CN106711457B - Nano-core-shell structure carbonaceous carrier, its preparation method and the application of rich nitrogen carbon shell cladding - Google Patents
Nano-core-shell structure carbonaceous carrier, its preparation method and the application of rich nitrogen carbon shell cladding Download PDFInfo
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- H01M4/00—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The invention discloses nano-core-shell structure carbonaceous carrier, its preparation method and the applications of a kind of rich nitrogen carbon shell cladding.The carbonaceous carrier includes carbonaceous kernel and the rich nitrogen carbon shell that is coated on carbonaceous kernel.The carbonaceous carrier provided by the invention not only has the doping of nitrogen abundant; and there is strong more sulphion physics and chemical adsorption capacity and excellent electrochemical stability; it is when being applied to lithium-sulfur cell; such as when using being the positive electrode of lithium-sulfur rechargeable battery; high capacity, circulation performance and superelevation electrochemical stability can also be kept even if long circulating charge and discharge; so that battery entirety chemical property gets a promotion; the preparation process condition of the carbonaceous carrier is mild simultaneously; low energy consumption; low cost is easy to large-scale production.
Description
Technical field
The present invention relates to a kind of nano material, in particular to a kind of nano-core-shell structure carbonaceous of rich nitrogen carbon shell cladding carries
Body, preparation method and application belong to electrochemical energy source domain.
Background technique
Novel high-energy metric density, long circulation life, environmentally protective, inexpensive secondary cell have become the neck of energy storage in recent years
The hot spot of domain research.Lithium-sulfur cell is cheap and rapid due to potentially having many advantages, such as high capacity, high-energy density, component
The concern and attention for causing energy sector, various countries and energy enterprise are increasingly becoming the research weight of high energy density cells of new generation
Point.The successful industrialization of lithium-sulfur cell will be in electric automobile power battery, smart grid and the extensive energy storage electricity of clean energy resource
The fields such as pond generate huge value.However, since the conductivity of sulphur is low, the dissolution migration of more lithium sulfides, volume expansion is shunk etc.
Problem, lithium-sulfur cell actual energy density is well below its theoretical energy density at present, and cycle life is poor, these are all serious
Hinder the industrialization process of lithium-sulfur cell.To overcome problem above, conductive carbon black, porous carbon, carbon fiber, carbon nanotube, stone
The various conductive carbon materials such as black alkene, hydridization carbon, hetero atom (nitrogen or oxygen) functional carbon are used for and the compound acquisition carbon sulphur of nano-sulfur
Positive electrode is effectively improved the chemical property of lithium-sulfur cell.But up to the present, the cycle life of lithium-sulfur cell is still
The requirement of industrialization cannot be reached.
Summary of the invention
In view of the deficiencies of the prior art, the main purpose of the present invention is to provide a kind of nano core-shells of rich nitrogen carbon shell cladding
Structure carbonaceous carrier, its preparation method and application.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
A kind of nano-core-shell structure carbonaceous carrier of rich nitrogen carbon shell cladding is provided in some embodiments comprising carbonaceous
Kernel and the rich nitrogen carbon shell being coated on carbonaceous kernel.
Further, the content of N element is 0.2at%~0.7at% (atomic percentage content) in the carbonaceous carrier；
Preferably, the molar ratio of N element and C element is 150:1~7:1 in the rich nitrogen carbon shell.
Preferably, the molar ratio of C element and N element is 140:1~6:1 in the carbonaceous kernel.
A kind of preparation method of the nano-core-shell structure carbonaceous carrier of rich nitrogen carbon shell cladding, packet are provided in some embodiments
It includes:
At least one carbon material is coated with polymer with nitrogen, forms the presoma with core-shell structure；
Carbonization treatment is carried out to the presoma, forms the nano-core-shell structure carbonaceous carrier of the rich nitrogen carbon shell cladding.
The application of the nano-core-shell structure carbonaceous carrier of the rich nitrogen carbon shell cladding is provided in some embodiments.
For example, providing a kind of sulphur carbon composite in some embodiments comprising:
The nano-core-shell structure carbonaceous carrier of the 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 percentage).
A kind of production method of sulphur carbon composite is provided in some embodiments comprising:
At least one carbon material is coated with polymer with nitrogen, forms the presoma with core-shell structure；
The presoma is uniformly mixed with sulphur, and carries out carbonization treatment in protective atmosphere, it is multiple to form the sulphur carbon
Condensation material.
In some embodiments, it can also successively be carried out in protective atmosphere by the presoma and sulphur after evenly mixing
Molten sulfur diffusion reaction and carbonization treatment form the sulphur carbon composite.
A kind of electrode material is provided in some embodiments, and it includes the nano core-shell knots of rich nitrogen carbon shell cladding
Structure carbonaceous carrier or the sulphur carbon composite.
A kind of cell positive material is provided in some embodiments, and it includes the sulphur carbon composites, conductive agent
And binder.
A kind of energy storage device is provided in some embodiments, and it includes the nano core-shell knots of rich nitrogen carbon shell cladding
Structure carbonaceous carrier, the sulphur carbon composite, the electrode material or the cell positive material.
Further, the energy storage device includes lithium battery, such as lithium-sulfur cell.
Compared with prior art, the invention has the advantages that
(1) nano-core-shell structure carbonaceous carrier provided by the invention not only has the doping of nitrogen abundant, and
With strong more sulphion physics and chemical adsorption capacity and excellent electrochemical stability, it is being applied to lithium-sulfur cell, such as is answering
When with positive electrode for lithium-sulfur rechargeable battery, high capacity, circulation performance and super can also be kept even if long circulating charge and discharge
High electrochemical stability, so that battery entirety chemical property is greatly improved.
(2) present invention has superior electrical conductivity and bigger serface etc. special using carbon materials such as carbon nanotube and graphenes
The nano-core-shell structure carbonaceous carrier has been made in intrinsic functional group, crosslinking and the cementation of point and polymer with nitrogen,
Process conditions are mild, energy conservation, low consumption, easy large-scale production.
Detailed description of the invention
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 is the scanning electron microscope (SEM) photograph of NG-NCNT@PANI material in embodiment 1；
Fig. 2 is that comparison diagram and NG-NCNT of the NCNT before and after cladding PANI and low-temperature carbonization are coating in embodiment 2
Comparison diagram before and after PANI and low-temperature carbonization；
Fig. 3 be in embodiment 3 NCNT@NCS@S material and NCNT@S material under 0.05C (1C=1675mAh/g) multiplying power
First charge-discharge voltage-specific capacity comparison diagram；
Fig. 4 is the first charge-discharge voltage-under 0.5C multiplying power of NCNT@NCS@S material and NCNT@S material in embodiment 4
Specific capacity comparison diagram；
Fig. 5 is NCNT@NCS@S material and NCNT@S material first charge-discharge voltage-ratio under 0.2C multiplying power in embodiment 5
Capacity comparison figure；
Fig. 6 is NG-NCNT@NCS@S material and NCNT@NCS@the S material middle long circulating pair under 0.5C multiplying power in embodiment 6
Than figure；
Fig. 7 is NG-NCNT@NCS@S and NCNT@NCS@S middle circulation comparison under different charge-discharge magnifications in embodiment 7
Figure.
Fig. 8 is the cyclic voltammogram of NG-NCNT@NCS@S-500 in embodiment 8.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution.The technical solution, 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 comprising carbon
Matter kernel and the rich nitrogen carbon shell being coated on carbonaceous kernel.
Further, the content of N element is 0.2at%~0.7at% (atomic percentage content) in the carbonaceous carrier.
Further, the molar ratio of N element and C element is 150:1~7:1 in the rich nitrogen carbon shell.
Further, the molar ratio of N element and C element is 140:1~6:1 in the carbonaceous kernel.
Further, the diameter of the carbonaceous kernel is 10nm~25nm, the richness nitrogen carbon shell with a thickness of 40nm~
65nm。
Further, the carbonaceous carrier has the porous structure that is formed in situ, the aperture of contained hole be 4nm~
30nm, specific surface area are 80~500m2g-1。
Further, the nano-core-shell structure carbonaceous carrier of rich nitrogen carbon shell cladding is applicable as electrode material.
One aspect of the present invention provides a kind of nano-core-shell structure carbonaceous carrier for making the rich nitrogen carbon shell cladding
Method, comprising:
At least one carbon material is coated with polymer with nitrogen, forms the presoma with core-shell structure；
Carbonization treatment is carried out to the presoma, forms the nano-core-shell structure carbonaceous carrier of the rich nitrogen carbon shell cladding.
In some more preferred embodiments, the preparation method includes: the temperature condition at 100 DEG C~500 DEG C
Under to the presoma carry out carbonization treatment.Further, the carbonization treatment time used is 12h~for 24 hours.
One aspect of the present invention provides a kind of sulphur carbon composite comprising:
The nano-core-shell structure carbonaceous carrier of the 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 comprising:
At least one carbon material is coated with polymer with nitrogen, forms the presoma with core-shell structure；
The presoma is uniformly mixed with sulphur, and carries out carbonization treatment in protective atmosphere, it is multiple to form the sulphur carbon
Condensation material.
In some embodiments, the production method may also include that the presoma and sulphur after evenly mixing, protect
Molten sulfur diffusion reaction and carbonization treatment are successively carried out in atmosphere, 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~for 24 hours.
More preferred, the carbonization treatment temperature is 100 DEG C~500 DEG C.
In some embodiments, the material of aforementioned carbonaceous kernel includes graphene, carbon nanotube, in carbon fiber and porous carbon
Any one or two or more combinations, but not limited to this.Preferably, the material of aforementioned carbonaceous kernel include graphene and/
Or carbon nanotube.
Further, the material of aforementioned carbonaceous kernel is selected from nitrogen-doped carbon material, such as preferably from nitrogen-doped carbon nanometer
Pipe and/or nitrogen-doped graphene.
In some embodiments, aforementioned polymer with nitrogen includes polyaniline, polypyrrole, amino protein matter polymer, and poly- third
Alkene nitrile, 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 having using carbon nanotube, graphene,
And functional group, crosslinking and the cementation of polymer with nitrogen feature itself, the doping with nitrogen abundant can be formed
And the nano-core-shell structure carbonaceous carrier of the rich nitrogen carbon shell cladding of Good All-around Property.More specifically, for example, utilizing carbon core
Superior electrical conductivity possessed by (such as carbon nanotube, graphene), can solve that active material utilization in lithium-sulfur cell is low to ask
Topic, and can have using the chemisorption and physical absorption ability of rich nitrogen carbon shell, carbon nanotube and/or graphene bigger serface
It imitates and the shuttle of polysulfide is inhibited to consolidate sulphur, realize that the efficient of sulphur anode utilizes and the high circulation service life.
Further, the nano-core-shell structure carbonaceous carrier of the invention is being applied to lithium-sulfur cell, such as lithium
The positive electrode of sulfur rechargeable battery is in use, compared with traditional carbon material and common nitrogen doped, and processing method is more
Heating and, energy conservation, the electric conductivity enhancing of nano-carbon material, and secondary battery after low consumption, especially introducing two-dimensional graphene
Pole structure can guarantee the stable structure of material in electrochemistry cyclic process, the electrochemical cycle stability sex expression under different multiplying
Prominent, the utilization rate of battery active material is significantly improved, so that battery entirety chemical property obtains very big mention
It rises, has great importance to the industrialization for accelerating lithium-sulfur cell.
The technique of postscript, the production nano-core-shell structure carbonaceous carrier provided by the invention has low cost, low energy consumption
The advantages of, the problems such as can effectively overcoming the high energy consumption generated using high temperature N doping, Gao Chengben, and easy large-scale production.
One aspect of the present invention provides a kind of electrode material, and it includes the nano core-shells of rich nitrogen carbon shell cladding
Structure carbonaceous carrier or the sulphur carbon composite.
For example, providing a kind of cell positive material in some embodiments, it includes the sulphur carbon composite, lead
Electric agent and binder.
For example, providing a kind of chemical energy storage device in some embodiments, it includes rich nitrogen carbon shell claddings
Nano-core-shell structure carbonaceous carrier, the sulphur carbon composite, the electrode material or the cell positive material.
Wherein, the chemical energy storage device includes lithium battery, such as lithium-sulfur cell, 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 in long circulating charge and discharge
Electricity also maintains the electrochemical stability of high capacity, circulation performance and superelevation.
Technical solution of the present invention is more specifically illustrated below in conjunction with attached drawing and several 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) processing carbon nanotube (CNT), then ammonia is passed through under the conditions of 750 DEG C of temperature
Gas carries out nitrogen treatment and obtains nitrogen-doped carbon nanometer pipe (NCNT), nitrogen content 0.62at%.Weigh the NCNT ultrasound of 100mg
It is dispersed in ultrapure water, aniline (ANI) solution of 150mg is slowly added dropwise, between salt acid for adjusting pH value to 1~2.In ice-water bath
Under the conditions of, suitable ammonium persulfate is slowly added dropwise, stirs 24 hours, reaction terminates filtration washing, and vacuum drying obtains PANI packet
NCNT material (NCNT@PANI) is covered, for one-dimensional rich nitrogen nano-material.
Nitrogen-doped graphene is introduced in certain proportion with NCNT together ultrasonic disperse, aniline solution is slowly added dropwise, uses salt
Acid for adjusting pH value is between 1-2.Under the conditions of ice-water bath, suitable ammonium persulfate is slowly added dropwise, stirs 24 hours, reaction terminates
Filtration washing, vacuum drying obtain the NG-NCNT material (NG-NCNT@PANI) of PANI cladding, receive for three-dimensional manometer richness nitrogen
Rice material.
Scanning electron microscope and transmission electron microscope picture shown in Fig. 1 a- Fig. 1 b can be seen that nitrogen-doped carbon nanometer pipe by in-situ polymerization
Caliber increases later, and surface becomes more coarse.
The scanning electron microscope (SEM) photograph shown in Fig. 1 c and Fig. 1 d can be seen that nitrogen-doped carbon nanometer pipe is mixed by in-situ polymerization in nitrogen
Miscellaneous graphene surface crosslinking is combined together, and surface becomes more coarse.
Embodiment 2: rich nitrogen carbon shell PANI coats the low-temperature carbonization preparation and characterization of rich carbon nanometer
Under the protection of argon gas, by one-dimensional richness nitrogen nano-material (NCNT@PANI) obtained in embodiment 1 first 155
DEG C carbonization 12 hours, then at 180 DEG C be carbonized 12 hours, obtain nano-carbon material (NCNT@NCS), nitrogen content is
11.1at%.
Three-dimensional manometer richness nitrogen nano-material (NG-NCNT@PANI) carries out low-temperature carbonization processing at identical conditions, obtains
Nano-carbon material (NG-NCNT@NCS) rich in nitrogen, nitrogen content is up to 12.6at%.
After it can be seen that PANI cladding in Raman spectrogram shown in Fig. 2, the NCNT@at 1402 and 1235 wave numbers
PANI and NG-NCNT@PANI can show the peak of PANI, and after low-temperature carbonization processing, the characteristic peak of PANI all weakens even
It disappears, XRD characterization shell is carbon material, this shows after low-temperature treatment, and PANI forms the nanometer rich in nitrogen after low-temperature treatment
Carbon shell (NCS), so as to form NCNT@NCS and NG-NCNT@NCS nano-carbon material.
Embodiment 3:
Embodiment 1 is obtained into one-dimensional rich nitrogen carbon nanomaterial (NCNT@PANI) and business sulphur mixes (mass ratio 35:65),
It seals in reaction kettle under argon gas protective condition, 155 DEG C of 12 hours of diffusion reaction by molten sulfur obtain positive electrode active materials
(NCNT@NCS@S)。
NCNT@NCS@S, carbon black (conductive agent) and binder (PVDF) are uniformly mixed by the mass ratio of 8:1:1 again, preparation
Anode sizing agent is uniformly coated on aluminium foil by anode sizing agent, the drying 24 hours of 50 DEG C of vacuum, is punched into the piece that diameter is 15mm and is made
For anode, lithium metal adds 1%LiNO as cathode3LiTFSI DOL/DME (volume ratio 1:1) solution as electrolysis
Liquid assembles button cell with 2025 type battery cases, the positive electrode pole piece of the compound of NCNT@S is prepared for same method.
Evaluate the performance of positive electrode.
From figure 3, it can be seen that for positive electrode, the low-temperature carbonization processing nitrogen-doped carbon material performance under 0.05C multiplying power
Higher battery reversible specific capacity and better circulating battery stability out.
Embodiment 4:
Embodiment 1 is obtained one-dimensional rich in nitrogen-doped carbon nano material (NCNT@PANI) and business sulphur mixing (mass ratio
35:65), it seals in reaction kettle under argon gas protective condition, 155 DEG C of 12 hours of diffusion reaction by molten sulfur, then at 180 DEG C
Lower low-temperature treatment carbonization, obtains positive electrode active materials (NCNT@NCS@S).
NCNT@NCS@S, carbon black (conductive agent) and binder (PVDF) are uniformly mixed by the mass ratio of 8:1:1, preparation is just
Anode sizing agent is uniformly coated on aluminium foil by pole slurry, the drying 24 hours of 50 DEG C of vacuum, is punched into the piece conduct that diameter is 15mm
Anode, lithium metal add 1%LiNO as cathode3LiTFSI DOL/DME (volume ratio 1:1) solution as electrolyte,
Button cell is assembled with 2025 type battery cases, the positive electrode pole piece of the compound of NCNT@S is prepared for same method.It comments
The performance of valence positive electrode.
From fig. 4, it can be seen that low-temperature carbonization processing nitrogen-doped carbon material is shown under 0.5C multiplying power for positive electrode
Utilization rate, battery specific capacity and the better circulating battery stability of higher active material.
Embodiment 5:
It weighs the obtained NCNT@PANI material of embodiment 1 to mix (mass ratio 35:65) with business sulphur, seals argon in reaction kettle
Under the conditions of gas shielded, low-temperature treatment is carbonized at 180 DEG C, obtains positive electrode active materials (NCNT@NCS@S).
NCNT@NCS@S, carbon black (conductive agent) and binder (PVDF) are uniformly mixed by the mass ratio of 8:1:1, preparation anode
Anode sizing agent is uniformly coated on aluminium foil by slurry, the drying 24 hours of 50 DEG C of vacuum, is punched into the piece that diameter is 15mm and is used as just
Pole, lithium metal add 1%LiNO as cathode3LiTFSI DOL/DME (volume ratio 1:1) solution as electrolyte, use
2025 type battery cases assemble button cell, and the positive electrode battery of the compound of NCNT@NCS@S is prepared for same method.
Evaluate the performance of positive electrode.
From fig. 5, it can be seen that not carrying out the anode of the cladding of carbon shell material at low range (0.2C) for positive electrode
The ratio of material capacity decaying is very fast, and low-temperature carbonization processing nitrogen-doped carbon material shows higher battery specific capacity and preferably electricity
Pond cyclical stability.
Embodiment 6:
The obtained NG-NCNT@PANI material of embodiment 2 and business sulphur (mass ratio 35:65) are weighed, argon gas in reaction kettle is sealed
Under protective condition, 155 DEG C of 12 hours of diffusion reaction by molten sulfur, then low-temperature treatment is carbonized at 180 DEG C, obtains anode
Active material (NG-NCNT@NCS@S).
NG-NCNT@NCS@S, carbon black (conductive agent) and binder (PVDF) are uniformly mixed by the mass ratio of 8:1:1, preparation
Anode sizing agent is uniformly coated on aluminium foil by anode sizing agent, the drying 24 hours of 50 DEG C of vacuum, is punched into the piece that diameter is 15mm and is made
For anode, lithium metal adds 1%LiNO as cathode3LiTFSI DOL/DME (volume ratio 1:1) solution as electrolysis
Liquid assembles button cell with 2025 type battery cases, the positive electrode of the compound of NCNT@NCS@S is prepared for same method
Battery.Evaluate the performance of positive electrode.
From fig. 6, it can be seen that low-temperature carbonization processing nitrogen-doped carbon material exists at low range (0.4C) for positive electrode
The utilization rate of higher active material, bigger battery specific capacity and better battery are shown after the introducing of nitrogen-doped graphene
Cyclical stability.
Embodiment 7:
The obtained NG-NCNT@PANI material of Example 2 and business sulphur (mass ratio 35:65) are added in sealing reaction kettle, and
Under the protection of argon gas, low-temperature treatment is carbonized at 180 DEG C, obtains positive electrode active materials (NG-NCNT@NCS@S).
NG-NCNT@NCS@S, carbon black (conductive agent) and binder (PVDF) are uniformly mixed by the mass ratio of 8:1:1, preparation
Anode sizing agent is uniformly coated on aluminium foil by anode sizing agent, the drying 24 hours of 50 DEG C of vacuum, is punched into the piece that diameter is 15mm and is made
For anode, lithium metal adds 1%LiNO as cathode3LiTFSI DOL/DME (volume ratio 1:1) solution as electrolysis
Liquid assembles button cell with 2025 type battery cases, the positive electrode of the compound of NCNT@NCS@S is prepared for same method
Battery.Evaluate the performance of positive electrode.
From figure 7 it can be seen that low-temperature carbonization processing nitrogen-doped carbon material is introducing under different multiplying for positive electrode
The material of the three-dimensional structure formed after nitrogen-doped graphene, electric conductivity are remarkably reinforced, and show the utilization of higher active material
Rate, bigger battery specific capacity and better circulating battery stability.
Embodiment 8
The obtained NG-NCNT@PANI material of embodiment 2 and business sulphur (mass ratio 35:65) are weighed, argon gas in reaction kettle is sealed
Under protective condition, first low-temperature treatment is carbonized at 500 DEG C, then 155 DEG C are obtained just by 12 hours of diffusion reaction of molten sulfur
Pole active material (NG-NCNT@NCS@S-500).
NG-NCNT@NCS@S-500, carbon black (conductive agent) and binder (PVDF) are uniformly mixed by the mass ratio of 8:1:1,
Anode sizing agent is prepared, anode sizing agent is uniformly coated on aluminium foil, the drying 24 hours of 50 DEG C of vacuum, being punched into diameter is 15mm's
Piece adds 1%LiNO as cathode as anode, lithium metal3LiTFSI DOL/DME (volume ratio 1:1) solution conduct
Electrolyte assembles button cell with 2025 type battery cases, the anode of the compound of NCNT@NCS@S is prepared for same method
Material cell.Evaluate the performance of positive electrode.
From figure 8, it is seen that, with the increase of cycle-index, active material is lost relatively more, capacity for positive electrode
Decaying shuttle effect it is obvious, the invertibity of circulation is poor, this shows in 500 DEG C of carbonizations, the chemical property of battery
Stability is not good enough.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with this
The personage of item technology cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all
Equivalent change or modification made by Spirit Essence according to the present invention, should be covered by the protection scope of the present invention.
Claims (14)
1. a kind of nano-core-shell structure carbonaceous carrier of richness nitrogen carbon shell cladding, it is characterised in that including carbonaceous kernel and cladding
In the rich nitrogen carbon shell on carbonaceous kernel, the material of the carbonaceous kernel includes in graphene, carbon nanotube, carbon fiber and porous carbon
Any one or two or more combinations, the molar ratio of C element and N element is 150:1~7:1, institute in the richness nitrogen carbon shell
The content for stating N element in carbonaceous carrier is 0.2at%~0.7at%, and the carbonaceous carrier has the porous structure being formed in situ,
The aperture of contained hole is 4nm ~ 30nm, and specific surface area is 80 ~ 500m2 g-1。
2. the nano-core-shell structure carbonaceous carrier of richness nitrogen carbon shell cladding according to claim 1, it is characterised in that: the carbon
The molar ratio of C element and N element is 140:1~6:1 in matter kernel.
3. the nano-core-shell structure carbonaceous carrier of richness nitrogen carbon shell cladding according to claim 1, it is characterised in that: the carbon
The diameter of matter kernel is 10nm~25nm, the richness nitrogen carbon shell with a thickness of 40nm~65nm.
4. the nano-core-shell structure carbonaceous carrier of richness nitrogen carbon shell cladding according to claim 1, it is characterised in that: the carbon
The material of matter kernel is selected from nitrogen-doped carbon material, and the nitrogen-doped carbon material is selected from nitrogen-doped carbon nanometer pipe and/or N doping stone
Black alkene.
5. the preparation method of the nano-core-shell structure carbonaceous carrier of the cladding of richness nitrogen carbon shell described in any one of claim 1-4, feature
Be include:
At least one carbon material is coated with polymer with nitrogen, forms the presoma with core-shell structure, the polymer with nitrogen packet
Polyaniline, polypyrrole, polyacrylonitrile, poly-dopamine, any one or two or more combinations in polyacrylamide are included, it is described
Carbon material includes any one or two or more combinations in graphene, carbon nanotube, carbon fiber and porous carbon；
Carbonization treatment is carried out to the presoma under the conditions of 100 DEG C~500 DEG C of temperature, forms the rich nitrogen carbon shell cladding
Nano-core-shell structure carbonaceous carrier.
6. preparation method according to claim 5, it is characterised in that: the carbon material is selected from nitrogen-doped carbon material, and the nitrogen is mixed
Miscellaneous carbon material is selected from nitrogen-doped carbon nanometer pipe and/or nitrogen-doped graphene.
7. a kind of sulphur carbon composite, characterized by comprising: richness nitrogen carbon shell cladding of any of claims 1-4
Nano-core-shell structure carbonaceous carrier, and, the sulphur being carried on the carbonaceous carrier；Wherein, the sulphur carbon composite includes
50 ~ 90wt% sulphur.
8. the production method of sulphur carbon composite as claimed in claim 7, characterized by comprising:
At least one carbon material is coated with polymer with nitrogen, forms the presoma with core-shell structure, the polymer with nitrogen packet
Polyaniline, polypyrrole, polyacrylonitrile, poly-dopamine, any one or two or more combinations in polyacrylamide are included, it is described
Carbon material includes any one or two or more combinations in graphene, carbon nanotube, carbon fiber and porous carbon；
After evenly mixing by the presoma and sulphur, it is successively carried out at molten sulfur diffusion reaction and carbonization in protective atmosphere
Reason, form the sulphur carbon composite, the reaction temperature of the molten sulfur diffusion reaction is 150 DEG C~300 DEG C, the time be 12h ~
For 24 hours, the carbonization treatment temperature is 100 DEG C~500 DEG C.
9. production method according to claim 8, it is characterised in that: the carbon material is selected from nitrogen-doped carbon material, described
Nitrogen-doped carbon material includes nitrogen-doped carbon nanometer pipe and/or nitrogen-doped graphene.
10. a kind of electrode material, it is characterised in that the nanometer comprising rich nitrogen carbon shell cladding of any of claims 1-4
Core-shell structure carbonaceous carrier and/or sulphur carbon composite as claimed in claim 7.
11. a kind of cell positive material, it is characterised in that comprising sulphur carbon composite as claimed in claim 7, conductive agent and glue
Tie agent.
12. a kind of chemical energy storage device, it is characterised in that include rich nitrogen carbon shell cladding of any of claims 1-4
Nano-core-shell structure carbonaceous carrier, sulphur carbon composite as claimed in claim 7, electrode material described in any one of claim 10 or power
Benefit require 11 described in cell positive material.
13. chemical energy storage device as claimed in claim 12, it is characterised in that: the chemical energy storage device is lithium battery.
14. chemical energy storage device as claimed in claim 13, it is characterised in that: the lithium battery is lithium-sulfur cell.
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| CN107195889B (en) * | 2017-06-26 | 2019-08-20 | 大连理工大学 | A kind of lithium sulfur battery anode material of boron-rich eggshell type, preparation method and applications |
| CN109248712B (en) * | 2017-07-14 | 2021-07-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Metal monoatomic doped nano carbon material catalytic carrier and preparation method and application thereof |
| CN107863509A (en) * | 2017-10-23 | 2018-03-30 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of polymer overmold sulphur carbon composite anode material |
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| CN108987119A (en) * | 2018-07-02 | 2018-12-11 | 桂林电子科技大学 | A kind of poly-dopamine/carbon nanotube@cobalt-nickel oxide composite material and preparation method and application |
| CN108962622B (en) * | 2018-07-16 | 2019-11-08 | 晋江瑞碧科技有限公司 | A kind of preparation method of Carbon anode electrode plate |
| CN109378485B (en) * | 2018-11-03 | 2022-07-12 | 东华大学 | Nanowire-based nonmetal pyridine nitrogen-doped carbon composite material and preparation method and application thereof |
| CN110112407B (en) * | 2019-06-14 | 2022-04-15 | 南昌工程学院 | Sulfur electrode material based on solid-solid reaction mechanism, lithium battery thereof and preparation methods of sulfur electrode material and lithium battery |
| CN110828810B (en) * | 2019-11-26 | 2022-09-16 | 桂林电子科技大学 | Iron-doped porous carbon-sulfur material based on polypyrrole and preparation method and application thereof |
| CN111933951B (en) * | 2020-08-25 | 2021-10-15 | 中南大学 | Lithium metal active precursor material and preparation and application thereof |
| CN115051107B (en) * | 2022-06-02 | 2023-08-22 | 哈尔滨工业大学 | Composite diaphragm modified by core-shell nano-tube type structural material and preparation method and application thereof |
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