CN108821249A - Carbon-nitrogen material and preparation method thereof and lithium sulfur battery anode material and lithium-sulfur cell comprising it - Google Patents
Carbon-nitrogen material and preparation method thereof and lithium sulfur battery anode material and lithium-sulfur cell comprising it Download PDFInfo
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Abstract
The present invention provides a kind of carbon-nitrogen material and preparation method thereof and comprising its lithium sulfur battery anode material and lithium-sulfur cell, it is related to new energy battery technology field, the preparation method of the carbon-nitrogen material includes the following steps：The mixture of catalyst and melamine is placed under inert atmosphere and is sintered, the carbon-nitrogen material is obtained.The carbon-nitrogen nano tube obtained using the preparation method can alleviate the lithium-sulfur cell of the prior art because intermediate product lithium polysulfide is easy dissolution in the electrolyte so as to cause the technical problem of lithium-sulfur cell cyclical stability difference, reach the technical effect for improving lithium-sulfur cell cyclical stability.
Description
Technical field
The present invention relates to new energy battery technology fields, more particularly, to a kind of carbon-nitrogen material and preparation method thereof and packet
Containing its lithium sulfur battery anode material and lithium-sulfur cell.
Background technique
Lithium-sulfur cell has many advantages, such as that light-weight, capacity is big, memory-less effect, wherein the theoretical specific capacity of lithium-sulfur cell
Up to 1675mAh/g, theoretical energy density are up to 2600Wh/kg, hence it is evident that higher than the theoretical capacity of commercial Li-ion battery.
But it is existing research shows that lithium-sulfur cell is in charge and discharge process, intermediate product lithium polysulfide, and lithium can be generated
Polysulfide can be dissolved in ether system electrolyte, be deteriorated so as to cause the cycle performance of lithium-sulfur cell.
Lithium polysulfide can be inhibited to be dissolved in electrolyte current study show that adulterating nitrogen in carbon material.Wherein exist
Nitrogen is adulterated in carbon material, usually using carbon material as skeleton, a small number of nitrogen-atoms are doped with carbon atom, atomic structure arrangement
Schematic diagram is as shown in Figure 1.As seen from Figure 1, wherein nitrogen content is less, and nitrogen-atoms mass percentage is not high under normal circumstances
In 16%, since nitrogen has the ability of absorption lithium polysulfide, when the mass percentage of nitrogen-atoms is lower, the big day of one's doom
Having made it inhibits lithium polysulfide to be dissolved in the ability in electrolyte, and then affects the cyclical stability of lithium-sulfur cell.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of carbon-nitrogen material and is obtained using the preparation method
Carbon-nitrogen material, with alleviate the lithium-sulfur cell of the prior art because intermediate product lithium polysulfide be easy dissolution in the electrolyte from
And lead to the technical problem of lithium-sulfur cell stable circulation performance difference.
The second object of the present invention is to provide a kind of lithium sulfur battery anode material and comprising the lithium-sulphur cell positive electrode material
The lithium-sulfur cell of material.
In order to realize above-mentioned purpose of the invention, spy uses following technical scheme：
A kind of preparation method of carbon-nitrogen material, includes the following steps：
The mixture of catalyst and melamine is placed under inert atmosphere and is sintered, the carbon-nitrogen material is obtained.
Further, the catalyst is NiCl.
Further, the mass ratio of the NiCl and the melamine is 1-3：7-9.
Further, sintering temperature is 450-700 DEG C, sintering time 3-5h.
A kind of carbon-nitrogen material obtained using above-mentioned preparation method.
Further, the carbon-nitrogen material is carbon-nitrogen nano tube.
Further, the caliber of the carbon-nitrogen nano tube is 50~500nm.
A kind of lithium sulfur battery anode material, including sulphur powder and above-mentioned carbon-nitrogen material.
Further, the carbon-nitrogen material is carbon-nitrogen nano tube, and the sulphur powder is filled in the carbon-nitrogen nano tube.
A kind of lithium-sulfur cell, including cathode of lithium, electrolyte and anode, it is described just extremely to utilize above-mentioned lithium-sulphur cell positive electrode material
Expect the anode being prepared.
Compared with the prior art, the present invention has the advantages that：
The preparation method of carbon-nitrogen material provided by the invention using melamine as reaction raw materials, catalyst (such as：Chlorination
Nickel) under the action of, (such as by high temperature sintering rapid synthesis carbon-nitrogen material：Carbon-nitrogen nano tube).Due to adopting in the preparation method
It is raw material with melamine, the Atomic Arrangement structural schematic diagram of the carbon-nitrogen material obtained after sintering is as shown in Fig. 2, by Fig. 2 and Fig. 1
Structural schematic diagram compare it can also be seen that nitrogen content significantly improves.
In general, the chemical formula of carbon-nitrogen material can be expressed as CnN(1-n), wherein the value range of n is 0.3 < n <
0.6, therefore, the mass percentage content of nitrogen-atoms can reach to 40% or more in carbon-nitrogen material.Carbon-nitrogen material of the invention,
It is likewise supplied with the general character of general carbon-nitrogen material, the mass percentage of nitrogen-atoms can also reach 40% or more, due to nitrogen-atoms
Ability with absorption lithium polysulfide, after its mass percentage reaches 40% or more, carbon-nitrogen material increases absorption lithium
The amount of polysulfide, therefore reduce the meltage of lithium polysulfide in the electrolytic solution, further increase the circulation of lithium-sulfur cell
Stability.
In addition, in the preparation process in accordance with the present invention, by controlling reaction condition, especially reaction temperature, carbon nitrogen can be made
Material forms carbon-nitrogen nano tube, when carbon-nitrogen material is carbon-nitrogen nano tube, due to the tubular structure of carbon-nitrogen nano tube itself, to
The lithium polysulfide generated in tubular structure plays certain barrier effect, reduces lithium polysulfide and is dissolved in the machine in electrolyte
Meeting further increases the cyclical stability of lithium-sulfur cell to be further reduced the meltage of lithium polysulfide in the electrolytic solution.
Lithium sulfur battery anode material provided by the invention, including sulphur powder and above-mentioned carbon-nitrogen material.Lithium sulfur battery anode material
Using carbon-nitrogen material as carrier, sulphur powder is carried on carbon-nitrogen material.On the one hand, carbon-nitrogen material can improve the electric conductivity of sulphur powder；It is another
Aspect can be improved the adsorbance to lithium polysulfide, subtract since in carbon-nitrogen material, the mass percentage of nitrogen is greater than 40%
Few lithium polysulfide is dissolved in the amount in electrolyte, to improve the cyclical stability of lithium-sulfur cell.When carbon-nitrogen material is carbon
When nitride nanotubes, on the one hand, due to the tubular structure of carbon-nitrogen nano tube itself, to the lithium polysulfide generated in tubular structure
Certain barrier effect is played, lithium polysulfide is reduced and is dissolved in the chance in electrolyte, is vulcanized to be further reduced lithium more
The meltage of object in the electrolytic solution, improves the cyclical stability of lithium-sulfur cell；On the other hand, due to sulphur simple substance load (filling) in
In the carbon-nitrogen nano tube, thus when can reduce charge and discharge positive electrode volume change, improve the circulation of lithium-sulfur cell
Stability.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the Atomic Arrangement structural schematic diagram of the carbon nanotube of existing N doping；
Fig. 2 is the Atomic Arrangement structural schematic diagram of carbon-nitrogen nano tube of the invention；
Fig. 3 is the SEM figure of carbon-nitrogen nano tube in the embodiment of the present invention 1；
Fig. 4 is the SEM figure of carbon-nitrogen nano tube in the embodiment of the present invention 3；
Fig. 5 is to be surveyed using cyclical stability of the lithium-sulfur cell of the lithium sulfur battery anode material production of embodiment 2 at 1C
Try curve graph；
Fig. 6 is to be surveyed using cyclical stability of the lithium-sulfur cell of the lithium sulfur battery anode material production of comparative example 2 at 1C
Try curve graph.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
On the one hand, the present invention provides a kind of preparation method of carbon-nitrogen material, include the following steps：
The mixture of catalyst and melamine is placed under inert atmosphere and is sintered, the carbon-nitrogen material is obtained.
The preparation method of carbon-nitrogen material provided by the invention using melamine as reaction raw materials, catalyst (such as：Chlorination
Nickel) under the action of, (such as by high temperature sintering rapid synthesis carbon-nitrogen material：Carbon-nitrogen nano tube).Due to adopting in the preparation method
It is raw material with melamine, the Atomic Arrangement structural schematic diagram of the carbon-nitrogen material obtained after sintering is as shown in Fig. 2, by Fig. 2 and Fig. 1
Structural schematic diagram compare it can also be seen that nitrogen content significantly improves.
In addition, in the preparation method of carbon-nitrogen nano tube provided by the invention, since reaction raw materials are only melamine, because
This, the production of carbon-nitrogen material is achieved that by controlling reaction temperature, it can also be made to generate carbon nitrogen by controlling reaction temperature
Nanotube, and can be by adjusting the caliber for the carbon-nitrogen nano tube that controlling reaction temperature obtains, this method is easy to operate, fast
Speed is suitble to industrialized production.
In the present invention, catalyst is, for example, NiCl, the inert gas in the preparation method for example can for argon gas, helium or
Neon etc..
In certain embodiments of the present invention, the mass ratio of the NiCl and the melamine is 1-3：7-9.It is logical
The weight ratio of control catalyst n iCl and reaction raw materials melamine is crossed, can react fully progress.Wherein, NiCl and trimerization
The mass ratio of cyanamide such as can be 1：9,1：8,1：7,2：9,2：8,2：7,3：9,3：8 or 3：7.
In certain embodiments of the present invention, sintering temperature is 450-720 DEG C, and sintering time 3-5h utilizes this
Sintering process (especially sintering temperature) available carbon-nitrogen nano tube, and the diameter range of carbon-nitrogen nano tube is 50-500nm.
Pass through control sintering temperature and sintering time, the carbon-nitrogen nano tube of available different tube diameters, for example, constant in other conditions
When, within the scope of temperature of the invention, when temperature is lower, the available relatively large carbon-nitrogen nano tube of caliber.
Wherein, sintering temperature unrestrictedly for example can be：450℃,480℃,500℃,530℃,550℃,560℃,
570℃、580℃、590℃、600℃、610℃、620℃、620℃、630℃、640℃、650℃、660℃、670℃、680
DEG C, 690 DEG C or 700 DEG C；Sintering time unrestrictedly for example can be 3h, 4h or 5h.
On the other hand, the present invention provides a kind of carbon-nitrogen materials being prepared using the above method.
In general, the chemical formula of carbon-nitrogen material can be expressed as CnN(1-n), wherein the value range of n is 0.3 < n <
0.6, therefore, the mass percentage content of nitrogen-atoms can reach to 40% or more in carbon-nitrogen material.Carbon-nitrogen material of the invention,
It is likewise supplied with the general character of general carbon-nitrogen material, the mass percentage of nitrogen-atoms can also reach 40% or more, due to nitrogen-atoms
Ability with absorption lithium polysulfide, after its mass percentage reaches 40% or more, carbon-nitrogen material increases absorption lithium
The amount of polysulfide, therefore reduce the meltage of lithium polysulfide in the electrolytic solution, further increase the circulation of lithium-sulfur cell
Stability.
In certain embodiments of the present invention, carbon-nitrogen material is carbon-nitrogen nano tube.Wherein, the caliber of carbon-nitrogen nano tube is
50~500nm.
When carbon-nitrogen material is carbon-nitrogen nano tube, due to the tubular structure of carbon-nitrogen nano tube itself, in tubular structure
The lithium polysulfide of generation plays certain barrier effect, reduces lithium polysulfide and is dissolved in the chance in electrolyte, thus into
One step reduces the meltage of lithium polysulfide in the electrolytic solution, further increases the cyclical stability of lithium-sulfur cell.
The third aspect, the present invention provides a kind of lithium sulfur battery anode materials, including sulphur powder and above-mentioned carbon-nitrogen material.
Lithium sulfur battery anode material provided by the invention, including sulphur powder and above-mentioned carbon-nitrogen material.Lithium sulfur battery anode material
Using carbon-nitrogen material as carrier, sulphur powder is carried on carbon-nitrogen material.On the one hand, carbon-nitrogen material can improve the electric conductivity of sulphur powder；It is another
Aspect can be improved the adsorbance to lithium polysulfide, subtract since in carbon-nitrogen material, the mass percentage of nitrogen is greater than 40%
Few lithium polysulfide is dissolved in the amount in electrolyte, to improve the cyclical stability of lithium-sulfur cell.
In certain embodiments of the present invention, carbon-nitrogen material is carbon-nitrogen nano tube, and sulphur powder is filled in the carbon nitrogen nanometer
Guan Zhong.Wherein, the weight ratio of sulphur powder and carbon-nitrogen nano tube such as can be (70-80)：(20-30).
When carbon-nitrogen material is carbon-nitrogen nano tube, on the one hand, due to the tubular structure of carbon-nitrogen nano tube itself, in tubulose
The lithium polysulfide generated in structure plays certain barrier effect, reduces lithium polysulfide and is dissolved in the chance in electrolyte,
To be further reduced the meltage of lithium polysulfide in the electrolytic solution, the cyclical stability of lithium-sulfur cell is improved；On the other hand,
Since sulphur simple substance load (filling) is in the carbon-nitrogen nano tube, the volume change of positive electrode when can reduce charge and discharge
Rate improves the cyclical stability of lithium-sulfur cell.
In the present invention, the weight ratio of sulphur powder and carbon-nitrogen nano tube unrestrictedly for example can be 70：30,70：25,70：20,
75：30,75：25,75：20,80：30,80：25 or 80：20.
The preparation method of above-mentioned lithium sulfur battery anode material includes that the sulphur powder is filled in the carbon-nitrogen nano tube and is obtained
To the lithium sulfur battery anode material.For example, keeping the temperature 10- at 130-170 DEG C after sulphur powder is mixed with carbon-nitrogen nano tube
13h obtains lithium sulfur battery anode material.
The method of high temperature sulfurizing is used to prepare the lithium-sulfur cell using carbon-nitrogen nano tube as carrier, sulphur can be made to penetrate into carbon
In nitride nanotubes internal structure, the uniformity that sulphur is mixed with carbon-nitrogen nano tube is improved, and then make each of lithium sulfur battery anode material
It is more consistent to performance.
In above embodiment, sulphur powder and the mixed sulfurizing temperature of the carbon-nitrogen nano tube for example can for 130 DEG C,
140 DEG C, 150 DEG C, 160 DEG C or 170 DEG C, soaking time for example can be 10h, 11h, 12h or 13h.
Sulphur powder and the mixing of the carbon-nitrogen nano tube can be mixed using high-energy-milling, Ball-milling Time 2-4h.
It is mixed using high-energy-milling, sulphur powder can be made to mix more uniformly with the carbon-nitrogen nano tube.
In another aspect, the present invention provides a kind of lithium-sulfur cell, including cathode of lithium, electrolyte and anode, this is just extremely sharp
The anode being prepared with above-mentioned lithium sulfur battery anode material.
Lithium-sulfur cell provided by the invention reduces lithium polysulfide meltage in the electrolytic solution since anode uses to have
Lithium sulfur battery anode material because the lithium-sulfur cell have higher cyclical stability.
Lithium-sulfur cell provided by the invention can be used in a variety of electrical equipments, such as automobile, move dining car, communicate base
It stands power supply unit etc., so as to use electric equipment to obtain more lasting power supply.
Below in conjunction with embodiment and comparative example, the present invention is further described in detail.
Embodiment 1
The present embodiment is a kind of carbon-nitrogen nano tube, and the preparation method of the carbon-nitrogen nano tube is：It is 2 by mass ratio：8 chlorination
Nickel and melamine are uniformly mixed by high-energy ball milling, are then heated to 600 DEG C under the conditions of argon atmosphere again, are kept the temperature 4h, are obtained
It is directly about the carbon-nitrogen nano tube of 100nm, structure is as shown in Figure 3.
Embodiment 2
The present embodiment is a kind of lithium sulfur battery anode material, including the carbon-nitrogen nano tube in sulphur powder and embodiment 1, wherein
The mass ratio of sulphur powder and carbon-nitrogen nano tube is 70：30.
The preparation method of the lithium sulfur battery anode material is：It is 70 by mass ratio：30 sulphur powders and carbon-nitrogen nano tube high energy ball
2h is ground, then the powder prepared is fitted into the reaction kettle of 200ml, is heated to 155 DEG C, 12h is kept the temperature, is obtaining lithium-sulfur cell just
Pole material.
Embodiment 3
The present embodiment is a kind of carbon-nitrogen nano tube, and the preparation method of the carbon-nitrogen nano tube is：It is 1 by mass ratio：9 chlorination
Nickel and melamine are uniformly mixed by high-energy ball milling, and 550 DEG C are then heated under the conditions of argon atmosphere, are kept the temperature 4h, are obtained
It is directly about the carbon-nitrogen nano tube of 200nm, structure is as shown in Figure 4.
Embodiment 4
The present embodiment is a kind of lithium sulfur battery anode material, including the carbon-nitrogen nano tube in sulphur powder and embodiment 3, wherein
The mass ratio of sulphur powder and carbon-nitrogen nano tube is 70：30.
The preparation method of the lithium sulfur battery anode material is：It is 70 by mass ratio：30 sulphur powders and carbon-nitrogen nano tube high energy ball
2h is ground, then the powder prepared is fitted into the reaction kettle of 200ml, is heated to 155 DEG C, 12h is kept the temperature, is obtaining lithium-sulfur cell just
Pole material.
Embodiment 5
The present embodiment is a kind of carbon-nitrogen nano tube, and the preparation method of the carbon-nitrogen nano tube is：It is 3 by mass ratio：7 chlorination
Nickel and melamine are uniformly mixed by high-energy ball milling, are then heated to 600 DEG C under the conditions of argon atmosphere again, are kept the temperature 4h, are obtained
It is directly about the carbon-nitrogen nano tube of 100nm.
Embodiment 6
The present embodiment is a kind of lithium sulfur battery anode material, including the carbon-nitrogen nano tube in sulphur powder and embodiment 5, wherein
The mass ratio of sulphur powder and carbon-nitrogen nano tube is 80：20.
The preparation method of the lithium sulfur battery anode material is：It is 80 by mass ratio：20 sulphur powders and carbon-nitrogen nano tube high energy ball
2h is ground, then the powder prepared is fitted into the reaction kettle of 200ml, is heated to 155 DEG C, 12h is kept the temperature, is obtaining lithium-sulfur cell just
Pole material.
Embodiment 7
The present embodiment is a kind of carbon-nitrogen nano tube, and the preparation method of the carbon-nitrogen nano tube is：It is 2 by mass ratio：8 chlorination
Nickel and melamine are uniformly mixed by high-energy ball milling, are then heated to 500 DEG C under the conditions of argon atmosphere again, are kept the temperature 4h, are obtained
It is directly about the carbon-nitrogen nano tube of 200nm.
Embodiment 8
The present embodiment is a kind of lithium sulfur battery anode material, including the carbon-nitrogen nano tube in sulphur powder and embodiment 7, wherein
The mass ratio of sulphur powder and carbon-nitrogen nano tube is 80：20.
The preparation method of the lithium sulfur battery anode material is：It is 80 by mass ratio：20 sulphur powders and carbon-nitrogen nano tube high energy ball
2h is ground, then the powder prepared is fitted into the reaction kettle of 200ml, is heated to 155 DEG C, 12h is kept the temperature, is obtaining lithium-sulfur cell just
Pole material.
Embodiment 9
The present embodiment is a kind of carbon-nitrogen nano tube, and the preparation method of the carbon-nitrogen nano tube is：It is 2 by mass ratio：8 chlorination
Nickel and melamine are uniformly mixed by high-energy ball milling, are then heated to 600 DEG C under the conditions of argon atmosphere again, are kept the temperature 2h, are obtained
It is directly about the carbon-nitrogen nano tube of 100nm.
Embodiment 10
The present embodiment is a kind of lithium sulfur battery anode material, including the carbon-nitrogen nano tube in sulphur powder and embodiment 9, wherein
The mass ratio of sulphur powder and carbon-nitrogen nano tube is 80：20.
The preparation method of the lithium sulfur battery anode material is：It is 80 by mass ratio：20 sulphur powders and carbon-nitrogen nano tube high energy ball
2h is ground, then the powder prepared is fitted into the reaction kettle of 200ml, is heated to 155 DEG C, 12h is kept the temperature, is obtaining lithium-sulfur cell just
Pole material.
Embodiment 11
The present embodiment is a kind of lithium sulfur battery anode material, including the carbon-nitrogen nano tube in sulphur powder and embodiment 9, wherein
The mass ratio of sulphur powder and carbon-nitrogen nano tube is 70：30.
The preparation method of the lithium sulfur battery anode material is：It is 70 by mass ratio：30 sulphur powders and carbon-nitrogen nano tube high energy ball
2h is ground, then the powder prepared is fitted into the reaction kettle of 200ml, is heated to 155 DEG C, 12h is kept the temperature, is obtaining lithium-sulfur cell just
Pole material.
Comparative example 1
This comparative example is a kind of carbon nanotube of N doping, and the preparation method of the carbon nanotube is：By commercial carbon nanotube
It is placed in ammonia atmosphere, is sintered 5h at 500 DEG C, obtain the carbon nanotube of N doping.
Comparative example 2
This comparative example is a kind of lithium sulfur battery anode material, the carbon nanotube including the N doping in sulphur powder and comparative example 1,
Wherein, the mass ratio of sulphur powder and the carbon nanotube of N doping is 70：30.
The preparation method of the lithium sulfur battery anode material is：It is 70 by mass ratio：The carbon nanotube of 30 sulphur powders and N doping
Then the powder prepared is fitted into the reaction kettle of 200ml by high-energy ball milling 2h, be heated to 155 DEG C, is kept the temperature 12h, is obtained lithium sulphur
Cell positive material.
Check experiment
It is utilized respectively the lithium sulfur battery anode material assembling lithium-sulfur cell that embodiment 2 and comparative example 2 provide.
Lithium-sulfur cell includes positive plate, negative electrode tab, diaphragm and electrolyte, and positive plate is by conductive agent, binder and reality
The positive electrode that example 2 and comparative example 2 provide respectively is applied, is coated on aluminium foil after NMP is ground into slurry, it is then 12 small at 60 DEG C
When drying be prepared；Negative electrode tab is lithium foil, and diaphragm is using Celegard2400 polypropylene screen, and electrolyte is by lithium salts, molten
Agent and three groups of additive are grouped as, wherein dimethyl ethane (DME) and 1,3- dioxolane (DOL) is with volume ratio for 1：1 is mixed
Conjunction forms mixed solvent, and it is molten that bis- (fluoroform sulphonyl) imine lithiums (LiTFSI) of lithium salts and additive lithium nitrate are dissolved in mixing respectively
In agent, concentration is respectively 1.0mol/L and 0.1mol/L.Electrolyte is molten by 1.0mol/LLiTFS solution and 0.1mol/LLiNO3
Liquid mixes, and the volume ratio of the two is 1：1；Said modules are assembled in 2032 types with positive plate/diaphragm/negative electrode tab structure
In button cell, entire cell assembling processes are completed in glove box.
Test the cycle performance of every group of lithium-sulfur cell, test result such as Fig. 5 and Fig. 6 institute after being completed at 1C respectively
Show.
From figure 5 it can be seen that the lithium-sulfur cell that forms of lithium sulfur battery anode material provided using embodiment 2
Cycle-index can achieve 500 times, and after circulation 500 times, specific capacity stills remain in 400mAh/g or more.
From fig. 6 it can be seen that the lithium-sulfur cell formed using the lithium sulfur battery anode material that comparative example 2 provides,
At cycle-index 10 times or so, specific capacity is reduced to 400mAh/g or so.When cycle-index is at 100 times, specific capacity
Almost it is down to 100mAh/g or less.
In addition, it can also be seen that forming to obtain using the lithium sulfur battery anode material that embodiment 2 provides from Fig. 5 and Fig. 6
Lithium-sulfur cell the initial charge/discharge specific capacity lithium-sulphur cell positive electrode that can achieve 1400mAh/g, and comparative example 2 is utilized to provide
The initial charge/discharge specific capacity for the lithium-sulfur cell that material forms is in 1000mAh/g or so.
To sum up, on the one hand, the lithium-sulfur cell for using carbon-nitrogen material provided by the invention to be prepared in the battery is just
Pole material, since the nitrogen content of carbon-nitrogen material is higher, the ability of absorption lithium polysulfide is improved, and it is molten to reduce lithium polysulfide
Amount of the solution in electrolyte；On the other hand, use carbon-nitrogen material provided by the invention for carbon-nitrogen nano tube in the battery, due to carbon
The tubular structure of nitride nanotubes itself can also stop more sulphur lithiumation objects to a certain extent, reduce it and be dissolved in electrolyte
Chance, reduce lithium polysulfide be dissolved in the amount in electrolyte；Based on these two aspects, using carbon-nitrogen material conduct of the invention
The positive electrode of lithium-sulfur cell, compared with the carbon material using nitrating is as the positive electrode of lithium-sulfur cell, it will be apparent that improve
The cyclical stability of lithium-sulfur cell.In addition, carbon nitrogen improves the electric conductivity of sulphur powder, therefore improves due to the addition of carbon-nitrogen material
The initial charge/discharge specific capacity of lithium-sulfur cell.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, those skilled in the art should understand that：Its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of carbon-nitrogen material, which is characterized in that include the following steps：
The mixture of catalyst and melamine is placed under inert atmosphere and is sintered, the carbon-nitrogen material is obtained.
2. preparation method according to claim 1, which is characterized in that the catalyst is NiCl.
3. preparation method according to claim 2, which is characterized in that the mass ratio of the NiCl and the melamine is
1-3：7-9.
4. any preparation method according to claim 1~3, which is characterized in that sintering temperature is 450-700 DEG C, sintering
Time is 3-5h.
5. a kind of carbon-nitrogen material that preparation method any according to claim 1~4 obtains.
6. carbon-nitrogen material according to claim 5, which is characterized in that the carbon-nitrogen material is carbon-nitrogen nano tube.
7. carbon-nitrogen material according to claim 6, which is characterized in that the caliber of the carbon-nitrogen nano tube is 50~500nm.
8. a kind of lithium sulfur battery anode material, which is characterized in that including sulphur powder and the described in any item carbon nitrogen of claim 5~7
Material.
9. lithium sulfur battery anode material according to claim 8, which is characterized in that the carbon-nitrogen material is carbon nitrogen nanometer
Pipe, the sulphur powder are filled in the carbon-nitrogen nano tube.
10. a kind of lithium-sulfur cell, which is characterized in that including cathode, electrolyte and anode, the just extremely exploitation right benefit requires 8
Or the anode that lithium sulfur battery anode material described in 9 is prepared.
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