CN109728246A - A kind of nitrogen-phosphor codoping ordered mesoporous carbon material and its preparation method and application - Google Patents
A kind of nitrogen-phosphor codoping ordered mesoporous carbon material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses the applications of a kind of preparation method of nitrogen-phosphor codoping ordered mesoporous carbon material and the nitrogen-phosphor codoping ordered mesoporous carbon material, the nitrogen-phosphor codoping ordered mesoporous carbon material is using organic sugar as carbon source, use mesoporous template synthesizing ordered mesoporous carbon, then solution and water bath method are mixed into the nitrogen phosphorus source of different proportion, gained mixture realizes nitrogen-phosphor codoping by high-temperature calcination pyrolysis, obtains high performance anode material of lithium-ion battery after removing mesoporous template after.Have preparation process easy using nitrogen-phosphor codoping ordered mesoporous carbon material prepared by the method for the present invention, doping is high, and excellent cycle performance and high rate charge-discharge performance are shown as anode material of lithium-ion battery, it is had broad application prospects in energy storage field.
Description
Technical field
The present invention relates to anode material of lithium-ion battery technical fields, and in particular, to a kind of negative for sodium-ion battery
The preparation method of the material of the nitrogen-phosphor codoping ordered mesopore carbon of pole.
Background technique
With the fast development of electric vehicle industry and renewable energy (such as wind energy, solar energy) worldwide,
Lithium ion battery is had received widespread attention due to its excellent chemical property and plurality of advantages.However the reserves of elemental lithium are deficient
Be unevenly distributed the higher cost for causing lithium ion battery, therefore develop new excellent combination property and be able to satisfy the following scale
The battery energy storage system of application demand has received widespread attention.Have benefited from the abundant reserves of sodium element and similar with lithium physico
Property is learned, sodium-ion battery is considered as that may substitute the optimal candidate of lithium ion battery in scale energy storage field from now on.Therefore
Research and development can match in excellence or beauty the high capacity of lithium electricity, and the electrode material of long-life and excellent high rate performance is that sodium-ion battery is pushed to send out
The key of exhibition and application.
Anode material of lithium-ion battery mainly includes carbon material and non-carbon material (metal and oxysulfide material, alloy material
Material etc.).Non-carbon material have high theoretical capacity, but its poorly conductive and cycle performance it is unstable, the service life is shorter；Compared to non-
Carbon material, carbon material have many advantages, such as resourceful, prepare simple, and cyclical stability is high, and safety is good.Therefore carbon material is
The great crucial negative electrode material for wishing to push sodium ion industrialization.Ordered mesopore carbon has abundant and stable meso-hole structure, has
Conducive to the infiltration and electrode reaction for reducing sodium ion diffusion energy barrier and raising electrolyte, and it has very big specific surface area to be conducive to
The adsorption of sodium ion and energy storage, therefore ordered mesopore carbon is a kind of anode material of lithium-ion battery of great prospect.However
Its electric conductivity of pure ordered mesopore carbon is simultaneously bad, and storage sodium capacity is also difficult to meet the needs of industrial application.
Research mostly uses electric conductivity of the Heteroatom doping to promote carbon precursor material greatly at present, causes on carbon skeleton structure surface
Defect improves its chemical property to promote carbon material to the adsorption capacity of sodium ion.([J] Journal of such as Wang
Materials Chemistry A, 2015,3,7849-7854) by 600-900oGelatin and citric acid are pyrolyzed under C
Magnesium obtains nitrogenous porous carbon, in 50 mA g-1Specific capacity under current density after 100 circle of circulation is 260 mA h g-1。Zhao
Deng ([J] Journal of Materials Chemistry A, 2017,5,24353-24360) with poly- Dithiophene methanol
For sulphur source, the porous carbon of sulfur doping is obtained by being pyrolyzed the durian peel through pre-treatment, in 100 mA g-1It is recycled under current density
264 mA h g still can be maintained after 200 circles-1Specific capacity.Monatomic doping is compared, diatomic codope not only can be simultaneous
Has respective advantage, the synergistic effect of the two can also have greatly improved to the performance of material.Ruan etc. ([J] Carbon,
2018,126,9-16) the nitrogen sulphur codope carbon film obtained by pyrolysis polypyrrole film and flowers of sulfur is as sodium-ion battery cathode
Preferable reversible capacity and cyclical stability are also showed that, in 100 mA g-1It still can reach after 1000 circle of circulation under current density
379.1 mA h g-1.It is mostly monatomic in existing report (such as: nitrogen, sulphur, phosphorus) doping, diatomic adulterate carbon material research compared with
The problems such as few, and part is there is complex process, and low yield is at high cost, security risk.
Summary of the invention
The present invention is intended to provide a kind of preparation process is simple, stable cycle performance and excellent nitrogen-phosphor codoping is order mesoporous
Carbon is used for anode material of lithium-ion battery.
The technical solution used in the present invention is as follows.
A kind of preparation method of nitrogen-phosphor codoping ordered mesoporous carbon material, which is characterized in that described according to mass fraction meter
Nitrogen-phosphor codoping ordered mesoporous carbon material is to be completely dissolved in the carbon source presoma of 1~3 part of organic monosaccharide or oligosaccharide in right amount
In deionized water, 0.05~0.15 part of concentrated sulfuric acid is then added and is dehydrated as dehydrating agent, it then will be before dewatered carbon source
Sonicated 5~the 15min of body is driven to be distributed in 1 part of mesoporous silicon template, it is then dry through gradient increased temperature again, orderly it is situated between
Hole carbon material intermediate；1 part of ordered mesoporous carbon material intermediate is taken, 3~7 parts of nitrogen phosphorus source monomers are added, are dissolved in after mixing
In appropriate amount of deionized water, be then evaporated deionized water, and obtained solid product is ground to it is powdered, then again in indifferent gas
High-temperature heat treatment under atmosphere removes mesoporous silicon template with strong base solution after high-temperature heat treatment, product is finally washed to neutrality, does
Dry, obtained solid product is nitrogen-phosphor codoping ordered mesoporous carbon material.
The preparation method of nitrogen-phosphor codoping ordered mesoporous carbon material as described above, which is characterized in that organic monosaccharide
For glucose or sucrose, the oligosaccharide is maltose or fructose；The mesoporous silicon template is SBA-1, SBA-15, MCM-
Any one in 48, KIT-6；The nitrogen phosphorus source monomer is ammonium dihydrogen phosphate, and ammonium phosphate is any one in chlordene tripolyphosphazene
Kind.
The preparation method of nitrogen-phosphor codoping ordered mesoporous carbon material as described above, which is characterized in that be evaporated deionized water
The step of be, utilize water-bath, the temperature of water-bath be 60~80 DEG C under conditions of, evaporate 8~12h.
The preparation method of nitrogen-phosphor codoping ordered mesoporous carbon material as described above, which is characterized in that gradient increased temperature is dry
Process be that the mixture of ordered mesopore carbon and mesoporous silicon template is placed in 80~110 DEG C of dry 4~6h, is then raised temperature to
150~180 DEG C are continued dry 4~6h；Product, which is washed to the process dried after neutrality, is, dry 8~12 at 50~80 DEG C
Hour.
The preparation method of nitrogen-phosphor codoping ordered mesoporous carbon material as described above, which is characterized in that high under inert atmosphere
The process of warm processing is, under conditions of argon atmosphere and temperature are 600~800 DEG C, 4~6h of high-temperature heat treatment.
The preparation method of nitrogen-phosphor codoping ordered mesoporous carbon material as described above, which is characterized in that after high-temperature heat treatment
The process that mesoporous silicon template is removed with strong base solution is that the strong base solution is the sodium hydroxide that mass percent is 8~12%
Or potassium hydroxide aqueous solution.
A kind of nitrogen-phosphor codoping ordered mesoporous carbon material prepared by above-mentioned preparation method, which is characterized in that the nitrogen phosphorus
The aperture of codope ordered mesoporous carbon material is 4~6nm, and the doping of nitrogen is 15~20%, and first circle discharge capacity is
1293.8~2136.7 mA h g-1, reversible capacity is 276~386.8 mA h g after circulation 100 is enclosed-1。
The invention further relates to above-mentioned nitrogen-phosphor codoping ordered mesopore carbons to be used for anode material of lithium-ion battery field, Yi Jiti
Supply a kind of preparation process simple, stable cycle performance and excellent sodium-ion battery cathode and preparation method thereof, feature exists
In, first by nitrogen-phosphor codoping ordered mesoporous carbon material be ground to partial size be less than 10um powder, then by the powder and carbon
Black, Kynoar mixes for 7:2:1 in mass ratio and grinds uniformly, appropriate dispersing and dissolving agent N-Methyl pyrrolidone is added dropwise,
It is uniformly mixing to obtain paste, the paste is finally coated uniformly on copper foil surface, under vacuum conditions in 80~100 DEG C
Dry 10~14h, is made sodium-ion battery cathode.
Compared with prior art, technical advantage of the invention and progress are:
(1) the present invention provides a kind of preparation methods of nitrogen-phosphor codoping ordered mesoporous carbon material, using organic carbohydrate as carbon source,
Using mesoporous silicon template, by adjusting the usage amount of nitrogen source and phosphorus source to change the doping of nitrogen phosphorus heteroatoms, in nitrogen phosphorus
After codope, a degree of destruction is had occurred in the duct of ordered mesopore carbon, increases surface defect, is conducive to the storage of sodium ion
It deposits, but has still maintained the ordered mesopore structure of ordered mesopore carbon on the whole simultaneously, this special surface texture makes this
The absorption that there is nitrogen-phosphor codoping ordered mesoporous carbon material prepared by inventive method very big specific surface area to be used for sodium ion, and
Its meso-hole structure abundant can effectively improve the wellability of electrolyte, be conducive to sufficient electrochemical reaction, therefore, this hair
Nitrogen-phosphor codoping ordered mesoporous carbon material prepared by bright method not only effectively improves the electric conductivity of ordered mesopore carbon, may be used also
To improve the ability of its adsorption sodium ion, to improve nitrogen-phosphor codoping ordered mesoporous carbon material as sodium-ion battery
The chemical property of cathode raw material.
(2) battery cathode further prepared using nitrogen-phosphor codoping ordered mesoporous carbon material prepared by the method for the present invention
Material, aperture are 4~6nm, and the doping of nitrogen is reachable 20% or more, and first circle discharge capacity can be improved to 2136.7
mA h g-1, reversible capacity mA h g after circulation 100 is enclosed-1Reach as high as 386.8 mA h g-1, compared to not carried out in comparative example
The ordered mesopore carbon of doping, the reversible capacity after its modified circulation 100 of nitrogen-phosphor codoping is enclosed improve 19~66%, sodium ion
The cyclical stability of battery and service life have also obtained apparent improvement.In addition, orderly using nitrogen-phosphor codoping provided by the invention
Nitrogen-phosphor codoping ordered mesoporous carbon material prepared by the preparation method and this method of meso-porous carbon material further prepare sodium from
The method of sub- battery cathode has integrated artistic simple flow, highly-safe, and shows as anode material of lithium-ion battery
Excellent cycle performance and high rate charge-discharge performance, has broad application prospects in energy storage field.
Detailed description of the invention
Fig. 1 is the nitrogen-phosphor codoping ordered mesopore carbon that is prepared of embodiment 1 and what comparative example was prepared is not mixed
The transmission electron microscope picture (TEM) of miscellaneous ordered mesopore carbon.
Fig. 2 is the X-ray diffracting spectrum (XRD) of embodiment 1 and comparative example.
Fig. 3 is the XPS figure for the nitrogen-phosphor codoping ordered mesopore carbon that embodiment 1 is prepared.
Fig. 4 is the electrochemical impedance map of embodiment 3 and comparative example.
Fig. 5 is the charging and discharging curve figure for the nitrogen-phosphor codoping ordered mesopore carbon that embodiment 4 is prepared.
Specific embodiment
Below by specific embodiment combination attached drawing, the following further describes the technical solution of the present invention, but of the invention
Embodiment is without being limited thereto.
Embodiment 1
It weighs 1.25 g sucrose to be placed in a beaker, then measures 5 mL deionized waters with graduated cylinder and be added in above-mentioned beaker, stir
The 0.14 g concentrated sulfuric acid is added dropwise until completely dissolved as dehydrating agent and stirs evenly.Weigh 1 g SBA-15 be slowly added into it is above-mentioned
In solution and thick white paste is continued stirring until, is ultrasonically treated 10 min then to improve its dispersibility.Place it in 100
It is 6 hours dry in DEG C baking oven, it then raises temperature to 160 DEG C of re-dries 6 hours, obtains the compound of ordered mesopore carbon and SBA-15
Object.
It weighs the above-mentioned composite solids of 1 g and is ground to powder, and mix and be dissolved in deionized water with 5 g ammonium dihydrogen phosphates,
It is subsequently placed at solvent evaporated water in 60 DEG C of water-baths, gained is ground to powder under tube furnace argon atmosphere after drying
It is calcined 5 hours at 800 DEG C, obtains black solid product and be subsequently placed in 10% sodium hydrate aqueous solution, stand 24 hours use
It with mesoporous silicon template of going out, then filters, and is cleaned with a large amount of deionized waters until sample is neutrality, collection obtained solid is simultaneously
It is 12 hours dry at 60 DEG C of baking oven, obtain nitrogen-phosphor codoping ordered mesopore carbon.
Gained nitrogen-phosphor codoping ordered mesoporous carbon material is ground and obtains cathode powder of the partial size less than 10 microns.
Then resulting cathode powder is mixed in mass ratio for 7:2:1 with conductive agent carbon black, binder Kynoar (PVDF)
Merge grinding uniformly, 0.8~1.2 gram of N-Methyl pyrrolidone is then added dropwise as dispersing and dissolving agent, is stirred for paste；It will
It is coated uniformly on copper foil surface, then obtains sodium-ion battery cathode material within dry 12 hours at 80~100 DEG C of vacuum drying oven
Material.
Select the pole piece of above-mentioned coating nitrogen-phosphor codoping ordered mesopore carbon as cathode, metallic sodium piece is as anode assembling sodium
Ion battery.Then battery is carried out in the voltage range of 0.01~3.0 V using LAND-CT2001A battery test system
Electrochemical property test.
Embodiment 2
It weighs 2.25 g glucose to be placed in a beaker, then measures 5 mL deionized waters with graduated cylinder and be added in above-mentioned beaker, stir
It mixes and the 0.24 g concentrated sulfuric acid is added dropwise until completely dissolved as dehydrating agent and stirs evenly.1 g SBA-15 is weighed to be slowly added into
Thick white paste is stated in solution and continued stirring until, is ultrasonically treated 10 min then to improve its dispersibility.It places it in
It is 6 hours dry in 100 DEG C of baking ovens, it then raises temperature to 160 DEG C of re-dries 6 hours, obtains ordered mesopore carbon and SBA-15
Compound.
It weighs the above-mentioned composite solids of 1 g and is ground to powder, and mix and be dissolved in deionized water with 5 g ammonium phosphate, then
Solvent evaporated water in 80 DEG C of water-baths is placed it in, gained is ground to powder 800 under tube furnace argon atmosphere after drying
It is calcined 5 hours at DEG C, obtains black solid product and be subsequently placed in 10% sodium hydrate aqueous solution, stand 24 hours to go out
Mesoporous silicon template is removed, is then filtered, and is cleaned with a large amount of deionized waters until sample is neutrality, collection obtained solid is simultaneously being dried
It is 12 hours dry at 60 DEG C of case, obtain nitrogen-phosphor codoping ordered mesopore carbon.
Gained nitrogen-phosphor codoping ordered mesoporous carbon material is ground and obtains cathode powder of the partial size less than 10 microns.
Then resulting cathode powder is mixed in mass ratio for 7:2:1 with conductive agent carbon black, binder Kynoar (PVDF)
Merge grinding uniformly, 0.8~1.2 gram of N-Methyl pyrrolidone is then added dropwise as dispersing and dissolving agent, is stirred for paste；It will
It is coated uniformly on copper foil surface, then obtains sodium-ion battery cathode material within dry 12 hours at 80~100 DEG C of vacuum drying oven
Material.
Select the pole piece of above-mentioned coating nitrogen-phosphor codoping ordered mesopore carbon as cathode, metallic sodium piece is as anode assembling sodium
Ion battery.Then battery is carried out in the voltage range of 0.01~3.0 V using LAND-CT2001A battery test system
Electrochemical property test.
Embodiment 3
It weighs 1.25 g fructose to be placed in a beaker, then measures 5 mL deionized waters with graduated cylinder and be added in above-mentioned beaker, stir
The 0.14 g concentrated sulfuric acid is added dropwise until completely dissolved as dehydrating agent and stirs evenly.Weigh 1 g SBA-15 be slowly added into it is above-mentioned
In solution and thick white paste is continued stirring until, is ultrasonically treated 10 min then to improve its dispersibility.Place it in 100
It is 6 hours dry in DEG C baking oven, it then raises temperature to 160 DEG C of re-dries 6 hours, obtains the compound of ordered mesopore carbon and SBA-15
Object.
It weighs the above-mentioned composite solids of 1 g and is ground to powder, and mixed with 7 g chlordene tripolyphosphazenes and be dissolved in deionized water
In, it is subsequently placed at solvent evaporated water in 60 DEG C of water-baths, gained is ground to powder in tube furnace argon atmosphere after drying
It is calcined 5 hours at lower 600 DEG C, obtains black solid product and be subsequently placed in 10% sodium hydrate aqueous solution, stand 24 hours
It to mesoporous silicon template of going out, then filters, and is cleaned with a large amount of deionized waters until sample is neutral, collection obtained solid
And it is 12 hours dry at 60 DEG C of baking oven, obtain nitrogen-phosphor codoping ordered mesopore carbon.
Gained nitrogen-phosphor codoping ordered mesoporous carbon material is ground and obtains cathode powder of the partial size less than 10 microns.
Then resulting cathode powder is mixed in mass ratio for 7:2:1 with conductive agent carbon black, binder Kynoar (PVDF)
Merge grinding uniformly, 0.8~1.2 gram of N-Methyl pyrrolidone is then added dropwise as dispersing and dissolving agent, is stirred for paste；It will
It is coated uniformly on copper foil surface, then obtains sodium-ion battery cathode material within dry 12 hours at 80~100 DEG C of vacuum drying oven
Material.
Select the pole piece of above-mentioned coating nitrogen-phosphor codoping ordered mesopore carbon as cathode, metallic sodium piece is as anode assembling sodium
Ion battery.Then battery is carried out in the voltage range of 0.01~3.0 V using LAND-CT2001A battery test system
Electrochemical property test.
Embodiment 4
2 g glucose are weighed to be placed in a beaker, then with graduated cylinder measure 5 mL deionized waters be added in above-mentioned beaker, stirring to
The 0.14 g concentrated sulfuric acid is added dropwise after being completely dissolved as dehydrating agent and stirs evenly.Weigh 1 g MCM-48 be slowly added into it is above-mentioned molten
In liquid and thick white paste is continued stirring until, is ultrasonically treated 10 min then to improve its dispersibility.Place it in 100
It is 6 hours dry in DEG C baking oven, it then raises temperature to 160 DEG C of re-dries 6 hours, obtains the compound of ordered mesopore carbon and MCM-48
Object.
It weighs the above-mentioned composite solids of 1 g and is ground to powder, and mixed with 3 g chlordene tripolyphosphazenes and be dissolved in deionized water
In, it is subsequently placed at solvent evaporated water in 60 DEG C of water-baths, gained is ground to powder in tube furnace argon atmosphere after drying
It is calcined 5 hours at lower 700 DEG C, obtains black solid product and be subsequently placed in 10% sodium hydrate aqueous solution, stand 24 hours
It to mesoporous silicon template of going out, then filters, and is cleaned with a large amount of deionized waters until sample is neutral, collection obtained solid
And it is 12 hours dry at 60 DEG C of baking oven, obtain nitrogen-phosphor codoping ordered mesopore carbon.
Gained nitrogen-phosphor codoping ordered mesoporous carbon material is ground and obtains cathode powder of the partial size less than 10 microns.
Then resulting cathode powder is mixed in mass ratio for 7:2:1 with conductive agent carbon black, binder Kynoar (PVDF)
Merge grinding uniformly, 0.8~1.2 gram of N-Methyl pyrrolidone is then added dropwise as dispersing and dissolving agent, is stirred for paste；It will
It is coated uniformly on copper foil surface, then obtains sodium-ion battery cathode material within dry 12 hours at 80~100 DEG C of vacuum drying oven
Material.
Select the pole piece of above-mentioned coating nitrogen-phosphor codoping ordered mesopore carbon as cathode, metallic sodium piece is as anode assembling sodium
Ion battery.Then battery is carried out in the voltage range of 0.01~3.0 V using LAND-CT2001A battery test system
Electrochemical property test.
Comparative example
It weighs 1.25 g sucrose to be placed in a beaker, then measures 5 mL deionized waters with graduated cylinder and be added in above-mentioned beaker, stir
The 0.14 g concentrated sulfuric acid is added dropwise until completely dissolved as dehydrating agent and stirs evenly.Weigh 1 g SBA-15 be slowly added into it is above-mentioned
In solution and thick white paste is continued stirring until, is ultrasonically treated 10 min then to improve its dispersibility.Place it in 100
It is 6 hours dry in DEG C baking oven, it then raises temperature to 160 DEG C of re-dries 6 hours, obtains the compound of ordered mesopore carbon and SBA-15
Object.
Above-mentioned compound is ground to powder at 800 DEG C of tube furnace argon atmosphere to calcine 5 hours, obtains black solid
Product is subsequently placed in 10% sodium hydrate aqueous solution, is stood 24 hours to mesoporous silicon template of going out, is then filtered, and
It is cleaned with a large amount of deionized waters until sample is neutrality, collection obtained solid is simultaneously 12 hours dry at 60 DEG C of baking oven, obtains not
The ordered mesopore carbon being doped.
The undoped ordered mesoporous carbon material of gained is ground and obtains cathode powder of the partial size less than 10 microns.With
Resulting cathode powder is mixed in mass ratio for 7:2:1 with conductive agent carbon black, binder Kynoar (PVDF) afterwards
And grind uniformly, 0.8~1.2 gram of N-Methyl pyrrolidone is then added dropwise as dispersing and dissolving agent, is stirred for paste；By its
It is coated uniformly on copper foil surface, then obtains sodium-ion battery cathode material within dry 12 hours at 80~100 DEG C of vacuum drying oven
Material.
Select the pole piece of above-mentioned coating ordered mesopore carbon as cathode, metallic sodium piece is as anode assembling sodium-ion battery.
Then battery is subjected to chemical property using LAND-CT2001A battery test system in the voltage range of 0.01~3.0 V
Test.
Fig. 1 is that the nitrogen-phosphor codoping ordered mesopore carbon (a) that embodiment 1 is prepared and comparative example (b) are prepared not
The transmission electron microscope picture (TEM) for the ordered mesopore carbon being doped.TEM figure is shown in Fig. 1, the ordered mesopore carbon not being doped
(b) there is very regular, good pore structure, aperture is about 4 ~ 6nm.After nitrogen-phosphor codoping (a), ordered mesopore carbon
A degree of destruction, degree of order decline has occurred in duct, but has still maintained the order mesoporous knot of ordered mesopore carbon on the whole
Structure.
Fig. 2 is the X-ray diffracting spectrum (XRD) of embodiment 1 and comparative example, order mesoporous compared to what is be not doped
The diffraction maximum of carbon (b), nitrogen-phosphor codoping (a) its XRD afterwards is deviated to the left and peak broadens, this illustrates nitrogen-phosphor codoping not only
The interlamellar spacing of ordered mesopore carbon has been widened, and has increased disordering degree, has increased its surface defect.
Fig. 1, Fig. 2 show the nitrogen-phosphor codoping ordered mesoporous carbon material of the method for the present invention preparation, by adjusting nitrogen source and phosphorus
The usage amount in source is to change the doping of nitrogen phosphorus heteroatoms, after nitrogen-phosphor codoping, the duct of ordered mesopore carbon has occurred one
The destruction for determining degree, increases surface defect, is conducive to the storage of sodium ion, but has still maintained orderly Jie on the whole simultaneously
The ordered mesopore structure of hole carbon, this special surface texture make nitrogen-phosphor codoping prepared by the method for the present invention order mesoporous
The absorption that there is carbon material very big specific surface area to be used for sodium ion, and its meso-hole structure abundant can effectively improve electrolysis
The wellability of liquid is conducive to sufficient electrochemical reaction.Therefore, nitrogen-phosphor codoping ordered mesopore carbon prepared by the method for the present invention
Material not only effectively improves the electric conductivity of ordered mesopore carbon, can also improve the ability of its adsorption sodium ion, thus
Improve chemical property of the nitrogen-phosphor codoping ordered mesoporous carbon material as sodium-ion battery cathode raw material.
Fig. 3 is the XPS figure for the nitrogen-phosphor codoping ordered mesopore carbon that embodiment 1 is prepared.
Fig. 4 is the electrochemical impedance map (EIS) of embodiment 3 and comparative example, and EIS map shows that the doping of nitrogen phosphorus atoms is orderly
Mesoporous carbon (a) impedance that the ordered mesopore carbon (b) not being doped is compared in its impedance afterwards reduces, and shows that its electric conductivity improves, has
Conducive to the transfer of electronics.
Fig. 5 is the charging and discharging curve figure for the nitrogen-phosphor codoping ordered mesopore carbon that embodiment 4 is prepared, and is with three times in figure
Illustrate the electric property of nitrogen-phosphor codoping ordered mesopore carbon of the present invention for charge and discharge, wherein (a) indicates first circle electric discharge, (b) table
Show that first circle charging, (c) indicate that the second circle electric discharge, (d) indicate that the second circle charging, (e) indicate that the electric discharge of third circle, (f) indicate third
Circle charging.Charging and discharging curve shows after nitrogen phosphorus doping in Fig. 5, and first circle discharge capacity may be up to 1412 mA h g-1, and
Capacity keeps good in subsequent charge and discharge process, it is shown that good stability.
Table 1 show chemical property contrast table (the 100 mA g of each embodiment and comparative example-1).By table 1 it is found that
The chemical property of the modified ordered mesoporous carbon material of nitrogen-phosphor codoping has apparent improvement, compared to what is be not doped
Ordered mesopore carbon, the reversible capacity after its modified circulation 100 of nitrogen-phosphor codoping is enclosed improve 19~66%.This can be attributed to
The improvement of its electrical conductance after doping, and because nitrogen, phosphorus atoms doping caused by defect sites increase, be conducive to the absorption of sodium ion
And storage.
Table 1
In conjunction with Fig. 3, Fig. 4, Fig. 5 and table 1, it can be seen that using nitrogen-phosphor codoping ordered mesopore carbon prepared by the method for the present invention
The cell negative electrode material that material is further prepared, aperture are 4~6nm, and the doping of nitrogen is reachable 20% or more, first
Circle discharge capacity can be improved to 2136.7 mA h g-1, reversible capacity mA h g after circulation 100 is enclosed-1Reach as high as 386.8 mA
h g-1, reversible after its modified 100 circle of circulation of nitrogen-phosphor codoping compared to the ordered mesopore carbon not being doped in comparative example
Capacity boost 19~66%, the cyclical stability of sodium-ion battery and service life also obtained apparent improvement.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, all in technical side of the invention
Made any modifications, equivalent replacements, and improvements etc. within case and design invention, should be included in protection scope of the present invention it
It is interior.
Claims (10)
1. a kind of preparation method of nitrogen-phosphor codoping ordered mesoporous carbon material, which is characterized in that according to mass fraction meter, the nitrogen
Phosphor codoping ordered mesoporous carbon material is to be completely dissolved in the carbon source presoma of 1~3 part of organic monosaccharide or oligosaccharide to go in right amount
In ionized water, 0.05~0.15 part of concentrated sulfuric acid is then added and is dehydrated as dehydrating agent, then by dewatered carbon source forerunner
Sonicated 5~the 15min of body is distributed in 1 part of mesoporous silicon template, then dry through gradient increased temperature again, is obtained order mesoporous
Carbon material intermediate；1 part of ordered mesoporous carbon material intermediate is taken, 3~7 parts of nitrogen phosphorus source monomers are added, are dissolved in after mixing suitable
Measure in deionized water, be then evaporated deionized water, and obtained solid product is ground to it is powdered, then again in inert atmosphere
Lower high-temperature heat treatment removes mesoporous silicon template with strong base solution after high-temperature heat treatment, product is finally washed to neutrality, does
Dry, obtained solid product is nitrogen-phosphor codoping ordered mesoporous carbon material.
2. the preparation method of nitrogen-phosphor codoping ordered mesoporous carbon material according to claim 1, which is characterized in that described to have
Machine monosaccharide is glucose or sucrose, and the oligosaccharide is maltose or fructose；The mesoporous silicon template be SBA-1, SBA-15,
Any one in MCM-48, KIT-6；The nitrogen phosphorus source monomer is ammonium dihydrogen phosphate, ammonium phosphate, appointing in chlordene tripolyphosphazene
It anticipates one kind.
3. the preparation method of nitrogen-phosphor codoping ordered mesoporous carbon material according to claim 1 or 2, which is characterized in that steam
The step of dry deionized water is to evaporate 8~12h under conditions of the temperature of water-bath is 60~80 DEG C using water-bath.
4. the preparation method of nitrogen-phosphor codoping ordered mesoporous carbon material according to claim 1 or 2, which is characterized in that ladder
The dry process of degree heating is that the mixture of ordered mesopore carbon and mesoporous silicon template is placed in 80~110 DEG C of dry 4~6h,
It then raises temperature to 150~180 DEG C and continues dry 4~6h；Product, which is washed to the process dried after neutrality, is, at 50~80 DEG C
It is 8~12 hours dry.
5. the preparation method of nitrogen-phosphor codoping ordered mesoporous carbon material according to claim 1 or 2, which is characterized in that lazy
Property atmosphere under the process of high-temperature heat treatment be, under conditions of argon atmosphere and temperature are 600~800 DEG C, high-temperature heat treatment 4
~6h.
6. the preparation method of nitrogen-phosphor codoping ordered mesoporous carbon material according to claim 1 or 2, which is characterized in that high
Removing the process of mesoporous silicon template with strong base solution after warm processing is that the strong base solution is that mass percent is 8~12%
Sodium hydroxide or potassium hydroxide aqueous solution.
7. prepared by the preparation method of nitrogen-phosphor codoping ordered mesoporous carbon material described in a kind of any one of claim 3 to 6
Nitrogen-phosphor codoping ordered mesoporous carbon material, which is characterized in that the aperture of the nitrogen-phosphor codoping ordered mesoporous carbon material be 4~
6nm, the doping of nitrogen are 15~20%, and first circle discharge capacity is 1293.8~2136.7 mA h g-1, after circulation 100 is enclosed
Reversible capacity is 276~386.8 mA h g-1。
8. a kind of application of nitrogen-phosphor codoping ordered mesoporous carbon material as claimed in claim 7 in sodium-ion battery cathode.
9. a kind of sodium-ion battery cathode of nitrogen-phosphor codoping ordered mesoporous carbon material preparation, which is characterized in that the sodium ion
Battery cathode is made by nitrogen-phosphor codoping ordered mesoporous carbon material as claimed in claim 7.
10. a kind of preparation method of sodium-ion battery cathode as claimed in claim 9 is, which is characterized in that be first total to nitrogen phosphorus
Doping ordered mesoporous carbon material is ground to powder of the partial size less than 10um and presses then by the powder and carbon black, Kynoar
Mass ratio is that 7:2:1 is mixed and ground uniformly, and appropriate dispersing and dissolving agent N-Methyl pyrrolidone is added dropwise, is uniformly mixing to obtain paste
The paste is finally coated uniformly on copper foil surface by object, under vacuum conditions in 80~100 DEG C of dry 10~14h, is made
Sodium-ion battery cathode.
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