CN110127663A - Nitrogen-doped carbon nanometer sheet and preparation method thereof, lithium ion cell electrode, lithium ion battery and electric device - Google Patents
Nitrogen-doped carbon nanometer sheet and preparation method thereof, lithium ion cell electrode, lithium ion battery and electric device Download PDFInfo
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- CN110127663A CN110127663A CN201910526593.8A CN201910526593A CN110127663A CN 110127663 A CN110127663 A CN 110127663A CN 201910526593 A CN201910526593 A CN 201910526593A CN 110127663 A CN110127663 A CN 110127663A
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The present invention provides a kind of nitrogen-doped carbon nanometer sheet and preparation method thereof, lithium ion cell electrode, lithium ion battery and electric devices, are related to the technical field of lithium ion battery material.The preparation method of nitrogen-doped carbon nanometer sheet provided by the invention, is nitrogen source by carbon source, melamine of asphalt, and using fused salt as reaction media, and calcining obtains nitrogen-doped carbon nanometer sheet；Wherein, asphalt is as carbon source, it can be achieved that its high value utilizes, melamine carries out N doping as nitrogen source, may make that there are a large amount of defect vacancy and dangling bonds around nitrogen, effectively enhance the amorphous degree of nitrogen-doped carbon nanometer sheet, wider interlamellar spacing is formed, a large amount of active site is provided；Fused salt is then that asphalt and melamine provide the liquid environment of stable uniform in calcining, to be conducive to the control of nitrogen-doped carbon nanometer sheet pattern.The present invention also provides nitrogen-doped carbon nanometer sheets, are made using above-mentioned preparation method, which is flake, morphology controllable.
Description
Technical field
The present invention relates to lithium ion battery material technical fields, more particularly, to a kind of nitrogen-doped carbon nanometer sheet and its preparation
Method, lithium ion cell electrode, lithium ion battery and electric device.
Background technique
With economic rapid development, conventional fossil fuel is rapidly depleted, people also further need with high-performance,
Inexpensive, environmentally protective energy storage device and operating technology.Lithium ion battery because energy density is high, have extended cycle life due to become one
One of very promising energy storage device of kind, causes the extensive concern of academia and industrial circle.However, commercial Li-ion is electric at present
Pond graphite cathode theoretical specific capacity is only 372mAhg-1, lower specific capacity limits it and is used for high power and extensive storage
It can, it is difficult to meet the needs of growing.To improve above situation, people start a kind of high performance novel carbon materials of exploratory development
Material, different types of carbonaceous material, including Nano carbon balls, carbon nano-fiber, graphene and their composite material etc. all by into
Research is gone.Wherein, the hot spot direction that Heteroatom doping has become research is carried out for carbon material.Existing preparation is used at present
Method is obtained to adulterate carbon material, and appearance structure is not easy to control, and chemical property is not good enough when using as electrode material, also
To further be promoted.
Asphalt is the byproduct in crude oil processing, have the characteristics that it is cheap and easy to get, be usually applied to traffic fortune
The fields such as defeated, construction industry, hydraulic engineering, but whole utilization value is lower.Therefore how according to the characteristic of asphalt itself by its
Realize that high value added utilization is the project for being worth research applied to energy storage field.
In view of this, the present invention is specifically proposed at least one of to solve the above technical problems.
Summary of the invention
The first purpose of this invention is to provide the preparation method of nitrogen-doped carbon nanometer sheet, using asphalt as carbon
Nitrogen-doped carbon nanometer sheet is prepared as nitrogen source, and using fused salt as reaction media in source, melamine, and the preparation method is real
The high value added utilization of asphalt, and obtained carbon nanosheet morphology controllable are showed, and with good performance, have made for it
It provides the foundation for electrode material.
Second object of the present invention is to provide a kind of nitrogen-doped carbon nanometer sheet, is made using above-mentioned preparation method.
Third object of the present invention is to provide a kind of lithium ion cell electrode, using above-mentioned nitrogen-doped carbon nanometer sheet system
?.
Fourth object of the present invention is to provide a kind of lithium ion battery, includes above-mentioned lithium ion cell electrode.
Of the invention the 5th is designed to provide a kind of electric device, includes above-mentioned lithium ion battery.
The preparation method of nitrogen-doped carbon nanometer sheet provided by the invention, comprising the following steps:
The mixture of asphalt, melamine and fused salt is calcined in protective atmosphere, obtains nitrogen-doped carbon nanometer
Piece.
Further, on above-mentioned technical proposal basis of the present invention, the matter of the asphalt, melamine and fused salt
Amount is than being 1:(0.5-4): (10-50), preferably 1:(0.5-3): (12-45), further preferably 1:(0.5-2): (15-
40)。
Further, on above-mentioned technical proposal basis of the present invention, the asphalt includes following mass fraction
Component: saturation divides 5-9%, and fragrance divides 23-27%, colloid 44-48% and asphalitine 16-20%；
Preferably, the Molten Binary Salts that the fused salt is 500-650 DEG C of fusing point；
Preferably, the Molten Binary Salts are potassium chloride-calcium chloride, sodium chloride-potassium chloride, magnesium chloride-calcium chloride or chlorination
In calcium-manganese chloride any one or at least two combination；
Preferably, the Molten Binary Salts are potassium chloride-calcium chloride, and the mass ratio of potassium chloride and calcium chloride is (1-4): 1.
Further, on above-mentioned technical proposal basis of the present invention, the protective atmosphere is nitrogen；
Preferably, the calcination temperature is 600-1000 DEG C, calcination time 1-3h；
Preferably, the heating rate when calcining is 0.5-10 DEG C/min.
Further, on above-mentioned technical proposal of the present invention basis, the asphalt, melamine and fused salt it is mixed
Close the preparation method of object, comprising the following steps:
It is ground again after asphalt, melamine and fused salt are mixed, obtains asphalt, melamine and fused salt
Mixture；
Preferably, the revolving speed of the grinding is 600-1000r/min, and the time of grinding is 10-40min；
Preferably, described to be ground to ball milling, ball powder mass ratio when ball milling is (4-10): 1.
Further, it on above-mentioned technical proposal basis of the present invention, by calcined product, is cleaned and is dried,
Obtain nitrogen-doped carbon nanometer sheet；
Preferably, it is cleaned when cleaning using acid solution；
Preferably, the mass fraction of the acid solution is 5-20%；
Preferably, the acid solution includes any one in hydrochloric acid solution, sulfuric acid solution or nitric acid solution or at least two
The combination of kind；
Preferably, drying temperature is 60-120 DEG C, drying time 8-24h；
Preferably, the nitrogen-doped carbon nanometer sheet with a thickness of 4-15nm.
The present invention also provides a kind of nitrogen-doped carbon nanometer sheets, using the preparation method system of above-mentioned nitrogen-doped carbon nanometer sheet
?；
Preferably, the nitrogen-doped carbon nanometer sheet with a thickness of 4-15nm.
The present invention also provides a kind of lithium ion cell electrodes, are made using above-mentioned nitrogen-doped carbon nanometer sheet.
The present invention also provides a kind of lithium ion batteries, include above-mentioned lithium ion cell electrode.
The present invention also provides a kind of electric devices, include above-mentioned lithium ion battery.
Compared with prior art, nitrogen-doped carbon nanometer sheet provided by the invention and preparation method thereof, lithium ion cell electrode,
Lithium ion battery and electric device have the advantages that
(1) the present invention provides a kind of preparation method of nitrogen-doped carbon nanometer sheet, the preparation method using asphalt as
Nitrogen-doped carbon nanometer sheet is prepared as nitrogen source, and using fused salt as reaction media in carbon source, melamine；Wherein, with petroleum
As carbon source, the high value for realizing asphalt is utilized, N doping is carried out using melamine as nitrogen source, then makes nitrogen pitch
Surrounding effectively enhances its amorphous degree, forms wider interlamellar spacing there are a large amount of defect vacancy and dangling bonds, provides big
The active site of amount, fused salt are then that asphalt and melamine provide the liquid environment of stable uniform in calcination process, from
And be conducive to the control of nitrogen-doped carbon nanometer sheet appearance structure；
In addition, the preparation method simple process, stabilization, friendly to environment green, and preparation-obtained nitrogen-doped carbon is received
Rice piece nitrogen content is high, and for flake, pattern size is controllable, provides foundation for industrialized production.
(2) the present invention provides a kind of nitrogen-doped carbon nanometer sheets, using the preparation method system of above-mentioned nitrogen-doped carbon nanometer sheet
, the nitrogen-doped carbon nanometer sheet lamella is very thin and fold rises and falls, and edge presentation is curly, and pattern size is controllable, and nitrogen content is high, nitrogen
It is entrained in carbon nanosheet, it is possible to provide richer surface drive charge stores behavior, provides and answers as electrode material for it
With basis.
(3) the present invention provides a kind of lithium ion cell electrodes, are made using above-mentioned nitrogen-doped carbon nanometer sheet, in view of above-mentioned
Advantage possessed by nitrogen-doped carbon nanometer sheet, so that using its lithium ion cell electrode with good cyclical stability and again
Rate performance.
(4) the present invention provides a kind of lithium ion batteries, include above-mentioned lithium ion cell electrode.In view of above-mentioned lithium-ion electric
Advantage possessed by the electrode of pond, so that the lithium ion battery has good chemical property.
(5) the present invention provides a kind of electric devices, include above-mentioned lithium ion battery.Had in view of above-mentioned lithium ion battery
Some advantages, so that the electric device comprising above-mentioned lithium ion battery can also obtain identical effect.
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 preparation flow schematic diagram of nitrogen-doped carbon nanometer sheet provided in an embodiment of the present invention；
Fig. 2 is the XRD diagram for the nitrogen-doped carbon nanometer sheet that the embodiment of the present invention 1, embodiment 2 and embodiment 3 provide；
The Raman spectrogram for the nitrogen-doped carbon nanometer sheet that Fig. 3 is 1-3 of the embodiment of the present invention and comparative example 1 provides；
Fig. 4 is the XPS map for the nitrogen-doped carbon nanometer sheet that 1-3 of the embodiment of the present invention is provided, wherein a is embodiment 1-3
The full spectrogram of the nitrogen-doped carbon nanometer sheet of offer, b are the nitrogen-doped carbon nanometer sheet N 1s high-resolution map that embodiment 1 provides, c
For the nitrogen-doped carbon nanometer sheet N 1s high-resolution map that embodiment 2 provides, d is the nitrogen-doped carbon nanometer sheet N that embodiment 3 provides
1s high-resolution map；
Fig. 5 is the electron microscope that the embodiment of the present invention 1 and comparative example 3 provide, wherein a is the N doping that embodiment 1 provides
The SEM of carbon nanosheet schemes, and b is the TEM figure for the nitrogen-doped carbon nanometer sheet that embodiment 1 provides, and c is the carbon nanometer that comparative example 3 provides
The SEM of piece schemes, and d is the TEM figure for the carbon nanosheet that comparative example 3 provides；
Fig. 6 is suction-desorption curve of the nitrogen-doped carbon nanometer sheet that provides of 1-3 of the embodiment of the present invention to nitrogen；
Fig. 7 is the DFT pore analysis figure for the nitrogen-doped carbon nanometer sheet that 1-3 of the embodiment of the present invention is provided；
Fig. 8 is the cycle performance figure of the corresponding lithium ion battery of 15 lithium ion cell electrode of the embodiment of the present invention, wherein a
For in 0.1mV s-1First three circle CV curve graph under speed is swept, b is in 0.1mV s-1Sweep first three circle voltage capacity figure under speed；
Fig. 9 is the impedance plot of the corresponding lithium ion battery of 15-17 of embodiment of the present invention lithium ion cell electrode；
Figure 10 is the corresponding lithium ion battery of 15-17 of embodiment of the present invention lithium ion cell electrode under different current densities
High rate performance figure；
Figure 11 is the corresponding lithium ion battery of 15-17 of embodiment of the present invention lithium ion cell electrode in 1A g-1Under constant current
Charge-discharge performance figure.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with embodiment, it is clear that described reality
Applying example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
According to an aspect of the present invention, the preparation method of the nitrogen-doped carbon nanometer sheet provided, comprising the following steps:
The mixture of asphalt, melamine and fused salt is calcined in protective atmosphere, obtains nitrogen-doped carbon nanometer
Piece.
The preparation method of nitrogen-doped carbon nanometer sheet provided by the invention, the preparation method is using asphalt as carbon source, three
Nitrogen-doped carbon nanometer sheet is prepared as nitrogen source, and with fused salt reaction media in poly cyanamid.
Structure is complicated for asphalt, and molecular weight is big, but its carboloy residue is very high, can be used as carbon source in the present invention, realizes
The high value of asphalt utilizes.
Melamine is also known as melamine, melamine, is a kind of triazines nitrogen heterocyclic ring organic compound, has a large amount of
Nitrogen, use in the present invention as nitrogen source, can be in situ to bring nitrogen into carbon skeleton by being directly pyrolyzed
In.
N doping is carried out to asphalt using melamine, then makes around nitrogen that there are a large amount of defect vacancy and hanging
Key effectively enhances its amorphous degree, forms wider interlamellar spacing, provides a large amount of active site.
Fused salt refers to the fusible salts substances for forming molten mass, usually metal cation under certain temperature, pressure
With salts substances composed by metalloid anion, such as halide, nitrate, the sulfate of alkali or alkaline earth metal etc..
The present invention is using asphalt as carbon source, and asphalt will form after high-temperature calcination (carbonization) and differ in size
Block structure is unfavorable for N doping.And fused salt is used as reaction media, it is asphalt, melamine in calcination process
Uniform and stable uniform liquid environment is provided, calcined product can be made to form a type graphene two-dimensional slice stratiform in liquid environment
Unordered close-packed arrays are presented in structure, to be conducive to the control of nitrogen-doped carbon nanometer sheet pattern.Meanwhile fused salt and melamine
Between also function to synergistic effect, melamine more efficiently nitrating during pyrolysis can be made.
In the present invention, the specific type of fused salt is not especially limited, and can be a kind of single fused salt, or a variety of
The mixture of fused salt, but need to ensure the fusing point (eutectic point) of fused salt and the basic phase of carburizing temperature of asphalt, melamine
Together, or slightly above carburizing temperature.For example, when the carburizing temperature of asphalt and melamine is in 400-550 DEG C, fused salt
The temperature of fusing point (eutectic point) be typically in 500-650 DEG C.
In addition, the preparation method simple process, stabilization, friendly to environment green, and preparation-obtained nitrogen-doped carbon is received
Rice piece nitrogen content is high, and for flake, pattern size is controllable, provides foundation for industrialized production.
As a kind of optional embodiment of the invention, the mass ratio of asphalt, melamine and fused salt is 1:(0.5-
4): (10-50), preferably 1:(0.5-3): (12-45), further preferably 1:(0.5-2): (15-40).
The mass ratio of asphalt, melamine and fused salt three directly affects the doping and shape of final products nitrogen
Looks.The mass ratio of typical but non-limiting asphalt, melamine and fused salt is 1:0.5:10,1:0.5:12,1:0.5:
15、1:0.5:20、1:0.5:30、1:0.5:40、1:0.5: 50、1:1:10、1:1:12、1:1:15、1:1:20、1:1:30、1:
1:40、1:1:50、 1:2:10、1:2:12、1:2:15、1:2:20、1:2:30、1:2:40、1:2:50、1: 3:10、1:3:12、
1:3:15、1:3:20、1:3:30、1:3:40、1:3:50、1:4: 10、1:4:12、1:4:15、1:4:20、1:4:30、1:4:40
Or 1:4:50.
As a kind of optional embodiment of the invention, asphalt includes the component of following mass fraction: saturation divides 5-
9%, fragrance divides 23-27%, colloid 44-48% and asphalitine 16-20%；The mass fraction of typical but non-limiting saturation point
It is 5%, 6%, 7%, 8% or 9%, the mass fraction of typical but non-limiting fragrance point is 23%, 24%, 25%, 26%
Or 27%, the mass fraction of typical but non-limiting colloid is 44%, 45%, 46%, 47% or 48%, typical but unrestricted
Property asphalitine mass fraction be 16%, 17%, 18%, 19% or 20%.
Since the ingredient of asphalt is complex, by the restriction to performances such as asphalt, so that it is more suitable for making
For carbon source use.
As a kind of optional embodiment of the invention, fused salt includes the Molten Binary Salts that fusing point is 500-650 DEG C；
Preferably, Molten Binary Salts are potassium chloride-calcium chloride, sodium chloride-potassium chloride, magnesium chloride-calcium chloride or calcium chloride-chlorine
Change manganese in any one or at least two combination.
It should be noted that "-" refers to the meaning of "and", i.e. potassium chloride-calcium chloride is that potassium chloride and calcium chloride mix
Molten Binary Salts, sodium chloride-potassium chloride are the Molten Binary Salts that sodium chloride and potassium chloride mix, magnesium chloride-calcium chloride be magnesium chloride and
The Molten Binary Salts of calcium chloride mixing, calcium chloride-manganese chloride are the Molten Binary Salts that calcium chloride and manganese chloride mix.
Above-mentioned Molten Binary Salts, two kinds of salts substances its eutectic points in fused salt can achieve 500-650 DEG C or so, just with
Asphalt in calcination process, melamine carburizing temperature is substantially consistent or slightly above carburizing temperature.For Molten Binary Salts
In, two kinds of salts substances can be any mass mixing, be not especially limited to the mass ratio of the two.
As a kind of optional embodiment of the invention, Molten Binary Salts are potassium chloride-calcium chloride, potassium chloride and calcium chloride
Mass ratio is (1-4): 1.The mass ratio of typical but non-limiting potassium chloride and calcium chloride is 1:1,2:1,3:1 or 4:1.
By the restriction of type and dosage to salts substances specific in Molten Binary Salts, so that its institute in calcination process
The molten mass of formation can provide more stable uniform liquid phase environment for asphalt and melamine, be more advantageous to nitrogen-doped carbon and receive
The control of rice piece pattern.
As a kind of optional embodiment of the invention, protective atmosphere is nitrogen.It employs nitrogen as protective atmosphere,
The air in calcination process can effectively be completely cut off, reduce air to the adverse effect in calcination process.
As a kind of optional embodiment of the invention, calcination temperature is 600-1000 DEG C, calcination time 1-3h；It is typical
But the temperature of unrestricted calcining be 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C or
1000℃；The time of typical but non-limiting calcining is 1.0h, 1.5h, 2.0h, 2.5h or 3.0h.
It should be noted that if calcination temperature is too low, fused salt particle does not melt also, plays the role of hard template, will affect material
Expect pattern, carbon material surface is caused to form irregular pit-hole, lamellar spacing increases；If calcination temperature is excessively high, it will lead to carbon materials
Tablet layer is thinner and sheet is more broken, and pattern is unstable and is difficult to maintain.Therefore calcination temperature and calcination time should be controlled suitable
In suitable range.
As a kind of optional embodiment of the invention, heating rate when calcining is 0.5-10 DEG C/min.It is typical but non-
Restrictive heating rate be 0.5 DEG C/min, 1 DEG C/min, 2 DEG C/min, 3 DEG C/min, 4 DEG C/min, 5 DEG C/min, 6 DEG C/min,
7 DEG C/min, 8 DEG C/min, 9 DEG C/min or 10 DEG C/min.
By the specific restriction to above-mentioned calcination parameter, more filled so that being acted between asphalt, melamine and fused salt
Point, the performance of obtained nitrogen-doped carbon nanometer sheet is more excellent.
As a kind of optional embodiment of the invention, the preparation side of the mixture of asphalt, melamine and fused salt
Method, comprising the following steps:
It is ground again after asphalt, melamine and fused salt are mixed, obtains asphalt, melamine and fused salt
Mixture；
As a kind of optional embodiment of the invention, the revolving speed of grinding is 600-1000r/min, and the time of grinding is
10-40min；The revolving speed of typical but non-limiting grinding be 600r/min, 650r/min, 700r/min, 750r/min,
The time of 800r/min, 850r/min, 900r/min, 950r/min or 1000r/min, typical but non-limiting grinding is
10min, 15min, 20min, 25min, 30min, 35min or 40min.
As a kind of optional embodiment of the invention, it is ground to ball milling, ball powder mass ratio when ball milling is (4-10): 1.
Typical but non-limiting ball powder mass ratio is 4:1,5:1,6:1,7:1,8:1,9:1 or 10:1.
By the restriction of the preparation method of the mixture to asphalt, melamine and fused salt, so that between three
Mixing more uniformly, is conducive to the progress of subsequent calcination process.
As a kind of optional embodiment of the invention, by calcined product, is cleaned and dried, obtain N doping
Carbon nanosheet.
Since asphalt comparison of ingredients is complicated, although high-temperature calcination can remove impurity small-molecule substance, but can deposit
In some small organic molecules or the metal salt impurity of some complicated components, therefore needs to clean it, dry, ability
Ensure that obtained nitrogen-doped carbon nanometer sheet impurity content is lower.
As a kind of optional embodiment of the invention, cleaned using acid solution when cleaning；
Preferably, the mass fraction of acid solution is 5-20%；The typical but non-limiting mass fraction of acid solution be 5%,
8%, 10%, 12%, 14%, 15%, 16%, 18% or 20%.
Preferably, acid solution includes any one in hydrochloric acid solution, sulfuric acid solution or nitric acid solution or at least two
Combination；
By the restriction to cleaning solution type, mass fraction employed in cleaning process, so that after calcining in product
Impurity can effectively be removed.
It is dried again after cleaning.As a kind of optional embodiment of the invention, drying temperature is 60-120 DEG C,
Drying time is 8-24h.Typical but non-limiting drying temperature is 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90
DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C or 120 DEG C.
As a kind of optional embodiment of the invention, the preparation method of nitrogen-doped carbon nanometer sheet, comprising the following steps:
Ball milling is carried out after asphalt, melamine and fused salt are mixed, by asphalt, melamine and fused salt three
Mixture calcined in protective atmosphere, calcined product is cleaned, nitrogen-doped carbon nanometer sheet, process flow are obtained
Schematic diagram is as shown in Figure 1.
The preparation method of the nitrogen-doped carbon nanometer sheet provided through the invention can obtain the relatively thin N doping of lamellar spacing
Carbon nanosheet.As a kind of optional embodiment of the invention, nitrogen-doped carbon nanometer sheet with a thickness of 4-15nm.Typical but non-limit
The nitrogen-doped carbon nanometer sheet of property processed with a thickness of 4nm, 5nm, 6nm, 8nm, 10nm, 12nm, 14nm or 15nm.
According to the second aspect of the invention, a kind of nitrogen-doped carbon nanometer sheet is additionally provided, is received using above-mentioned nitrogen-doped carbon
The preparation method of rice piece is made.
Nitrogen-doped carbon nanometer sheet provided by the invention is made, the nitrogen using the preparation method of above-mentioned nitrogen-doped carbon nanometer sheet
Adulterating carbon nanosheet is flake, and pattern size is controllable, and nitrogen content is high, and N doping is in carbon nanosheet, it is possible to provide richer
Surface drive charge stores behavior, provides application foundation as electrode material for it.
According to the third aspect of the present invention, a kind of lithium ion cell electrode is additionally provided, is received using above-mentioned nitrogen-doped carbon
Rice piece is made.
Lithium ion cell electrode provided by the invention is made using above-mentioned nitrogen-doped carbon nanometer sheet, in view of above-mentioned nitrogen-doped carbon
Advantage possessed by nanometer sheet, so that the lithium ion cell electrode using it has good cyclical stability and high rate performance.
The conventional method of this field can be used in the preparation method of lithium ion cell electrode.As a kind of optional reality of the invention
Apply mode, the preparation method of lithium ion cell electrode the following steps are included:
After nitrogen-doped carbon nanometer sheet, binder and conductive agent are sufficiently mixed according to certain mass ratio, dispersing agent is added,
Obtain pasty slurry；
Pasty slurry is coated on collector, vacuum drying, slice obtains lithium ion cell electrode.
The preparation method simple process of the lithium ion cell electrode, operates conveniently.
As a kind of optional embodiment of the invention, binder includes Kynoar, polyvinyl alcohol, polytetrafluoroethylene (PTFE)
Or any one in butadiene-styrene rubber, preferably Kynoar；
Preferably, dispersing agent includes any one in N-Methyl pyrrolidone, N- dimethylformamide or N- diethylamide
Kind, preferably N-Methyl pyrrolidone；
Preferably, conductive agent includes any in acetylene black, carbon fiber, carbon nanotube, graphene or nitrogen-doped graphene
One or more, preferably acetylene black.
As a kind of optional embodiment of the invention, the mass ratio of nitrogen-doped carbon nanometer sheet, binder and conductive agent is
(2-10): (0.5-2): (0.5-2), preferably (5-9): (0.8-1.5): (0.8-1.5), further preferably 8:1:1.
As a kind of optional embodiment of the invention, collector is metal foil, preferably copper foil.
By the restriction to the specific preparation method of lithium ion cell electrode, there is obtained lithium ion cell electrode good
Good chemical property.
According to the fourth aspect of the present invention, a kind of lithium ion battery is provided, includes above-mentioned lithium ion cell electrode.
In view of advantage possessed by above-mentioned lithium ion cell electrode, so that the lithium ion battery has good electrochemistry
Can, for example, stable cycle performance and good high rate performance.
The assemble method of lithium ion battery assembles knob according to lithium ion cell electrode, diaphragm, metal lithium sheet, electrolyte
Detain battery.
According to the fifth aspect of the present invention, a kind of electric device is additionally provided, includes above-mentioned lithium ion battery.
In view of advantage possessed by above-mentioned lithium ion battery, in the electronic of the lithium ion battery using embodiment of the present invention
Device can also obtain identical effect.Electric device be use lithium ion battery as driving power come moving parts (for example,
Drill bit) electric device.
It should be noted that lithium ion battery provided by the invention is not limited to apply in electric device field, can also answer
For electronic device, electric vehicle or power storage system.Electronic device is that lithium ion battery is used to hold as the power supply of operation
The electronic device of the various functions (for example, performing music) of row.Electric vehicle is to run by lithium ion battery as driving power
Electric vehicle, and can be automobile (including the hybrid power that other driving sources are also equipped with other than lithium ion battery
Vehicle).Electric power storage system is to use lithium ion battery as the electric power storage system of electric power storage source.For example, in household power
In stocking system, it is stored in electric power in the lithium ion battery as electric power storage source, and consumption is stored in lithium as needed
Electric power in ion battery is to be able to use the various devices of such as domestic electronic appliances.
Combined with specific embodiments below and comparative example, the invention will be further described.
Embodiment 1
Present embodiments provide a kind of preparation method of nitrogen-doped carbon nanometer sheet, comprising the following steps:
(a) mixture (mass ratio 1:1:20) of asphalt, melamine and fused salt is provided；
By 0.5g asphalt, 0.5g melamine and 10g Molten Binary Salts (KCl-CaCl2, mass ratio 2:1) and it is ground in agate
It is premixed in alms bowl, then above-mentioned mixture is added in planetary ball mill and carries out ball milling, rotational speed of ball-mill 800r/min, Ball-milling Time
For 30min, ball powder mass ratio is 10:1, obtains the mixture of asphalt, melamine and fused salt after ball milling；
Wherein, asphalt is purchased from China Petrochemical Industry Company, and asphalt includes the component of following mass fraction: saturation point 5%,
Fragrance point 27%, colloid 48% and asphalitine 20%；
(b) mixture of asphalt, melamine and fused salt is placed in corundum boat and is calcined, under nitrogen atmosphere, with 5
DEG C/min is warming up to 800 DEG C, constant temperature 2h, then Temperature fall, obtains calcined product；
(c) after using hydrochloric acid solution (mass fraction 10%) to clean calcined product, it is subsequently placed in forced air drying
In 60 DEG C of dry 8h in baking oven, nitrogen-doped carbon nanometer sheet is obtained.
Embodiment 2
A kind of preparation method of nitrogen-doped carbon nanometer sheet is present embodiments provided, the dosage of melamine is in step (a)
0.25g, the mass ratio of asphalt, melamine and fused salt is 1 in the mixture of asphalt, melamine and fused salt:
0.5:20, remaining raw material, dosage and preparation method are same as Example 1.
Embodiment 3
A kind of preparation method of nitrogen-doped carbon nanometer sheet is present embodiments provided, the dosage of melamine is in step (a)
1.0g, the mass ratio of asphalt, melamine and fused salt is 1:2 in the mixture of asphalt, melamine and fused salt:
20, remaining raw material, dosage and preparation method are identical as embodiment 1.
Embodiment 4
A kind of preparation method of nitrogen-doped carbon nanometer sheet is present embodiments provided, the dosage of melamine is in step (a)
2.0g, the dosage of fused salt are 25g, asphalt, melamine and fused salt in the mixture of asphalt, melamine and fused salt
Mass ratio be 1:4:50, remaining raw material, dosage and preparation method are same as Example 1.
Embodiment 5
A kind of preparation method of nitrogen-doped carbon nanometer sheet is present embodiments provided, the dosage of melamine is in step (a)
1.5g, the dosage of fused salt are 6g, asphalt, melamine and fused salt in the mixture of asphalt, melamine and fused salt
Mass ratio be 1:3:12, remaining raw material, dosage and preparation method are same as Example 1.
Embodiment 6
A kind of preparation method of nitrogen-doped carbon nanometer sheet is present embodiments provided, the dosage of melamine is in step (a)
0.2g, the mass ratio of asphalt, melamine and fused salt is 1:4.5 in the mixture of asphalt, melamine and fused salt:
20, remaining raw material, dosage and preparation method are same as Example 1.
Embodiment 7
A kind of preparation method of nitrogen-doped carbon nanometer sheet is present embodiments provided, asphalt is purchased from middle stone in step (a)
Change company, asphalt include the component of following mass fraction: saturation point 9%, fragrance point 27%, colloid 44% and asphalitine
20%, remaining raw material, dosage and preparation method are same as Example 1.
Embodiment 8
Present embodiments provide a kind of preparation method of nitrogen-doped carbon nanometer sheet, Molten Binary Salts KCl-CaCl in step (a)2
Total amount it is constant (same as Example 1), KCl and CaCl2Mass ratio 4:1, remaining raw material, dosage and preparation method and implementation
Example 1 is identical.
Embodiment 9
A kind of preparation method of nitrogen-doped carbon nanometer sheet is present embodiments provided, Molten Binary Salts are NaCl- in step (a)
The total amount of KCl is constant (same as Example 1), NaCl and KCl mass ratio 1:1, remaining raw material, dosage and preparation method and reality
It is identical to apply example 1.
Embodiment 10
A kind of preparation method of nitrogen-doped carbon nanometer sheet is present embodiments provided, calcination temperature is 600 DEG C in step (b),
Remaining step and parameter are same as Example 1.
Embodiment 11
A kind of preparation method of nitrogen-doped carbon nanometer sheet is present embodiments provided, calcination temperature is 1000 DEG C in step (b),
Remaining step and parameter are same as Example 1.
Embodiment 12
A kind of preparation method of nitrogen-doped carbon nanometer sheet is present embodiments provided, calcination temperature is 580 DEG C in step (b),
Remaining step and parameter are same as Example 1.
Embodiment 13
A kind of preparation method of nitrogen-doped carbon nanometer sheet is present embodiments provided, calcination temperature is 1050 DEG C in step (b),
Remaining step and parameter are same as Example 1.
Embodiment 14
Present embodiments provide a kind of preparation method of nitrogen-doped carbon nanometer sheet, comprising the following steps:
(a) mixture (mass ratio 1:3:45) of asphalt, melamine and fused salt is provided；
By 0.5g asphalt, 1.5g melamine and 22.5g Molten Binary Salts (KCl-CaCl2, mass ratio 3:1) and in agate
It is premixed in mortar, then above-mentioned mixture is added in planetary ball mill and carries out ball milling, rotational speed of ball-mill 1000r/min, ball milling
Time is 10min, and ball powder mass ratio is 4:1, obtains the mixture of asphalt, melamine and fused salt after ball milling；
Wherein, asphalt is purchased from China Petrochemical Industry Company, and asphalt includes the component of following mass fraction: saturation point 9%,
Fragrance point 27%, colloid 48% and asphalitine 16%；
(b) mixture of asphalt, melamine and fused salt is placed in corundum boat and is calcined, under nitrogen atmosphere, with 8
DEG C/min is warming up to 900 DEG C, constant temperature 1.5h, then Temperature fall, obtains calcined product；
(c) after using nitric acid solution (mass fraction 20%) to clean calcined product, it is subsequently placed in forced air drying
In 70 DEG C of dry 10h in baking oven, nitrogen-doped carbon nanometer sheet is obtained.
Embodiment 15-28
Embodiment 15-28 is each provided with a kind of lithium ion cell electrode, and the N doping of embodiment 1-14 offer is respectively adopted
Carbon nanosheet is made, comprising the following steps:
(a) the nitrogen-doped carbon nanometer sheet that embodiment 15-28 is provided respectively with binder (Kynoar) and conductive agent
After (acetylene black) is sufficiently mixed according to the mass ratio of 8:1:1, it is added dispersing agent (N- methyl pyrrolidone), obtains pasty slurry；
(b) pasty slurry is coated in the copper foil current collector matte surface of surfacing, is placed in a vacuum drying oven 80 DEG C
Vacuum drying 12h, after cooling, slice obtains lithium ion cell electrode.
Comparative example 1
This comparative example provides a kind of preparation method of carbon material, is not added with melamine in step (a), remaining raw material,
Dosage and step are same as Example 1.
Comparative example 2
This comparative example provides a kind of preparation method of carbon material, is not added with fused salt in step (a), remaining raw material, dosage
And step is same as Example 1.
Comparative example 3
This comparative example provides a kind of preparation method of carbon material, is not added with melamine and fused salt in step (a), remaining
Raw material, dosage and step are same as Example 1.
Comparative example 4
This comparative example provides a kind of preparation method of carbon material, and asphalt is replaced with glucose in step (a),
Remaining raw material, dosage and step are same as Example 1.
Comparative example 5-8
Comparative example 5-8 is each provided with a kind of lithium ion cell electrode, and the carbon material system of comparative example 1-4 offer is respectively adopted
, the specific preparation method of lithium ion cell electrode is identical as embodiment 15-28.
For the technical effect for verifying the various embodiments described above and comparative example, ad hoc following experimental example.
Experimental example 1
By taking embodiment 1-3 as an example, the nitrogen-doped carbon nanometer sheet provided it carries out XRD test and Raman test, specifically such as
Shown in Fig. 2 and Fig. 3.
Figure it is seen that nearby there are two diffraction maximums at 26 ° and 44 ° in the corresponding XRD spectrum of embodiment 1-3, point
(002) crystal face and (100) crystal face of graphite are not corresponded to.This illustrates that nitrogen-doped carbon nanometer sheet is amorphous structure, also illustrates that nitrogen is mixed
The degree of graphitization of miscellaneous carbon nanosheet is low, and interplanar distance degree is big, is conducive to the insertion and abjection of lithium ion.
The defect level of nitrogen-doped carbon nanometer sheet in embodiment 1-3 is further analyzed using Raman map, specifically such as Fig. 3 institute
Show.From figure 3, it can be seen that the nitrogen-doped carbon nanometer sheet that embodiment 1-3 is provided is in 1380cm-1And 1600cm-1Place occurs
By sp3Hydbridized carbon atoms vibrate the peak D to be formed and by sp2Hydbridized carbon atoms vibrate the peak G to be formed, by its relative intensity ratio (ID/
IG) it can be seen that defect level present in nitrogen-doped carbon nanometer sheet；Relative intensity ratios are bigger, lacking in nitrogen-doped carbon nanometer sheet
Sunken degree is higher, and defect sites are conducive to store lithium ion.Comparative example 1, embodiment 1, the peak intensity of embodiment 2 and embodiment 3
Spending ratio is respectively 0.81,0.87,1.21,1.26 and 1.34.As can be seen that the amorphous degree of nitrogen-doped carbon nanometer sheet material
In comparison it all increased.This illustrates the addition of melamine so that nitrogen-atoms is incorporated into carbon skeleton, and generation is more
Defect vacancy, and then the more active sites of exposure, are conducive to the transport and storage of lithium ion, this is the same as the XRD result one in Fig. 2
It causes.
Experimental example 2
For element doping situation in further research material, nitrogen-doped carbon nanometer sheet is carried out by taking embodiment 1-3 as an example
X-ray electron spectroscopy analysis (XPS), it is specific as shown in Figure 4.
The full spectrogram of nitrogen-doped carbon nanometer sheet as shown in fig. 4 a, 284.6eV, 401.0eV and 532.0 positions eV in figure
Peak corresponds respectively to C 1s, N 1s and O 1s, this illustrates there is carbon, three kinds of nitrogen, oxygen elements in nitrogen-doped carbon nanometer sheet.And with
The additive amount of melamine increase, the peak intensity of nitrogen dramatically increases.The peak N 1s of nitrogen-doped carbon nanometer sheet in Fig. 4 b-d
Be divided into three main peaks, i.e. pyridine N (N-6,397.9eV), pyrroles N (N-5,400.1eV) and graphite N (NQ, 403.8eV), and
It can ask to obtain the percentage composition of different type nitrogen from integral area.The pyridine nitrogen and pyrroles's nitrogen content of embodiment 1 are much higher than real
Apply example 2 and embodiment 3.Especially pyrroles's nitrogen, high pyrroles's nitrogen content can lead to local electronic defect, to former from neighbouring lithium
The electronics of son has extra high affinity.Compared with comparative example 1, this can cause material surface active site to increase.
Experimental example 3
In order to study influence of the N doping to carbon nanosheet pattern, the nitrogen-doped carbon provided embodiment 1 and comparative example 3 is received
Rice piece and carbon nanosheet have carried out electron-microscope scanning, specific as shown in Figure 5.A and b in Fig. 5 are respectively that the nitrogen of the offer of embodiment 1 is mixed
The SEM figure and TEM of miscellaneous carbon nanosheet are schemed, and the c and d in Fig. 5 are respectively the SEM figure and TEM for the carbon nanosheet that comparative example 3 provides
Figure.As can be seen that the layer assembling structure for arrangement of being scattered, random fold stack and lamella is presented in nitrogen-doped carbon nanometer sheet from Fig. 5 a
Very thin, the presentation of lamella edge is curly, provides more sites for the storage of lithium ion；It can be seen from figure 5b that nitrogen
Doping carbon nanosheet is integrally in the sheet of folding, has class graphene-structured, lamella is very thin and a large amount of folds rise and fall.From Fig. 5 c
It can be seen that the carbon nanosheet for not carrying out N doping shows the block structure of rough surface and random arrangement, the size of particle
It is differed for 50-100 μm, and it is also seen that apparent block structure is presented in carbon nanosheet from 5d TEM figure.Comparison is it is found that nitrogen
Adulterating carbon nanosheet has better structure and morphology feature.
In order to probe into the cellular structure for generating nitrogen-doped carbon nanometer sheet, to nitrogen-doped carbon nanometer sheet by taking embodiment 1-3 as an example
Nitrogen suction-detachment assays are carried out, it is specific as shown in Figure 6.The result shows that nitrogen-doped carbon nanometer sheet is the absorption of IV type, and with trimerization
The specific surface area of the increase of cyanamide incorporation, nitrogen-doped carbon nanometer sheet is bigger.Facts proved that this porous surface can pass through original
Position pyrolysis nitrating is realized.The specific surface area about 126.0m for the nitrogen-doped carbon nanometer sheet that embodiment 1 provides2g-1, specific surface appropriate
Product can provide active site abundant and shorten Li+Transport channel.
Using the nitrogen desorption data of embodiment 1-3 nitrogen-doped carbon nanometer sheet, N doping has been calculated according to BJH method
The pore-size distribution of carbon nanosheet is as shown in Figure 7.The pore volume difference of the nitrogen-doped carbon nanometer sheet of embodiment 1-3 offer is provided
For 0.40cm3g-1、0.08cm3g-1And 0.98cm3g-1, and most of is mesoporous distribution (2-50nm), this corresponds to nitrogen-doped carbon
The unique defects vacancy of nanometer sheet and topological marginal texture.Therefore nitrogen-doped carbon nanometer sheet has suitable pore volume to be more advantageous to electricity
The transmission of the entrance and lithium ion of liquid ion in charge and discharge process is solved, and then increases capacitivity.
Experimental example 4
By taking embodiment 15 as an example, the lithium ion cell electrode that embodiment 15 provides is respectively applied in lithium ion battery.
A is the corresponding lithium ion battery of embodiment 15 in voltage range 0.01~3V sweep speed 0.1mV s in Fig. 8-1When
Preceding cyclic voltammetry curve three times.Scheme in a as can be seen that occurring on the curve of cathodic scan for the first time of material, at 0.8V larger
Irreversible reduction peak is attributable to the formation of solid electrolytic liquid medium (SEI) film, is the weight for leading to irreversible capacity loss
Reason is wanted, this peak disappears after recycling for the first time.In addition, the redox peaks of 0.01V and 0.20V and 1.2V respectively correspond Li+
The process of deintercalation in defective bit and lamella.Second preferable with third time CV curve co-insides, illustrates in first scan process
In, more stable SEI film is formd, and electrode material has stable cycle performance.Scheme b be the corresponding lithium of embodiment 15 from
Sub- battery is 100mA g in current density-1When voltage capacity figure, for the first time circulation in, the corresponding lithium-ion electric of embodiment 15
The electric discharge in pond and charge specific capacity are 1653 mAh g-1With 964mAh g-1, first circle coulombic efficiency is 58.3%, lower coulomb
Efficiency is attributed to the formation of above-mentioned SEI film.
It is carried out using electric conductivity of the electrochemical impedance to the corresponding lithium ion battery of embodiment 15-17 lithium ion cell electrode
Analysis, it is specific as shown in Figure 9.The impedance of the corresponding lithium ion battery of embodiment 15 is minimum, show the corresponding lithium of embodiment 15 from
The electric conductivity of sub- battery is best, there is faster electronic transmission performance.
Experimental example 5
Embodiment 15-28 and comparative example the 4-6 lithium ion cell electrode provided are respectively applied to lithium ion battery, and surveyed
Its high rate performance under different current densities is measured, concrete outcome is shown in Table 1.
The high rate performance of the corresponding lithium ion battery of each embodiment and comparative example of table 1
It can be seen from the data in Table 1 that the corresponding lithium ion of the lithium ion cell electrode that various embodiments of the present invention are provided
Battery has good high rate performance.
Specifically, Figure 10 is high rate performance of the corresponding lithium ion battery of embodiment 15-17 under different current densities.Electricity
Current density is from 0.1A g-1It is gradually increased to 10A g-1, 10 circulations are carried out under each current density, eventually pass back to 0.1A g-1.It is evident from figure 8 that the corresponding lithium ion battery of embodiment 15 is in 0.1A g-1、0.2A g-1、0.5A g-1、1A
g-1、2A g-1、5A g-1、10A g-1Corresponding capacity is 807mAh g under current density-1、702mAh g-1、593mAh
g-1、 507mAh g-1、405mAh g-1、306mAh g-1With 231mAh g-1, when turning again to 0.1A g-1When current density,
Capacity is still up to 780mAh g-1, it can be seen that, the corresponding lithium ion battery of embodiment 15 is provided by the invention a kind of preferred
Mode, high rate performance are substantially better than other embodiments and the corresponding lithium ion battery of comparative example.
Experimental example 6
The lithium ion cell electrode that embodiment 15-28 and comparative example 4-6 are provided is applied to lithium ion battery, and measures it
In 1A g-1Under current density, in 100mA g-1After lower 5 circle of activation, the specific capacity after 800 charge and discharge cycles, specifically
It the results are shown in Table 2.
The cycle performance of the corresponding lithium ion battery of each embodiment and comparative example of table 2
It can be seen from the data in Table 2 that the lithium ion cell electrode that various embodiments of the present invention provide has good circulation
Performance.
Specifically, Figure 11 is the corresponding lithium ion battery of embodiment 15-17 in 1A g-1Under current density, in 100mA g-1
After lower 5 circle of activation, by 800 charge and discharge cycles contrast curve charts.As can be seen that after cycle charge-discharge 800 times, embodiment
15 corresponding capacity of lithium ion battery may remain in 848 mAh g-1, hence it is evident that it is better than other embodiments and the corresponding lithium of comparative example
Ion battery capacity.After by 800 charge and discharge, the coulombic efficiency of the embodiment of the present invention is nearly all able to maintain 100%,
Illustrate that the corresponding lithium ion battery of various embodiments of the present invention all has good stable circulation performance.
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
Pipe present invention has been described in detail with reference to the aforementioned embodiments, 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 nitrogen-doped carbon nanometer sheet, which comprises the following steps:
The mixture of asphalt, melamine and fused salt is calcined in protective atmosphere, obtains nitrogen-doped carbon nanometer sheet.
2. the preparation method of nitrogen-doped carbon nanometer sheet according to claim 1, which is characterized in that the asphalt, three
The mass ratio of poly cyanamid and fused salt is 1:(0.5-4): (10-50), preferably 1:(0.5-2): (12-45), further preferably
1:(0.6-1.5):(15-40)。
3. the preparation method of nitrogen-doped carbon nanometer sheet according to claim 2, which is characterized in that the asphalt includes
The component of following mass fraction: saturation divides 5-9%, and fragrance divides 23-27%, colloid 44-48% and asphalitine 16-20%；
Preferably, the fused salt includes the Molten Binary Salts that fusing point is 500-650 DEG C；
Preferably, the Molten Binary Salts are potassium chloride-calcium chloride, sodium chloride-potassium chloride, magnesium chloride-calcium chloride or calcium chloride-chlorine
Change manganese in any one or at least two combination；
Preferably, the Molten Binary Salts are potassium chloride-calcium chloride, and the mass ratio of potassium chloride and calcium chloride is (1-4): 1.
4. the preparation method of nitrogen-doped carbon nanometer sheet according to claim 1 to 3, which is characterized in that the guarantor
Shield property atmosphere is nitrogen；
Preferably, the temperature of the calcining is 600-1000 DEG C, and the time of calcining is 1-3h；
Preferably, the heating rate when calcining is 0.5-10 DEG C/min.
5. the preparation method of nitrogen-doped carbon nanometer sheet according to claim 1 to 3, which is characterized in that the stone
The preparation method of the mixture of oil asphalt, melamine and fused salt, comprising the following steps:
It is ground again after asphalt, melamine and fused salt are mixed, obtains the mixed of asphalt, melamine and fused salt
Close object；
Preferably, the revolving speed of the grinding is 600-1000r/min, and the time of grinding is 10-40min；
Preferably, described to be ground to ball milling, ball powder mass ratio when ball milling is (4-10): 1.
6. the preparation method of nitrogen-doped carbon nanometer sheet according to claim 1 to 3, which is characterized in that will calcine
Product afterwards is cleaned and is dried, and nitrogen-doped carbon nanometer sheet is obtained；
Preferably, it is cleaned when cleaning using acid solution；
Preferably, the mass fraction of the acid solution is 5-20%；
Preferably, the acid solution includes any one in hydrochloric acid solution, sulfuric acid solution or nitric acid solution or at least two
Combination；
Preferably, drying temperature is 60-120 DEG C, drying time 8-24h；
Preferably, the nitrogen-doped carbon nanometer sheet with a thickness of 4-15nm.
7. a kind of nitrogen-doped carbon nanometer sheet, which is characterized in that use nitrogen-doped carbon nanometer as claimed in any one of claims 1 to 6
The preparation method of piece is made；
Preferably, the nitrogen-doped carbon nanometer sheet with a thickness of 4-15nm.
8. a kind of lithium ion cell electrode, which is characterized in that be made using nitrogen-doped carbon nanometer sheet as claimed in claim 7.
9. a kind of lithium ion battery, which is characterized in that include lithium ion cell electrode according to any one of claims 8.
10. a kind of electric device, which is characterized in that include lithium ion battery as claimed in claim 9.
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| CN111362249A (en) * | 2020-02-24 | 2020-07-03 | 中国科学院深圳先进技术研究院 | Two-dimensional porous nitrogen-doped carbon, preparation method thereof and application thereof in lithium ion battery |
| CN112259745A (en) * | 2020-09-09 | 2021-01-22 | 温州大学新材料与产业技术研究院 | Oxygen reduction electrocatalyst based on nitrogen and sulfur co-doped carbon microsphere/carbon sheet material and application thereof |
| CN112259745B (en) * | 2020-09-09 | 2023-01-17 | 温州大学新材料与产业技术研究院 | Oxygen reduction electrocatalyst based on nitrogen and sulfur co-doped carbon microsphere/carbon sheet material and application thereof |
| CN114180571A (en) * | 2020-09-14 | 2022-03-15 | 华中科技大学 | Nitrogen-doped carbon-based lithium storage material and preparation method and application thereof |
| CN112234181A (en) * | 2020-10-27 | 2021-01-15 | 合肥工业大学 | Two-dimensional silicon oxide/carbon composite lithium ion battery cathode material and preparation method thereof |
| CN113224295A (en) * | 2021-05-19 | 2021-08-06 | 东北大学 | Preparation method and application of asphalt-based nano carbon sheet |
| CN113340955A (en) * | 2021-05-25 | 2021-09-03 | 中国石油大学(北京) | All-solid-state ion selective electrode based on nitrogen-doped asphalt-based porous carbon and preparation method thereof |
| CN114715875A (en) * | 2022-03-31 | 2022-07-08 | 宁波大学 | Preparation method of thin-layer carbon-based material and application of thin-layer carbon-based material as battery material |
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