CN106711457A - Nitrogen-enriched carbon shell cladded nano core-shell-structure carbonaceous carrier as well as preparation method and application thereof - Google Patents
Nitrogen-enriched carbon shell cladded nano core-shell-structure carbonaceous carrier as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nitrogen-enriched carbon shell cladded nano core-shell-structure carbonaceous carrier as well as a preparation method and application thereof. The carbonaceous carrier comprises a carbonaceous inner core and a nitrogen-enriched carbon shell covering the carbonaceous inner core. The carbonaceous carrier provided by the invention not only has abundant doping amount of a nitrogen element, but also has high polysulfide ion physical and chemical adsorption capabilities and excellent electrochemical stability; when the carbonaceous carrier is applied to a lithium-sulfur battery and is used as a positive electrode of a lithium-sulfur secondary battery, high capacity and rate circulating performance, and ultrahigh electrochemical stability can be kept even if the lithium-sulfur secondary battery is circularly charged and discharged for a long period, so that the whole electrochemical performance of the battery is improved; and meanwhile, a preparation process of the carbonaceous carrier has moderate conditions, low energy consumption and low cost and large-scale production is easy to realize.
Description
Technical field
The present invention relates to a kind of nano material, more particularly to a kind of nano-core-shell structure carbonaceous carrier, its preparation of rich nitrogen carbon shell cladding
Method and application, belong to electrochemical energy source domain.
Background technology
Novel high-energy metric density, long circulation life, environmental protection, inexpensive secondary cell have become energy storage area research in recent years
Focus.Lithium-sulfur cell has the advantages that high power capacity, high-energy-density, component are cheap and cause rapidly each due to potential
Energy sector of state and the concern and attention of energy enterprise, are increasingly becoming the research emphasis of high energy density cells of new generation.Lithium-sulfur cell
Successful industrialization will the fields such as electric automobile power battery, intelligent grid and the extensive energy-storage battery of clean energy resource produce it is huge
Value.However, because the electrical conductivity of sulphur is low, the dissolving migration of many lithium sulfides, the problems such as volumetric expansion is shunk, current lithium-sulfur cell
Actual energy density is well below its theoretical energy density, and cycle life is poor, and these all seriously hinder the industry of lithium-sulfur cell
Change process.To overcome problem above, conductive carbon black, porous carbon, carbon fiber, CNT, Graphene, hydridization carbon, hetero atom
The various conductive carbon materials such as (nitrogen or oxygen) functional carbon be used to be combined acquisition carbon sulphur positive electrode with nano-sulfur, be effectively improved lithium sulphur
The chemical property of battery.But, up to the present, the cycle life of lithium-sulfur cell still can not reach the requirement of industrialization.
The content of the invention
In view of the shortcomings of the prior art, it is a primary object of the present invention to provide a kind of nano-core-shell structure carbonaceous of rich nitrogen carbon shell cladding
Carrier, its preparation method and application.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
Provide a kind of nano-core-shell structure carbonaceous carrier of rich nitrogen carbon shell cladding in certain embodiments, it include carbonaceous kernel and
It is coated on the rich nitrogen carbon shell on carbonaceous kernel.
Further, the content of N element is 0.2at%~0.7at% (atomic percentage conc) in the carbonaceous carrier；
Preferably, N element and the mol ratio of C element are 150 in the rich nitrogen carbon shell:1~7:1.
Preferably, C element and the mol ratio of N element are 140 in the carbonaceous kernel:1~6:1.
A kind of preparation method of the nano-core-shell structure carbonaceous carrier of rich nitrogen carbon shell cladding is provided in certain embodiments, and it includes：
At least one carbon material is coated with polymer with nitrogen, the presoma with core shell structure is formed；
Carbonization treatment is carried out to the presoma, the nano-core-shell structure carbonaceous carrier of the rich nitrogen carbon shell cladding is formed.
The application of the nano-core-shell structure carbonaceous carrier of the rich nitrogen carbon shell cladding is provided in certain embodiments.
For example, providing a kind of sulphur carbon composite in certain embodiments, it includes：
The nano-core-shell structure carbonaceous carrier of described rich nitrogen carbon shell cladding；
And, it is carried on the sulphur on the carbonaceous carrier；
Wherein, the sulphur carbon composite includes 50~90wt% sulphur (weight/mass percentage composition).
A kind of preparation method of sulphur carbon composite is provided in certain embodiments, and it includes：
At least one carbon material is coated with polymer with nitrogen, the presoma with core shell structure is formed；
The presoma is uniformly mixed with sulphur, and carbonization treatment is carried out in protective atmosphere, form the sulphur carbon composite.
In certain embodiments, after also the presoma uniformly can be mixed with sulphur, molten sulfur expansion is carried out in protective atmosphere successively
Reaction and carbonization treatment are dissipated, the sulphur carbon composite is formed.
A kind of electrode material is provided in certain embodiments, and its nano-core-shell structure carbonaceous for including described rich nitrogen carbon shell cladding is carried
Body or described sulphur carbon composite.
A kind of cell positive material is provided in certain embodiments, and it includes described sulphur carbon composite, conductive agent and bonding
Agent.
A kind of energy storage device is provided in certain embodiments, and its nano-core-shell structure carbonaceous for including described rich nitrogen carbon shell cladding is carried
Body, described sulphur carbon composite, described electrode material or described cell positive material.
Further, the energy storage device includes lithium battery, such as lithium-sulfur cell.
Compared with prior art, advantages of the present invention includes：
(1) the nano-core-shell structure carbonaceous carrier that the present invention is provided not only has the doping of abundant nitrogen, and with strong many
Sulphion physics and chemical adsorption capacity and excellent electrochemical stability, it is being applied to lithium-sulfur cell, and such as application is secondary for lithium sulphur
During the positive electrode of battery, even if long circulating discharge and recharge can also keep high power capacity, circulation performance and superelevation electrochemical stability,
So that battery entirety chemical property is greatly improved.
(2) the features such as present invention has superior electrical conductivity and bigger serface using carbon materials such as CNT and Graphenes, Yi Jihan
The intrinsic functional group of nitrogen polymer, crosslinking and cementation, have been obtained the nano-core-shell structure carbonaceous carrier, process conditions temperature
With, energy-conservation, low consumption, easy large-scale production.
Brief description of the drawings
Fig. 1 a- Fig. 1 b be in embodiment 1 nitrogen-doped carbon nanometer pipe by the scanning electron microscope (SEM) photograph before and after polyaniline-coated；
Fig. 1 c- Fig. 1 d are the scanning electron microscope (SEM) photographs of NG-NCNT@PANI materials in embodiment 1；
Fig. 2 be in embodiment 2 comparison diagrams and NG-NCNT of the NCNT before and after cladding PANI and low-temperature carbonization in cladding
Comparison diagram before and after PANI and low-temperature carbonization；
Fig. 3 be in embodiment 3 NCNT@NCS@S materials and NCNT@S materials in 0.05C (1C=1675mAh/g) multiplying power
Lower first charge-discharge voltage-specific capacity comparison diagram；
Fig. 4 is the first charge-discharge voltage under 0.5C multiplying powers of NCNT@NCS@S materials and NCNT@S materials in embodiment 4
- specific capacity comparison diagram；
Fig. 5 be in embodiment 5 NCNT@NCS@S materials and NCNT@S materials under 0.2C multiplying powers first charge-discharge voltage-
Specific capacity comparison diagram；
Fig. 6 is that NG-NCNT@NCS@S materials and NCNT@NCS@S materials middle length under 0.5C multiplying powers are followed in embodiment 6
Ring comparison diagram；
Fig. 7 is that NG-NCNT@NCS@S and NCNT@NCS@S middle circulations under different charge-discharge magnifications are right in embodiment 7
Than figure.
Fig. 8 is the cyclic voltammogram of NG-NCNT@NCS@S-500 in embodiment 8.
Specific embodiment
In view of deficiency of the prior art, inventor is able to propose technical side of the invention through studying for a long period of time and largely putting into practice
Case.The technical scheme, its implementation process and principle etc. will be further explained as follows.
One aspect of the present invention provides a kind of nano-core-shell structure carbonaceous carrier of rich nitrogen carbon shell cladding, it include carbonaceous kernel with
And it is coated on the rich nitrogen carbon shell on carbonaceous kernel.
Further, the content of N element is 0.2at%~0.7at% (atomic percentage conc) in the carbonaceous carrier.
Further, N element and the mol ratio of C element are 150 in the rich nitrogen carbon shell:1~7:1.
Further, N element and the mol ratio of C element are 140 in the carbonaceous kernel:1~6:1.
Further, a diameter of 10nm~25nm of the carbonaceous kernel, the thickness of the rich nitrogen carbon shell is 40nm~65nm.
Further, the carbonaceous carrier has the loose structure being formed in situ, and the aperture of its contained hole is 4nm~30nm, than
Surface area is 80~500m2g-1。
Further, the nano-core-shell structure carbonaceous carrier of described rich nitrogen carbon shell cladding is applicable as electrode material.
One aspect of the present invention provides a kind of method of the nano-core-shell structure carbonaceous carrier for making the rich nitrogen carbon shell cladding, bag
Include：
At least one carbon material is coated with polymer with nitrogen, the presoma with core shell structure is formed；
Carbonization treatment is carried out to the presoma, the nano-core-shell structure carbonaceous carrier of the rich nitrogen carbon shell cladding is formed.
In some more preferred embodiment, described preparation method includes：To described under 100 DEG C~500 DEG C of temperature conditionss
Presoma carries out carbonization treatment.Further, the carbonization treatment time for using is 12h~24h.
One aspect of the present invention provides a kind of sulphur carbon composite, and it includes：
The nano-core-shell structure carbonaceous carrier of described rich nitrogen carbon shell cladding；
And, it is carried on the sulphur on the carbonaceous carrier；
Wherein, the sulphur carbon composite includes 50~90wt% sulphur (mass percent).
One aspect of the present invention provides a kind of method for making the sulphur carbon composite, and it includes：
At least one carbon material is coated with polymer with nitrogen, the presoma with core shell structure is formed；
The presoma is uniformly mixed with sulphur, and carbonization treatment is carried out in protective atmosphere, form the sulphur carbon composite.
In certain embodiments, described preparation method may also include：After the presoma is uniformly mixed with sulphur, in atmosphere is protected
Molten sulfur diffusion reaction and carbonization treatment are carried out successively, form the sulphur carbon composite.
More preferred, the reaction temperature of the molten sulfur diffusion reaction is 150 DEG C~180 DEG C, and the time is 12h~24h.
More preferred, the carbonization treatment temperature is 100 DEG C~500 DEG C.
In certain embodiments, the material of foregoing carbonaceous kernel includes Graphene, CNT, any in carbon fiber and porous carbon
One or more combination, but not limited to this.Preferably, the material of foregoing carbonaceous kernel includes Graphene and/or carbon nanometer
Pipe.
Further, the material of foregoing carbonaceous kernel is selected from nitrogen-doped carbon material, such as preferably from nitrogen-doped carbon nanometer pipe and/or nitrogen
Doped graphene.
In certain embodiments, foregoing polymer with nitrogen include polyaniline, polypyrrole, amino protein matter polymer, polyacrylonitrile,
Poly-dopamine, any one in polyacrylamide or two or more combinations, but not limited to this.
In these embodiments, the features such as superior electrical conductivity and bigger serface for possessing using CNT, Graphene, Yi Jihan
The nitrogen polymer functional group of feature, crosslinking and cementation in itself, can form doping with abundant nitrogen and excellent comprehensive
Close the nano-core-shell structure carbonaceous carrier of the rich nitrogen carbon shell cladding of performance.More specifically, for example, using carbon core (such as CNT,
Graphene) superior electrical conductivity that has, active material utilization is low in can solving the problems, such as lithium-sulfur cell, and utilizes rich nitrogen carbon
Shell, the chemisorbed of CNT and/or Graphene bigger serface and physical absorption ability can effectively suppress the shuttle of polysulfide
Gu sulphur, realizes that the efficient of sulphur positive pole utilizes and the high circulation life-span.
Further, the nano-core-shell structure carbonaceous carrier of the invention is being applied to lithium-sulfur cell, such as the secondary electricity of lithium sulphur
When the positive electrode in pond is used, compared with traditional carbon material and conventional nitrogen doped, processing method is gentleer, section
Can, low consumption particularly introduces the electric conductivity enhancing of nano-carbon material after two-dimensional graphene, and electrode for secondary battery structure is in electrification
The Stability Analysis of Structures that cyclic process ensure that material is learned, electrochemical cycle stability sex expression is protruded under different multiplying, battery-active material
The utilization rate of material is significantly improved, so that battery entirety chemical property is greatly improved, to accelerating lithium-sulfur cell
Industrialization has great importance.
Postscript, the technique of the making nano-core-shell structure carbonaceous carrier that the present invention is provided has inexpensive, the advantage of low energy consumption,
The problems such as high energy consumption, the high cost produced using high temperature N doping can effectively be overcome, and easily large-scale production.
One aspect of the present invention provides a kind of electrode material, its nano-core-shell structure carbonaceous for including described rich nitrogen carbon shell cladding
Carrier or described sulphur carbon composite.
For example, provide a kind of cell positive material in certain embodiments, its include described sulphur carbon composite, conductive agent and
Binding agent.
For example, a kind of chemical energy storage device is provided in certain embodiments, its nano core-shell for including described rich nitrogen carbon shell cladding
Structure carbonaceous carrier, described sulphur carbon composite, described electrode material or described cell positive material.
Wherein, described chemical energy storage device includes lithium battery, and such as lithium-sulfur cell is specific such as lithium-sulfur rechargeable battery.
When the nano-core-shell structure carbonaceous carrier of the invention is applied to lithium-sulfur rechargeable battery, even if also being kept in long circulating discharge and recharge
The electrochemical stability of high power capacity, circulation performance and superelevation.
Technical scheme is more specifically illustrated below in conjunction with accompanying drawing and some embodiments.
Embodiment 1：The preparation of rich nitrogen carbon shell persursor material (NCNT@NCS and NG-NCNT@NCS)
Concentrated acid (volume ratio H2SO4:HNO3=3:1) treatment CNT (CNT), then it is passed through ammonia under 750 DEG C of temperature conditionss
Carry out nitrogen treatment and obtain nitrogen-doped carbon nanometer pipe (NCNT), its nitrogen content is 0.62at%.The NCNT for weighing 100mg surpasses
Sound is dispersed in ultra-pure water, aniline (ANI) solution of 150mg is slowly added dropwise, between salt acid for adjusting pH value to 1~2.
Under the conditions of ice-water bath, appropriate ammonium persulfate is slowly added dropwise, stirred 24 hours, reaction terminates filtration washing, vacuum drying is obtained
PANI coats NCNT materials (NCNT@PANI), and it is one-dimensional rich nitrogen nano-material.
Introduce nitrogen-doped graphene in certain proportion with NCNT together ultrasonic disperse, be slowly added dropwise aniline solution, adjusted with hydrochloric acid
PH value is between 1-2.Under the conditions of ice-water bath, appropriate ammonium persulfate is slowly added dropwise, stirred 24 hours, reaction terminates filtering
Washing, vacuum drying obtains the NG-NCNT materials (NG-NCNT@PANI) of PANI claddings, and it is three-dimensional manometer richness nitrogen
Nano material.
Can be seen that nitrogen-doped carbon nanometer pipe by caliber after in-situ polymerization from the ESEM and transmission electron microscope picture shown in Fig. 1 a- Fig. 1 b
Increase, surface becomes more coarse.
Scanning electron microscope (SEM) photograph shown in Fig. 1 c and Fig. 1 d can be seen that nitrogen-doped carbon nanometer pipe by in-situ polymerization in nitrogen-doped graphene
Surface-crosslinked to be combined together, surface becomes more coarse.
Embodiment 2：The low-temperature carbonization of the rich rich carbon nanometer of nitrogen carbon shell PANI claddings is prepared and characterized
Under the protection of argon gas, by the one-dimensional rich nitrogen nano-material (NCNT@PANI) obtained in embodiment 1 first at 155 DEG C
12 hours of carbonization, then be carbonized 12 hours at 180 DEG C, nano-carbon material (NCNT@NCS) is obtained, its nitrogen content is
11.1at%.
Three-dimensional manometer richness nitrogen nano-material (NG-NCNT@PANI) carries out low-temperature carbonization treatment at identical conditions, obtains richness
Nitrogenous nano-carbon material (NG-NCNT@NCS), its nitrogen content is up to 12.6at%.
After PANI claddings are can be seen that from the Raman spectrogram shown in Fig. 2, at 1402 and 1235 wave numbers
NCNT@PANI and NG-NCNT@PANI can show the peak of PANI, after low-temperature carbonization treatment, the feature of PANI
Peak all weakens even disappearance, and it is carbon material that XRD characterizes shell, and this shows after low-temperature treatment, and PANI is formd after low-temperature treatment
Nano-sized carbon shell (NCS) rich in nitrogen, so as to form NCNT@NCS and NG-NCNT@NCS nano-carbon materials.
Embodiment 3：
Embodiment 1 is obtained into one-dimensional rich nitrogen carbon nanomaterial (NCNT@PANI) and business sulphur mixes (mass ratio 35：65),
In sealed reactor under argon gas protective condition, 155 DEG C of 12 hours of diffusion reaction by molten sulfur, positive electrode active materials are obtained
(NCNT@NCS@S)。
NCNT@NCS@S, carbon black (conductive agent) and binding agent (PVDF) are pressed 8 again：1：1 mass ratio mixing is equal
It is even, anode sizing agent is prepared, anode sizing agent is uniformly coated on aluminium foil, the drying 24 hours of 50 DEG C of vacuum is punched into a diameter of
Used as positive pole, lithium metal adds 1%LiNO to the piece of 15mm as negative pole3The DOL/DME of LiTFSI (volume ratio is 1:1)
Solution assembles button cell as electrolyte with 2025 type battery cases, and the compound of NCNT@S is prepared for same method
Positive electrode pole piece.Evaluate the performance of positive electrode.
From figure 3, it can be seen that for positive electrode, low-temperature carbonization treatment nitrogen-doped carbon material shows higher under 0.05C multiplying powers
Battery reversible specific capacity and more preferable circulating battery stability.
Embodiment 4：
Embodiment 1 is obtained and one-dimensional mixes (mass ratio 35 rich in nitrogen-doped carbon nano material (NCNT@PANI) and business sulphur：
65), in sealed reactor under argon gas protective condition, 155 DEG C of 12 hours of diffusion reaction by molten sulfur, then at 180 DEG C
Low-temperature treatment is carbonized, and obtains positive electrode active materials (NCNT@NCS@S).
NCNT@NCS@S, carbon black (conductive agent) and binding agent (PVDF) are pressed 8：1：1 mass ratio is well mixed,
Anode sizing agent is prepared, anode sizing agent is uniformly coated on aluminium foil, the drying 24 hours of 50 DEG C of vacuum is punched into a diameter of 15mm
Piece as positive pole, lithium metal adds 1%LiNO as negative pole3The DOL/DME of LiTFSI (volume ratio is 1:1) solution is made
It is electrolyte, button cell is assembled with 2025 type battery cases, the positive pole material of the compound of NCNT@S is prepared for same method
Material pole piece.Evaluate the performance of positive electrode.
From fig. 4, it can be seen that for positive electrode, low-temperature carbonization treatment nitrogen-doped carbon material shows higher under 0.5C multiplying powers
The utilization rate of active material, battery specific capacity and more preferable circulating battery stability.
Embodiment 5：
Weigh embodiment 1 and obtain NCNT@PANI materials and mix (mass ratio 35 with business sulphur：65), argon in sealed reactor
Under the conditions of gas shielded, low-temperature treatment carbonization, obtains positive electrode active materials (NCNT@NCS@S) at 180 DEG C.
NCNT@NCS@S, carbon black (conductive agent) and binding agent (PVDF) press 8：1：1 mass ratio is well mixed, system
Standby anode sizing agent, anode sizing agent is uniformly coated on aluminium foil, and the drying 24 hours of 50 DEG C of vacuum is punched into a diameter of 15mm's
Used as positive pole, lithium metal adds 1%LiNO to piece as negative pole3The DOL/DME of LiTFSI (volume ratio is 1:1) solution conduct
Electrolyte, button cell is assembled with 2025 type battery cases, and the compound for being prepared for NCNT@NCS@S with same method is just
Pole material cell.Evaluate the performance of positive electrode.
From fig. 5, it can be seen that for positive electrode, the positive electrode of the cladding of carbon shell material is not carried out under low range (0.2C)
The ratio of capacity attenuation is very fast, and low-temperature carbonization treatment nitrogen-doped carbon material shows battery specific capacity higher and more preferable circulating battery is steady
It is qualitative.
Embodiment 6：
Weigh embodiment 2 and obtain NG-NCNT@PANI materials and business sulphur (mass ratio 35：65), argon gas in sealed reactor
Under protective condition, 155 DEG C of 12 hours of diffusion reaction by molten sulfur, then the low-temperature treatment carbonization at 180 DEG C, obtain positive pole
Active material (NG-NCNT@NCS@S).
NG-NCNT@NCS@S, carbon black (conductive agent) and binding agent (PVDF) press 8：1：1 mass ratio is well mixed,
Anode sizing agent is prepared, anode sizing agent is uniformly coated on aluminium foil, the drying 24 hours of 50 DEG C of vacuum is punched into a diameter of 15mm
Piece as positive pole, lithium metal adds 1%LiNO as negative pole3The DOL/DME of LiTFSI (volume ratio is 1:1) solution is made
It is electrolyte, button cell is assembled with 2025 type battery cases, the compound of NCNT@NCS@S is prepared for same method
Positive electrode battery.Evaluate the performance of positive electrode.
From fig. 6, it can be seen that for positive electrode, low-temperature carbonization treatment nitrogen-doped carbon material is mixed in nitrogen under low range (0.4C)
The utilization rate of active material higher, bigger battery specific capacity and more preferable circulating battery stabilization are shown after the introducing of miscellaneous Graphene
Property.
Embodiment 7：
Example 2 obtains NG-NCNT@PANI materials and business sulphur (mass ratio 35：65) in addition sealed reactor,
And under argon gas protective condition, low-temperature treatment carbonization, obtains positive electrode active materials (NG- at 180 DEG C
NCNT@NCS@S)。
NG-NCNT@NCS@S, carbon black (conductive agent) and binding agent (PVDF) press 8：1：1 mass ratio is well mixed,
Anode sizing agent is prepared, anode sizing agent is uniformly coated on aluminium foil, the drying 24 hours of 50 DEG C of vacuum is punched into a diameter of 15mm
Piece as positive pole, lithium metal adds 1%LiNO as negative pole3The DOL/DME of LiTFSI (volume ratio is 1:1) solution is made
It is electrolyte, button cell is assembled with 2025 type battery cases, the compound of NCNT@NCS@S is prepared for same method
Positive electrode battery.Evaluate the performance of positive electrode.
From figure 7 it can be seen that for positive electrode, low-temperature carbonization treatment nitrogen-doped carbon material is introducing N doping under different multiplying
The material of the three-dimensional structure formed after Graphene, electric conductivity is remarkably reinforced, and shows the utilization rate of active material higher, bigger
Battery specific capacity and more preferable circulating battery stability.
Embodiment 8
Weigh embodiment 2 and obtain NG-NCNT@PANI materials and business sulphur (mass ratio 35：65), argon gas in sealed reactor
Under protective condition, the first low-temperature treatment carbonization at 500 DEG C, then 155 DEG C of 12 hours of diffusion reaction by molten sulfur obtain positive pole
Active material (NG-NCNT@NCS@S-500).
NG-NCNT@NCS@S-500, carbon black (conductive agent) and binding agent (PVDF) press 8：1：1 mass ratio mixing is equal
It is even, anode sizing agent is prepared, anode sizing agent is uniformly coated on aluminium foil, the drying 24 hours of 50 DEG C of vacuum is punched into a diameter of
Used as positive pole, lithium metal adds 1%LiNO to the piece of 15mm as negative pole3The DOL/DME of LiTFSI (volume ratio is 1:1)
Solution assembles button cell as electrolyte with 2025 type battery cases, and answering for NCNT@NCS@S is prepared for same method
The positive electrode battery of compound.Evaluate the performance of positive electrode.
From figure 8, it is seen that for positive electrode, with the increase of cycle-index, active material is lost in relatively more, and capacity declines
Subtract shuttle effect substantially, the invertibity of circulation is poor, this shows when being carbonized for 500 DEG C, the stability of the chemical property of battery
It is not good enough.
It should be appreciated that above-described embodiment is only explanation technology design of the invention and feature, technique is familiar with its object is to allow
Personage will appreciate that present disclosure and implement according to this that it is not intended to limit the scope of the present invention.It is all smart according to the present invention
The equivalent change or modification that refreshing essence is made, should all be included within the scope of the present invention.
Claims (17)
1. a kind of nano-core-shell structure carbonaceous carrier of rich nitrogen carbon shell cladding, it is characterised in that including carbonaceous kernel and be coated on carbonaceous
Rich nitrogen carbon shell on kernel.
2. the nano-core-shell structure carbonaceous carrier that rich nitrogen carbon shell according to claim 1 is coated, it is characterised in that：
The content of N element is 0.2at%~0.7at% in the carbonaceous carrier；
Preferably, C element and the mol ratio of N element are 150 in the rich nitrogen carbon shell:1~7:1；
And/or, it is preferred that C element and the mol ratio of N element are 140 in the carbonaceous kernel:1~6:1.
3. the nano-core-shell structure carbonaceous carrier that rich nitrogen carbon shell according to claim 1 is coated, it is characterised in that in the carbonaceous
A diameter of 10nm~25nm of core, the thickness of the rich nitrogen carbon shell is 40nm~65nm.
4. the nano-core-shell structure carbonaceous carrier that rich nitrogen carbon shell according to claim 1 is coated, it is characterised in that：
The material of the carbonaceous kernel include Graphene, CNT, in carbon fiber and porous carbon any one or it is two or more
Combination；
Preferably, the material of the carbonaceous kernel is selected from nitrogen-doped carbon material, and the nitrogen-doped carbon material includes nitrogen-doped carbon nanometer pipe
And/or nitrogen-doped graphene.
5. the nano-core-shell structure carbonaceous carrier that rich nitrogen carbon shell according to claim 1 is coated, it is characterised in that the carbonaceous is carried
Body has the loose structure being formed in situ, and the aperture of its contained hole is 4nm~30nm, and specific surface area is 80~500m2g-1。
6. a kind of preparation method of the nano-core-shell structure carbonaceous carrier of rich nitrogen carbon shell cladding, it is characterised in that including：
At least one carbon material is coated with polymer with nitrogen, the presoma with core shell structure is formed；
Carbonization treatment is carried out to the presoma, the nano-core-shell structure carbonaceous carrier of the rich nitrogen carbon shell cladding is formed.
7. preparation method according to claim 6, it is characterised in that including：To before described under 100 DEG C~500 DEG C of the temperature conditionss
Driving body carries out carbonization treatment.
8. preparation method according to claim 7, it is characterised in that：
The polymer with nitrogen includes polyaniline, polypyrrole, amino protein matter polymer, polyacrylonitrile, poly-dopamine, polypropylene
Any one in acid amides or two or more combinations；
And/or, the carbon material includes Graphene, CNT, any one in carbon fiber and porous carbon or two or more groups
Close；
Preferably, the carbon material is selected from nitrogen-doped carbon material, and the nitrogen-doped carbon material includes that nitrogen-doped carbon nanometer pipe and/or nitrogen are mixed
Miscellaneous Graphene.
9. a kind of sulphur carbon composite, it is characterised in that including：
The nano-core-shell structure carbonaceous carrier of the rich nitrogen carbon shell cladding any one of claim 1-5；
And, it is carried on the sulphur on the carbonaceous carrier；
Wherein, the sulphur carbon composite includes 50~90wt% sulphur.
10. a kind of preparation method of sulphur carbon composite, it is characterised in that including：
At least one carbon material is coated with polymer with nitrogen, the presoma with core shell structure is formed；
The presoma is uniformly mixed with sulphur, and carbonization treatment is carried out in protective atmosphere, form the sulphur carbon composite.
11. preparation methods according to claim 10, it is characterised in that also include：The presoma is uniformly mixed with sulphur
Afterwards, molten sulfur diffusion reaction and carbonization treatment are carried out in protective atmosphere successively, the sulphur carbon composite is formed.
12. preparation method according to claim 10 or 11, it is characterised in that：
The polymer with nitrogen includes polyaniline, polypyrrole, amino protein matter polymer, polyacrylonitrile, poly-dopamine, polypropylene
Any one in acid amides or two or more combinations；
And/or, the carbon material includes Graphene, CNT, any one in carbon fiber and porous carbon or two or more groups
Close；Preferably, the carbon material is selected from nitrogen-doped carbon material, and the nitrogen-doped carbon material includes that nitrogen-doped carbon nanometer pipe and/or nitrogen are mixed
Miscellaneous Graphene；
Preferably, the carbonization treatment temperature is 100 DEG C~500 DEG C.
13. preparation methods according to claim 11, it is characterised in that the reaction temperature of the molten sulfur diffusion reaction for-
150 DEG C~300 DEG C, the time is 12h~24h.
A kind of 14. electrode materials, it is characterised in that the nano core-shell comprising the rich nitrogen carbon shell cladding any one of claim 1-5
Sulphur carbon composite described in structure carbonaceous carrier and/or claim 9.
15. a kind of cell positive materials, it is characterised in that comprising the sulphur carbon composite described in claim 9, conductive agent and bonding
Agent.
A kind of 16. chemical energy storage devices, it is characterised in that the nanometer comprising the rich nitrogen carbon shell cladding any one of claim 1-5
Electrode material described in sulphur carbon composite, claim 14 or claim described in core shell structure carbonaceous carrier, claim 9
Cell positive material described in 15.
17. chemical energy storage devices as claimed in claim 16, it is characterised in that the chemical energy storage device includes lithium battery, described
Lithium battery includes lithium-sulfur cell.
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