carried out: by the C of obtained apertures3N4It is mixed with Mg powder, heating reaction obtains apertures after a certain period of time
C3N4-x, wherein 0 < x < 4；The C of apertures3N4Mass ratio with magnesium powder is 3:1；Heating temperature be 600 DEG C, the reaction time be 1~
5h；It is washed after the reaction was completed with diluted acid and deionized water；The concentration of diluted acid is the sulfuric acid or hydrochloric acid of 0.5~1.5mol/L.
Finally carry out step S2: in the C of apertures3N4-xMiddle sulfur loaded, obtains positive electrode.By the C of apertures3N4-xIt is mixed with S
After heat certain time, positive electrode is obtained after cooling.The C of apertures3N4-xMass ratio with S is 3~1:1；Heating temperature is
150~155 DEG C, the reaction time is 5~20h.
Embodiment 2
Embodiment 2 and other conditions of embodiment 1 are all the same, the difference is that, chlorination is not added in embodiment 2
Ammonium.
Comparative example 1
The comparative example and 2 other conditions of embodiment are all the same, the difference is that, step is not included in the comparative example
S1, in the C of apertures3N4In loaded sulphur, loading condition is identical with the step S2 in embodiment 2.
Embodiment 3
Other conditions of the embodiment and embodiment 1 are all the same, the difference is that the C of apertures3N4Mass ratio with Mg is
2:1.
Embodiment 4
Other conditions of the embodiment and embodiment 1 are all the same, the difference is that the C of apertures3N4Mass ratio with Mg is
1.5:1.
Comparative example 2
The other conditions of the comparative example and embodiment 1 are all the same, the difference is that the C of apertures3N4Mass ratio with Mg is
4:1.
Comparative example 3
The other conditions of the comparative example and embodiment 1 are all the same, the difference is that the C of apertures3N4Mass ratio with Mg is
1:1.
Embodiment 5
Other conditions of the embodiment and embodiment 1 are all the same, the difference is that heating temperature in step sl is
700℃。
Embodiment 6
Other conditions of the embodiment and embodiment 1 are all the same, the difference is that heating temperature in step sl is
800℃。
Comparative example 4
Other conditions of the comparative example and embodiment 1 are all the same, the difference is that heating temperature in step sl is
500℃。
Comparative example 5
Other conditions of the comparative example and embodiment 1 are all the same, the difference is that heating temperature in step sl is
900℃。
Embodiment 7
Other conditions of the embodiment and embodiment 1 are all the same, the difference is that, the mass ratio of thiocarbamide and ammonium chloride is
1:1.5.
Embodiment 8
Other conditions of the embodiment and embodiment 2 are all the same, the difference is that, the mass ratio of thiocarbamide and ammonium chloride is
1:2.
Comparative example 6
Other conditions of the comparative example and embodiment 2 are all the same, the difference is that, the mass ratio of thiocarbamide and ammonium chloride is
1:0.5.
Comparative example 7
Other conditions of the comparative example and embodiment 2 are all the same, the difference is that, the mass ratio of thiocarbamide and ammonium chloride is
1:3.
The positive electrode that applicant obtains embodiment 1-8 and comparative example 1~7 is assembled into lithium sulphur electricity by following conditions
The sequence in pond, " negative electrode casing-lithium piece-electrolyte-diaphragm-electrolyte-positive plate-anode cover " assembles button cell, battery specifications
Be 2025, whole process full of argon gas glove box in complete, wherein electrolyte be (0.6M LITFSI+DOL/DME), every
Film is Celgard2400.
Applicant carries out the detection of cycle performance of battery to the lithium-sulfur cell being assembled into, with blue electric tester in 0.1C multiplying power
The cycle performance of lower test button electricity.
Testing result is as shown in table 1.
Table 1
Pass through the data of comparative example 2 and comparative example 1, it can be seen that be prepared just using method of the invention
Pole material, due to using C3N4-xNitrogen content is reduced, its intrinsic conductivity is improved, so as to significantly improve lithium sulphur
The cyclical stability of battery.
Pass through comparative example 1, the data of embodiment 2 and comparative example 1, it can be seen that method of the invention is used, into one
The C that step is prepared using thiocarbamide and sal-ammoniac3N4, since it contains high porosity, improves it and store up sulphur ability, so as to
Further improve the cyclical stability of lithium-sulfur cell.
Pass through the data of comparative example 1,3 and 4 and comparative example 2 and 3, it will thus be seen that the C of apertures3N4With the quality of Mg
When than within the scope of 3~1.5:1, the cyclical stability of lithium-sulfur cell is best.
Pass through embodiment 1,5,6, the data of comparative example 4 and 5, it can be seen that the heating temperature in step S1 is 600
~800 DEG C, the cyclical stability of lithium-sulfur cell is best.
Pass through comparative example 1,7,8, the data of comparative example 6 and 7, it can be seen that the mass ratio of thiocarbamide and ammonium chloride is
When 1:1~2, the cyclical stability of lithium-sulfur cell is best.
The above described is only a preferred embodiment of the present invention, being not the limitation for doing other forms to the present invention, appoint
What those skilled in the art can use the equivalence enforcement that technology contents disclosed above were changed or be modified as equivalent variations
Example.But without departing from the technical solutions of the present invention, according to the technical essence of the invention to the above embodiments
What simple modification, equivalent variations and remodeling, still falls within the protection scope of technical solution of the present invention.
Claims (10)
1. a kind of positive electrode, which is characterized in that the positive electrode includes:
The C of apertures3N4-x, wherein 0 < x < 4；And
It is carried on the C3N4-xSulphur.
2. positive electrode according to claim 1, which is characterized in that the C of the apertures3N4-xPorosity be 20~
30m2/g。
3. a kind of preparation method of positive electrode, which is characterized in that comprising steps of
S1: by the C of apertures3N4It is mixed with Mg, heating reaction obtains the C of apertures after a certain period of time3N4-x, wherein 0 < x < 4；
S2: in the C of the apertures3N4-xMiddle sulfur loaded, obtains positive electrode.
4. preparation method according to claim 3, which is characterized in that in step sl, the C of the apertures3N4With the matter of Mg
Amount is than being 3~1.5:1；
Heating temperature is 600~800 DEG C, and the reaction time is 1~5h.
5. the preparation method according to claim 4, which is characterized in that in step sl, further comprise after the reaction was completed
The post-processing operation washed with diluted acid and deionized water；
The diluted acid is the sulfuric acid or hydrochloric acid that concentration is 0.5~1.5mol/L.
6. preparation method according to claim 3, which is characterized in that in step s 2, by the C of the apertures3N4-xIt is mixed with S
It is heated after conjunction certain time, positive electrode is obtained after cooling.
7. preparation method according to claim 6, which is characterized in that
The C of the apertures3N4-xMass ratio with S is 3~1:1；
The heating temperature is 150~155 DEG C, and the reaction time is 5~20h.
8. preparation method according to claim 3, which is characterized in that the C of the apertures3N4It is by thiocarbamide and ammonium chloride
Hybrid Heating obtains.
9. preparation method according to claim 8, which is characterized in that
The mass ratio of the thiocarbamide and the ammonium chloride is 1:1~2；
The temperature of heating is 500~600 DEG C, and heating time is 1~5h.
10. a kind of lithium-sulfur cell, characterized by comprising: anode, cathode, electrolyte, wherein wanted in the anode including right
Positive electrode described in asking 1 or 2, or
It include the positive electrode that any preparation method of claim 3~9 obtains in the anode.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811156935.3A CN109360956A (en) | 2018-09-30 | 2018-09-30 | A kind of positive electrode and preparation method thereof, lithium-sulfur cell |
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| CN201811156935.3A CN109360956A (en) | 2018-09-30 | 2018-09-30 | A kind of positive electrode and preparation method thereof, lithium-sulfur cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112164778A (en) * | 2020-09-23 | 2021-01-01 | 长沙矿冶研究院有限责任公司 | Lithium cathode and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103700859A (en) * | 2013-12-30 | 2014-04-02 | 温州大学 | Graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material for cathode of lithium sulfur battery, as well as preparation method and application of graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material |
| CN104409733A (en) * | 2014-12-24 | 2015-03-11 | 华南师范大学 | Nitrogen doped porous carbon/sulfur composite positive material as well as preparation method and application thereof |
| CN105126893A (en) * | 2015-08-31 | 2015-12-09 | 中国科学院过程工程研究所 | Graphite-phase carbon nitride (g-C3N4) material and preparation method and application thereof |
| US20160233487A1 (en) * | 2015-02-06 | 2016-08-11 | Mitsubishi Chemical Corporation | Pnictide containing catalysts for electrochemical conversion reactions and methods of use |
| CN106505183A (en) * | 2015-09-08 | 2017-03-15 | 中国科学院宁波材料技术与工程研究所 | Carbonitride-sulphur composite and its preparation method and application |
| CN106549157A (en) * | 2015-09-18 | 2017-03-29 | 中国科学院宁波材料技术与工程研究所 | Hollow ball shape class graphite-phase C3N4With elemental sulfur composite material and its preparation method and application |
| CN107732208A (en) * | 2017-10-16 | 2018-02-23 | 河源广工大协同创新研究院 | The preparation method of nano-sulfur/nitridation carbon composite anode material |
-
2018
- 2018-09-30 CN CN201811156935.3A patent/CN109360956A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103700859A (en) * | 2013-12-30 | 2014-04-02 | 温州大学 | Graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material for cathode of lithium sulfur battery, as well as preparation method and application of graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material |
| CN104409733A (en) * | 2014-12-24 | 2015-03-11 | 华南师范大学 | Nitrogen doped porous carbon/sulfur composite positive material as well as preparation method and application thereof |
| US20160233487A1 (en) * | 2015-02-06 | 2016-08-11 | Mitsubishi Chemical Corporation | Pnictide containing catalysts for electrochemical conversion reactions and methods of use |
| CN105126893A (en) * | 2015-08-31 | 2015-12-09 | 中国科学院过程工程研究所 | Graphite-phase carbon nitride (g-C3N4) material and preparation method and application thereof |
| CN106505183A (en) * | 2015-09-08 | 2017-03-15 | 中国科学院宁波材料技术与工程研究所 | Carbonitride-sulphur composite and its preparation method and application |
| CN106549157A (en) * | 2015-09-18 | 2017-03-29 | 中国科学院宁波材料技术与工程研究所 | Hollow ball shape class graphite-phase C3N4With elemental sulfur composite material and its preparation method and application |
| CN107732208A (en) * | 2017-10-16 | 2018-02-23 | 河源广工大协同创新研究院 | The preparation method of nano-sulfur/nitridation carbon composite anode material |
Non-Patent Citations (2)
| Title |
|---|
| JINGJING CHEN ET AL.: "《Nitrogen-Deficient Graphitic Carbon Nitride with Enhanced Performance for Lithium Ion Battery Anodes》", 《ACS NANO》 * |
| QUAN PANG ET AL.: "《Long-life and high-areal-capacity Li-S batteries enabled by a light-weight polar host with intrinsic polysulfide adsorption》", 《ACS NANO》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112164778A (en) * | 2020-09-23 | 2021-01-01 | 长沙矿冶研究院有限责任公司 | Lithium cathode and preparation method thereof |
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