CN106006599A - Synthesizing method and application of high-S-content P-S-N-codoped mesoporous carbon material - Google Patents
Synthesizing method and application of high-S-content P-S-N-codoped mesoporous carbon material Download PDFInfo
- Publication number
- CN106006599A CN106006599A CN201610311775.XA CN201610311775A CN106006599A CN 106006599 A CN106006599 A CN 106006599A CN 201610311775 A CN201610311775 A CN 201610311775A CN 106006599 A CN106006599 A CN 106006599A
- Authority
- CN
- China
- Prior art keywords
- snppc
- content
- carbon material
- meso
- codope
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a synthesizing method and application of a high-S-content P-S-N-codoped mesoporous carbon material. The preparation method of the material comprises the following steps that 2-aminothiazol and sodium dihydrogen phosphate are taken as raw materials, ZnCl2 is taken as a solvent and a catalyst, and 2-aminothiazol, sodium dihydrogen phosphate and ZnCl2 are put into a tubular furnace to be subjected to high-temperature carbonization through a one-step method to obtain the high-S-content P-S-N-codoped mesoporous carbon material SNPPC, wherein the specific surface area of the SNPPC-800 reaches up to 1,122.46 m<2>/g, the pore diameter ranges from 20 nm to 50 nm, the sulphur content reaches up to 12.58%, and the SNPPC-800 shows the excellent lithium battery performance, oxygen reduction performance and supercapacitor performance compared with low-S-content SNPC. In addition, the method is easy to operate and high in yield and has wide application prospects.
Description
Technical field
The invention belongs to inorganic nano material and technical field of electrochemistry, be specifically related to the P of a kind of high S content, S, N are co-doped with
The synthetic method of miscellaneous meso-porous carbon material and application thereof.
Background technology
In the last few years, caused in the most potential application of aspect such as catalysis, energy storage, gas separation due to porous carbon materials
Everybody interest.It is mainly due to them and there is the highest specific surface area of unrivaled characteristic, chemical stability, adjustable
Pore structure and hetero atom are modified.But, original porous carbon illustrates more weak electricity owing to lacking the active center being anchored on surface
Chemism.Owing to specific surface area is three-dimensional and the adjustability of electronics, modifications various for carbon framework or surface are permissible
Strengthen absorption, spread and activate.Therefore, foreign atom is to carbon framework, it will changes the energy and activity shown, becomes enhancingization
Learn the flexible strategy of activity.Since Jasinski reports the material with carbon element of N doping for the first time, everybody has begun to pay close attention to doping carbon
Design and synthesis.The doping of atom N, due to odd electron configuration and electronegativity feature, effectively raises electronics distribution and electricity
Lotus spin densities, introduces active site to neighbouring carbon.Except atom N, S atom is also considered as an effective side
Method changes porous carbon performance the most spatially and electronically active, due to S outer layer bielectron to the atom bigger compared to C, N half
Footpath.
Due to respective chemical property and the electronic structure of coupling, the porous carbon materials of S, N codope has caused huge
Big concern, major part presents the performance of excellence in fuel cell, lithium battery and capacitor.Now, the porous of S, N doping
The synthesis of material with carbon element mainly includes that carbonization contains the presoma of S, N, such as biomass molecule and ionic liquid etc..Subject matter is
The porous carbon materials of S, the N doping of synthesis cause S content relatively low due to gasification and the post processing of S.This can weaken S atom to many
The electronic structure of hole carbon and the impact of geometry, therefore can reduce the synergistic action effect of N, S, therefore, limit S atom at frame
Frame for raising S atom content is and important.The structure activity relationship of previous research mainly SNPC rather than simple
Synthetic method.Up to now, improve S content method and also rarely have report.
Summary of the invention
The problem existed for prior art, it is an object of the invention to provide the P of a kind of high S content, S, N codope
The synthetic method of meso-porous carbon material and application thereof, it introduces NaH by high temperature cabonization2PO4S, N presoma, it is thus achieved that S, N,
The porous carbon materials of P codope has bigger specific surface area and the high SNPC containing S amount, illustrates compared to the SNPC of low S
Excellent lithium electrical property, hydrogen reduction performance and ultracapacitor performance, and these differences can carry owing to due to high S content
The high synergism of S, N.
The P of described a kind of high S content, the synthetic method of the meso-porous carbon material of S, N codope, it is characterised in that with 2-ammonia
Base thiazole and sodium dihydrogen phosphate are raw material, ZnCl2For catalysts and solvents, under nitrogen atmosphere, above-mentioned raw materials is put into tube furnace
The P of middle one-step synthesis method height S content, the meso-porous carbon material of S, N codope.
The P of described a kind of high S content, the synthetic method of the meso-porous carbon material of S, N codope, it is characterised in that specifically walk
Rapid as follows:
1) with thiazolamine for N source and S source, sodium dihydrogen phosphate is P source, and manual mixing is uniform, and forms three with zinc chloride
Mingzhi's structure, places in quartz boat;
2) quartz boat that step 1) obtains is put in tube furnace, at N2It is warming up to 800 DEG C with 5 DEG C/min, Mei Gewen under atmosphere
Degree section keeps 2h, and one-step method obtains the P of high S content, the meso-porous carbon material of S, N codope;
3) step 2 is taken out) reacted quartz boat, by the product in quartz boat with the salt acid elution of 35%, remove zinc chloride, then
Remove hydrochloric acid by deionized water and washing with alcohol, then product is dried at vacuum drying oven, obtains SNPPC-800 after drying.
The P of described a kind of high S content, the synthetic method of the meso-porous carbon material of S, N codope, it is characterised in that step 2)
Middle N2Flow velocity is 28-35 ml/min, preferably 30ml/min.
The P of described a kind of high S content, the synthetic method of the meso-porous carbon material of S, N codope, it is characterised in that step 3)
Middle vacuum drying oven temperature is 75-85 DEG C, and drying time is 2.5-3.5h.
The P of described a kind of high S content, the synthetic method of the meso-porous carbon material of S, N codope, it is characterised in that step 3)
Middle vacuum drying oven temperature is 80 DEG C, and drying time is 3h.
The P of described a kind of high S content, the synthetic method of the meso-porous carbon material of S, N codope, it is characterised in that SNPPC-
In 800 products, its S content is up to 12.58%, and specific surface area reaches 1122.46m2/g。
The S of described high S content, the meso-porous carbon material of N, P codope is as the application of cathode of lithium battery catalyst.
The S of described high S content, the meso-porous carbon material of N, P codope is as the application of fuel cell oxygen reduction catalyst.
The S of described high S content, the meso-porous carbon material of N, P codope is as the application of ultracapacitor catalyst.
By using above-mentioned technology, compared with prior art, beneficial effects of the present invention is as follows:
The S of a kind of novelty of successful design of the present invention, effective method 4 kinds high S content of synthesis, the mesoporous carbon material of N, P codope
Material, obtains high S content by introducing sodium dihydrogen phosphate to high temperature cabonization one-step method in the presoma thiazolamine containing S, N
SNPPC;Wherein SNPPC-800 S content is up to 12.58%, and specific surface area reaches 1122.46m2/g;High S content is owing to phosphorus
In acid dihydride sodium, oxygen-containing functional group promotes the absorption to S, and the sodium during biphosphate is received has catalysis to the formation of dopant material
Effect.Compared with other SNPPC materials, SNPPC-800 has a high lithium battery specific capacity, excellent high rate performance, preferably
Long-range circulation ability, in addition, SNPPC-800 shows preferable ORR and ultracapacitor performance.One made through the present invention
Series of tables performance test of seeking peace shows that the performance of excellence comes from the synergism of S, N of high S content.Therefore, this research provides
One potential catalyst of ORR without metal and lithium cell cathode material, improve the probability of the actual application of this kind of material.
Accompanying drawing explanation
Fig. 1 a is the scanning electron microscope (SEM) photograph of the SNPPC-800 of 1 micron;
Fig. 1 b is the transmission electron microscope picture of the SNPPC-800 of 100 nanometers;
Fig. 1 c is the transmission electron microscope picture of the SNPPC-800 of 20 nanometers;
Fig. 1 d is the transmission electron microscope picture of the SNPPC-800 of 5 nanometers;
Fig. 1 e is the X-ray energy spectrogram scanning area of SNPPC-800;
Fig. 1 g is that the X-ray energy spectrogram nitrogen of SNPPC-800 is swept;
Fig. 1 h is that the X-ray energy spectrogram sulfur of SNPPC-800 is swept;
Fig. 1 f is that the X-ray energy spectrogram carbon of SNPPC-800 is swept;
Fig. 1 i is that the X-ray energy spectrogram phosphorus of SNPPC-800 is swept;
Fig. 2 is the X-ray diffractogram of 4 kinds of different SNPPC products;
Fig. 3 is the Raman x ray diffration pattern x of 4 kinds of different SNPPC products;
Fig. 4 is the x-ray photoelectron spectroscopy wide range figure of 4 kinds of different SNPPC products;
Fig. 5 is the N of 4 kinds of different SNPPC products2Adsorption curve;
Fig. 6 is the graph of pore diameter distribution of 4 kinds of different SNPPC products;
Fig. 7 is that SNPPC-800 and SNPPC-700 is at 100mA.g-1Cycle performance figure;
Fig. 8 is that SNPPC-800 and SNPPC-700 is at 500mA.g-1Cycle performance figure;
Fig. 9 is that SNPPC-800 and SNPPC-700 is at 1000mA.g-1Cycle performance figure;
Figure 10 is the high rate performance figure of SNPPC-800 and SNPPC-700;
Figure 11 all material is at the linear voltammogram of 1600rpm;
Figure 12 is all material K-L line when 0.365V;
Figure 13 is SNPPC-800, NPC-800 and the electron number of business Pt/C (20% load capacity);
Figure 14 is the mithridatism of SNPPC-800 and Pt/C (20 % load capacity);
Figure 15 is the ultracapacitor CV figure of SNPPC-800;
Figure 16 is the ultracapacitor high rate performance figure of SNPPC-800;
Figure 17 is the ultracapacitor high rate performance figure of SNPPC-800, SNPPC-700 and SNPC-800;
Figure 18 is SNPPC-800 ultracapacitor cycle life figure.
Detailed description of the invention
With specific embodiment, technical scheme is described further below, but protection scope of the present invention does not limits
In this:
The preparation of embodiment 1 meso-porous carbon material SNPPC-800
Weigh thiazolamine (0.1282g), sodium dihydrogen phosphate (0.1536g), and manual mixing uniform, afterwards by 2-amino
Thiazole is placed on two-layer ZnCl2In the middle of (each 0.1736g) material, in sandwich-like, then it is placed in quartz boat, is placed in tube furnace,
N2(speed is 30ml/min) it is warmed up to each temperature section with 5 DEG C/min under atmosphere and keeps 2h, obtain black powder, with 35%
Hydrochloric acid washes away the ZnCl of residual2, wash 3 times with deionized water and ethanol, at 80 DEG C of vacuum drying oven, be dried 3h, finally in tubular type
N in stove2Under (speed is 30ml/min) atmosphere, 200 DEG C keep 2h, obtain the P of high S content, the meso-porous carbon material of S, N codope
SNPPC-800, S content is up to 12.58%, and specific surface area reaches 1122.46m2/g。
The S of the high S content that the present invention obtains, the meso-porous carbon material of N, P codope is as fuel cell oxygen reduction catalyst
Application, its performance test methods is as follows:
Weigh 2mg catalyst SNPPC-800,0.2ml 5% nafion solution and the ethanol of 1.8ml in 10ml centrifuge tube
In, ultrasonic disperse is uniform.The aluminium oxide of the glass-carbon electrode 0.05/0.3mm of 4mm is polished, next rinses well with water.Will
The above-mentioned solution of 10 μ l is added dropwise on glass-carbon electrode, is dried under infrared lamp.Cyclic voltammetry is from Shanghai occasion China
CHI760E electrochemical workstation, this test is carried out in the electrolysis bath of three-electrode system, and Ag/AgCl is reference electrode, platinum filament
Electrode is to electrode, and glass-carbon electrode is working electrode, and electrolyte is 0.1M KOH, first leads to O230 min, make electricity
Solving liquid and be in saturated oxygen state, surface sweeping speed is 10mVs-1, voltage range is-1.0 to 0.2V.Linear volt-ampere test be
CHI760E electrochemical workstation and RRDE-3A(ALS) on carry out, surface sweeping speed is 10mVs-1, working electrode is the glass carbon of 4mm
Electrode, Ag/AgCl is reference electrode, and platinum electrode is to electrode, and electrolyte is 0.1M KOH, first leads to O2 30
Min, rotating speed is from 400 to 2025rpm, and the electrode difference between Ag/AgCl electrode and RHE is 0.965V.
The S of the high S content that the present invention obtains, the meso-porous carbon material of N, P codope answering as cathode of lithium battery catalyst
With, its performance test methods is as follows:
Under an argon atmosphere, in glove box, complete CR2025 button half-cell assemble.Active substance, Kynoar
(PVDF), transduction agent (super-P) mix in N-Methyl pyrrolidone with the ratio of 75:15:15, above-mentioned mixed liquor is coated with uniformly
On the Copper Foil of a diameter of 12nm, being dried, tabletting obtains working electrode, and working electrode sample size is about 3mg(2-3mg. cm-2), lithium sheet is as reference electrode with to electrode.The LiPF of 1M6/ (EC+DMC) (volume ratio is 1:1) is electrolyte, and barrier film is
Celgard(2300).Constant current charge-discharge test uses certain electric current density that simulated battery is carried out charge-discharge performance test, fills
Discharge test voltage range is 0.0-3 .0 V, uses secondary cell performance detecting system < Shenzhen new Weir limited public affairs of electronics
Department) gather its charging and discharging curve and capacity.Cyclic voltammetry sweep speed is during 0.1mV/S, voltage to be 0.0-3 .0
V, the instrument of use is CHI660D electrochemical workstation.Electrochemical impedance test electrochemical impedance test frequency is 0.01 to arrive
105Hz, instrument is CHI660D and Zahner Zenniwn electrochemical workstation.
The S of the high S content that the present invention obtains, the meso-porous carbon material of N, P codope answering as ultracapacitor catalyst
With, its performance test methods is as follows:
Ultracapacitor three-electrode system is tested, and Hg/HgO electrode is as reference electrode.Platinum electrode as to electrode,
6 M KOH are as electrolyte.Working electrode is by the active substance of mixing 80%, the super-P of 15%, poly-the four of 5% in ethanol solution
Fluorothene binding agent is dried to obtain.Charge-discharge test, cyclic voltammetry and the instrument that EIS test is used and lithium battery test is same
Device.
Fig. 1 can be seen that, obvious SNPPC-800 lamellar is stacked, there is hierarchical porous structure, this explains
SNPPC-800 has 1235m2/ g surface area.
The preparation of embodiment 2 meso-porous carbon material SNPPC-700
Weigh ZnCl2(0.8815g), thiazolamine (0.1282g), ZnCl2(0.8815g), by ZnCl2Thiazolamine is put
In two-layer ZnCl2In the middle of material, in sandwich-like, then it is placed in quartz boat, is placed on N in tube furnace2(30ml/min) under atmosphere with
5 DEG C/min is warmed up to 700 DEG C, keeps 8h, obtains black powder, wash away the ZnCl of residual with the hydrochloric acid of 35%2, use deionized water
Wash 5 times with ethanol, at 80 DEG C of vacuum drying oven, be dried 3h, finally N in tube furnace2(30ml/min) under atmosphere, 200 DEG C of guarantors
Hold 2h, obtain final products S, the meso-porous carbon material SNPPC-700 of N, P codope.
Catalytic oxygen reduction reaction performance test conditions is identical with embodiment 1.
The preparation of embodiment 3 meso-porous carbon material SNPPC-600
Weigh ZnCl2(0.8815g), thiazolamine (0.1282g), ZnCl2(0.8815g), by ZnCl2Thiazolamine is put
In two-layer ZnCl2In the middle of material, in sandwich-like, then it is placed in quartz boat, is placed on N in tube furnace2(30ml/min) under atmosphere with
5 DEG C/min is warmed up to 600 DEG C, keeps 8h, obtains black powder, wash away the ZnCl of residual with the hydrochloric acid of 35%2, use deionized water
Wash several times with ethanol, at 80 DEG C of vacuum drying oven, be dried 3h, finally N in tube furnace2(30ml/min) under atmosphere, 200 DEG C
Keep 2h, obtain final products S, the meso-porous carbon material SNPPC-600 of N, P codope.
Catalytic oxygen reduction reaction performance test conditions is identical with embodiment 1.
The preparation of embodiment 4 meso-porous carbon material SNPPC-500
Weigh ZnCl2(0.8815g), thiazolamine (0.1282g), ZnCl2(0.8815g), by ZnCl2Thiazolamine is put
In two-layer ZnCl2In the middle of material, in sandwich-like, it is placed on N in tube furnace2(30ml/min) it is warmed up to 5 DEG C/min under atmosphere
500 DEG C, keep 8h, obtain black powder, wash away the ZnCl of residual with the hydrochloric acid of 35%2, wash several times with deionized water and ethanol,
3h, finally N in tube furnace it is dried at 80 DEG C of vacuum drying oven2(30ml/min), under atmosphere, 200 DEG C keep 2h, obtain
Finished product S, the meso-porous carbon material SNPPC-500 of N, P codope.
Catalytic oxygen reduction reaction performance test conditions is identical with embodiment 1.
The 4 kinds of products obtaining the present invention and SNPPC-800 carry out elementary analysis and x-ray photoelectron analysis of spectrum, its knot
Fruit is as shown in table 1:
Table 1 SNPPC-500, the elementary analysis of SNPPC-600, SNPPC-700 and SNPPC-800 and x-ray photoelectron
Spectrum result
As seen from Table 1, the S content 3.86% in SNPPC-800 is the highest.
Comparative example:
With business-like 20% Pt/C as comparative sample, its performance test methods is as follows: by 2 mg Pt/C catalyst, 1.8mL
Ethanol: the nafion solution of 200 μ L, ultrasonic disperse 30 minutes, take 10 μ L and drop on platinum carbon electrode, room temperature the most in atmosphere
Condition is dried makes electrode;With this electrode as working electrode, with platinum plate electrode for electrode, with Ag/AgCl as reference electrode
Three-electrode system, carries out linear scanning test in the KOH solution of saturated 0.1 mol/L of oxygen and RDE tests, scanning speed
It is 100 mV/s.
In the accompanying drawing of the present invention, Fig. 4 is the x-ray photoelectron spectroscopy wide range figure of 4 kinds of different SNPPC products;Fig. 5 be 4 kinds not
N with SNPPC product2Adsorption curve;Fig. 6 is the graph of pore diameter distribution of 4 kinds of different SNPPC products;Fig. 7 be SNPPC-800 and
SNPPC-700 is at 100mA.g-1Cycle performance figure;Fig. 8 is that SNPPC-800 and SNPPC-700 is at 500mA.g-1Cyclicity
Can figure;Fig. 9 is that SNPPC-800 and SNPPC-700 is at 1000mA.g-1Cycle performance figure;Figure 10 is SNPPC-800 and SNPPC-
The high rate performance figure of 700;Figure 11 all material is at the linear voltammogram of 1600rpm;Figure 12 is that all material is when 0.365V
K-L line;Figure 13 is SNPPC-800, SNPC-800, SNPPC-700 and the electron number of business Pt/C (20% load capacity);Figure 14
Mithridatism for SNPPC-800 and Pt/C (20 % load capacity);Figure 15 is the ultracapacitor CV figure of SNPPC-800;Figure 16 is
The ultracapacitor high rate performance figure of SNPPC-800;Figure 17 is the super capacitor of SNPPC-800, SNPPC-700 and SNPC-800
Device high rate performance figure;Figure 18 is SNPPC-800 ultracapacitor cycle life figure.
SNPPC-500, SNPPC-600, SNPPC-700, NPC-800 and SNPPC-800 that the present invention is obtained and contrast
Embodiment NPC-800, the various performance tests of business Pt/C (20% load capacity), it is aobvious that its result sees Fig. 1-Figure 11, Fig. 1
The apparent form showing synthesized S, N doping material with carbon element is porous fold impalpable structure;Fig. 2 shows that C, N, S are evenly distributed on
On material with carbon element, the NPC-800 scanning electron microscope of Fig. 3 and the transmission electron microscope photo of Fig. 4 find out that NPC has porous graphene structure, figure
5a has the obvious graphite peaks 002 crystal face corresponding to graphite at 26 °, shows that SNPPC has certain regular graphitization brilliant
District, along with carbonization temperature raises, that peak of 43 ° is significantly raised, and Fig. 5 b shows Raman ID/IGIt is raised to 1.45 by 1.25, Fig. 5 c's
S2p peak in X photoelectron spectroscopy is gradually increased and shows that the unordered doping of more N, S is entered, and Fig. 5 d display specific surface area is up to
1235m2/g;Fig. 6 d display aperture is distributed between 10-45nm;Fig. 8 a showing, SNPPC-800 has 38.77% most pyrroles
Pyridine nitrogen and 43.25% pyrroles's nitrogen;Fig. 9 illustrates that SNPPC-800 has the heat stability being better than Graphene;Figure 10 d illustrates SNPPC-
800 have preferable methanol mithridatism.
SNPPC ORR concrete outcome is shown in accompanying drawing 7,10,800 DEG C of roastings that the best sample of catalytic effect provides for embodiment 1
The nitrogen-doped carbon material burnt, its take-off potential is-0.11V, and electric current density is 2.1mA.cm-2, electrode process transfer electron number is
4;(play spike potential is-0.15V to the nitrogen-doped carbon material that NPC-800 catalyst provides for embodiment 5, and electric current density is
1.2mA.cm-2, electrode process transfer electron number is 2.2);
The SNPPC-800 that embodiment 1 obtains is used for the S of lithium battery by the present invention, the application of the meso-porous carbon material of N, P codope,
When being used as cathode of lithium battery, its performance test methods is as follows:
SNPPC-800 installs to be evaluated in CR2025 battery in glove box, and SNPPC-800, super-P, PVDF are with 70:15:15
Ratio be dispersed in nmp solution, 3mg on working electrode figure, lithium paper tinsel is used for doing electrode and reference electrode, EC and DMC1:1 of 1M
LiPF6For electrolyte.
SNPPC-800 negative material first lap charge/discharge capacity is 1340.66 and 678.35mAhg-1(100 mAg-1), storehouse
Human relations efficiency 99%, after 50 circles, capacity can reach 675.1 mAhg-1, 0.1,0.25,0.5, and 1 mAg-1Under appearance
Amount is respectively 720.2,671.3,570.6, and 467.5 mAhg-1, after 55 circles, return to 630.5 mAhg-1, have preferably
Cycle performance and high rate performance, NPC-800 poor-performing.Concrete outcome is shown in accompanying drawing 11.
The foregoing is only the section Example of the present invention, be not used for limiting the present invention.In every case according to present invention institute
Impartial change and the modification done, within being all protection scope of the present invention.
We characterize the loose structure of SNPPC with scanning electron microscope and transmission electron microscope.Fig. 1 a can be seen that SNPPC-800 has
There is hierarchical porous structure, aperture about 2-5 μm.Fig. 1 b-1c low power transmission electron microscope can be seen that SNPPC-800 has obvious exception
Carbon-coating is around cavity structure, the similar porous carbon structure reported before.Fig. 1 d high power transmission electron microscope can see aperture 5-20nm's
Unformed mesoporous carbon structure.Fig. 1 e-i element cap is it can be seen that C, N, S, P are evenly distributed on porous carbon skeleton.
Fig. 2 illustrates the XRD of SNPPC-500, SNPPC-600, SNPPC-700 and SNPPC-800, and these materials are at 26 °
Two obvious graphite peaks are had, corresponding to 002 crystal face and 100 crystal faces, along with temperature raises, 002 crystal face place peak angle degree with 43 °
Taper into, show that carbon-coating spacing becomes larger along with temperature raises.The peak of 43 ° is gradually increased, and shows that 100 crystal faces stack more
In order.When temperature increases to 900 DEG C, we have obtained ZnS, XRD and have demonstrated a bit further, this is because organic point of high temperature
Whole decomposition of son.
Raman spectrum is further utilized to probe into the internal structure of SNPC, 1330cm-1Corresponding to sp3Defect, 1585cm-1Corresponding
Sp in face2Carbon shakes.Fig. 3 is it can be seen that along with the increase of carburizing temperature, ID/IGFrom 1.17 gradually to 1.37, SNPPC-
The I of 800D/IGMore than other samples, this shows owing to the substantial amounts of defect of high temperature is introduced in SNPPC-800.Table 1 elementary analysis
(EA) content of C, N, S of SNPPC is tested.SNPPC-500 has the N content of the highest 14.03%, but, it is not institute
Some N enter in lattice.The N content of SNPPC-600, SNPPC-700 and SNPPC-800 is respectively 12.63wt%,
6.94 wt% and 8.17 wt%.Along with temperature increases to 25.05wt% from 500 to 700 DEG C of risings, S content from 8.25 wt%,
SNPPC-800 S content drops to 12.58%, and this is due to the vaporization of fractional load S on carbon framework.ICP-OES can see
Go out the P content of SNPPC-800 and SNPPC-700 be respectively 1.07 wt% and 0.31%, SNPPC-500 and SNPPC-600 XPS and
ICP-OES is not detected by P, shows that low temperature P can not be doped in C framework.The S content of SNPPC-700 and SNPPC-800
Higher than other documents of report, this is owing to the doping of P and phosphorus source.When with triphenylphosphine as phosphorus source, SNPPC-800 only has
The S of 8.69%.The difference of S content is mainly due to oxy radical in sodium dihydrogen phosphate can improve S in SNPPC-800 with receiving
Content.
XPS illustrates composition and the chemical environment of each element in SNPPC.Fig. 4 XPS illustrates C1s peak (284.5 eV
), O1s peak (532.5 eV), N1s peak (399.2 eV) and visible S2p peak (162.3 eV).SNPPC-
It is found that P2p (133.30 eV) peak in 700 and SNPPC-800, but does not send out in SNPPC-500 and SNPPC-600
Existing.The existence at O1s peak is owing to the oxygen in the air of the oxygen in sodium dihydrogen phosphate in raw material and absorption and water.
N2Adsorption/desorption is used for studying specific surface area and the pore-size distribution of SNPPC.From fig. 5, it can be seen that SNPPC-500 and
SNPPC-600 sample is at P/P00.4 does not has hysteresis loop, and SNPPC-700 and SNPPC-800 has hysteresis loop, is typical Jie
Porous materials.SNPPC-500 and SNPPC-600 simply have accumulated the fragment of cracking presoma, and orderly loose structure is 700 Hes
800 DEG C of generations, PXRD and TGA demonstrates this result.By calculating BET specific surface area, SNNPC-500, SNNPC-600,
The specific surface area of SNNPC-700 and SNNPC-800 is respectively 48.93,569.92,712.4 and 1122.46 m2/g .Fig. 6
It can be seen that the BJH pore diameter range of SNPPC-800 is 20-50nm.Along with carburizing temperature raises, specific surface area is gradually increased.Relatively
Big specific surface area and wider pore-size distribution advantageously reduce energy barrier, improve substrate transmission.
Lithium cell cathode material is tested
SNPPC-800 and SNPPC-700 installs to use three-electrode system in CR2025 battery as cathode of lithium battery in glove box
Being evaluated, all of specific capacity obtains according to active substance.7 illustrate 0.1A.g-1Lower lithium battery cycle performance, SNPPC-
800 negative material first lap charge/discharge capacities are 2475.89 and 1134.11 mAhg-1, coulombic efficiency is 45.81%, owing to by
The irreversible capacity that SEI layer causes.Coulombic efficiency after SNPPC-800 50 circle is 99.47%, shows higher storage lithium and de-lithium
Performance.After enclosing 50, SNPPC-800 illustrates the highest reversible capacity 977.68 mA.h.g-1, NPC-800, SPC-800,
SNPC-800 and SNPPC-700 is respectively 346,386,630 and 855 mA.h.g-1。
Long-range circulation cyclical stability under checking high current density further.Fig. 8-9 shows, SNPPC-800 is at 500mA
g─1Under, circulation 150 circle, capacity still can reach 799.15 mA.h.g─1, 1000mA g─1Under, circulation 200 circle, capacity is
599.63 mA.h.g─1.Even if showing SNPPC-800 at higher current densities, preferable cyclical stability still can be kept.
S content lithium preferable for SNPPC-800 electrical property plays a vital effect.
Figure 10 illustrates from 100 to 1000 mA g-1High rate performance, corresponding irreversible capacity is respectively 0.10,
0.25, 0.50, 1.0 A∙g-1Under 1098.07,928.86,750.63 and 606.54 mA.h.g─1.Along with electric current is close
Degree is gradually increased.Irreversible capacity is gradually reduced owing to the dynamics Controlling electrochemically converted.When electric current density returns to 0. 1A
∙g-1, after 80 circles, irreversible capacity still reaches 1023.19 mA.h g─1.Reversible capacity be always better than SNPPC-700 (
890.92 mA.h.g─1) and SNPC-800 (630.5 mA.h.g─1 ).
The preferable lithium battery capacity of SNPPC-800 is owing to high S content and bigger specific surface area, three-dimensional SNPPC-800
High specific surface area and orderly passage, it is provided that substantial amounts of lithium ion stores and diffusion admittance.Compare and SNPC and forefathers
Report, S content higher for SNPPC-800, create substantial amounts of defect, neighbouring carbon is created effective electronic effect, carries
The absorption of high lithium ion and transmission.Therefore, big specific surface area and N, S synergism is for storage lithium excellent for SNPPC-800
Performance plays an important role.
Fuel battery negative pole oxygen reduction reaction
In order to study the ORR activity of SNPPC, at full O20.1 M KOH in three-electrode system in test, scanning speed
Rate is 10 mV. s-1.Figure 11 illustrates the RDE scan line of different materials 1600rpm.SNPPC-800 no matter electric current density or
Take-off potential is all better than 20 wt% Pt/C and other SNPPC material, and this causes substantial amounts of avtive spot owing to doping.
From the LSV line of different electromotive forces, we have obtained K-L line (Figure 12), and these lines illustrate preferable linear relationship, and it is right to imply that
O2First order kinetics reaction and same electron transfer number.The K-L line of SNPC-800 is higher than other SNPC sample and SPC-
800 and NPC-800 samples, and close to Pt/C.Based on K-L line, Figure 13 can be seen that SNPPC-800, SNPPC-700, SNPC-
800 and the Pt/C ORR electron numbers shifted at 0.365V are respectively 3.5, and 4.3,4.1,4.2(units are J), show SNPPC-
800 and Pt/C ORR follow 4 electronics mechanism, and this result is similar with the doping porous material reported before.In order to contrast, figure
4.26 to 4.28 RDE and the K-L lines illustrating SNPPC-500, SNPPC-600 and SNPPC-700.
The life test of SNPPC-800 and Pt/C is obtained by chronoamperometry.In fig. 14, we are under 0.365V
Testing 2000 circles, SNPPC-800 illustrates the electric current density reserved of higher 96.08%, and after Pt/C encloses 2000
Have lost 33.06%.Show that SNPPC-800 has the cyclical stability more than Pt/C.
Ultracapacitor performance test
In order to study the ultracapacitor performance of SNPPC-800, CV first in 6 M KOH electrolyte three-electrode system enter
Row test.Figure 15 illustrates SNPPC-800 CV under the sweep speed different for 100 mV/s from 5, when sweep speed is from 5
to 20 mV s−1, we can see that CV is a similar rectangular configuration, show the existence of double layer capacitor.Work as scanning
Speed is from 50 to 100mV/s, it has been found that the deformation of rectangle, owing to the existence of the fake capacitance that doping causes.And SNPPC
700 compare with SNPC 800, and SNPPC-800 has the area of maximum, represents the high electric capacity caused due to high S content.
Figure 16 further illustrate under different electric current densities SNPPC 800, SNPPC 700 and SNPC 800 super
Capacitor charging/discharging curve.GCD result somewhat with linearly have a deviation, corresponding to N, S, P doping porous carbon current response.From
Figure 17 is it can be seen that SNPC 800, SNPPC 700 and SNPPC 800 are at 0.5 A g−1Under specific capacity be respectively
142.3,202.5 and 227.5 F.g−1, at 10 A g−1Under specific capacity be respectively 96.25,141.25 and 160.0 F
g −1.Figure 18 illustrates at 10 A g−1Under, the cyclical stability of 6000 circles.After enclosing 6,000, specific capacity is 160.29
F g−1, show the cyclical stability of excellence.
Claims (9)
1. a P for high S content, the synthetic method of the meso-porous carbon material of S, N codope, it is characterised in that with thiazolamine and
Sodium dihydrogen phosphate is raw material, ZnCl2For catalysts and solvents, under nitrogen atmosphere, above-mentioned raw materials is put into one-step method in tube furnace
Synthesize the P of high S content, the meso-porous carbon material of S, N codope.
The P of a kind of high S content the most according to claim 1, the synthetic method of the meso-porous carbon material of S, N codope, it is special
Levy and be to specifically comprise the following steps that
1) with thiazolamine for N source and S source, sodium dihydrogen phosphate is P source, and manual mixing is uniform, and forms three with zinc chloride
Mingzhi's structure, places in quartz boat;
2) quartz boat that step 1) obtains is put in tube furnace, at N2It is warming up to 800 DEG C with 5 DEG C/min, each temperature under atmosphere
Section keeps 2h, and one-step method obtains the P of high S content, the meso-porous carbon material of S, N codope;
3) step 2 is taken out) reacted quartz boat, by the product in quartz boat with the salt acid elution of 35%, remove zinc chloride, then
Remove hydrochloric acid by deionized water and washing with alcohol, then product is dried at vacuum drying oven, obtains product SNPPC-after drying
800。
The P of a kind of high S content the most according to claim 2, the synthetic method of the meso-porous carbon material of S, N codope, it is special
Levy and be step 2) in N2Flow velocity is 28-35 ml/min, preferably 30ml/min.
The P of a kind of high S content the most according to claim 2, the synthetic method of the meso-porous carbon material of S, N codope, it is special
Levying and be in step 3) that vacuum drying oven temperature is 75-85 DEG C, drying time is 2.5-3.5h.
The P of a kind of high S content the most according to claim 2, the synthetic method of the meso-porous carbon material of S, N codope, it is special
Levying and be in step 3) that vacuum drying oven temperature is 80 DEG C, drying time is 3h.
The P of a kind of high S content the most according to claim 1, the synthetic method of the meso-porous carbon material of S, N codope, it is special
Levying and be in SNPPC-800 product, its S content is up to 12.58%, and specific surface area reaches 1122.46m2/g。
7. a S for high S content according to claim 1, the meso-porous carbon material of N, P codope is urged as cathode of lithium battery
The application of agent.
8. a S for high S content according to claim 1, the meso-porous carbon material of N, P codope is as fuel cell oxygen also
The application of raw catalyst.
9. a S for high S content according to claim 1, the meso-porous carbon material of N, P codope is urged as ultracapacitor
The application of agent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610311775.XA CN106006599B (en) | 2016-05-11 | 2016-05-11 | A kind of P of high S contents, S, the synthetic method of the meso-porous carbon material of N codopes and its application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610311775.XA CN106006599B (en) | 2016-05-11 | 2016-05-11 | A kind of P of high S contents, S, the synthetic method of the meso-porous carbon material of N codopes and its application |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106006599A true CN106006599A (en) | 2016-10-12 |
CN106006599B CN106006599B (en) | 2018-06-12 |
Family
ID=57100509
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610311775.XA Active CN106006599B (en) | 2016-05-11 | 2016-05-11 | A kind of P of high S contents, S, the synthetic method of the meso-porous carbon material of N codopes and its application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106006599B (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106629723A (en) * | 2016-12-30 | 2017-05-10 | 扬州大学 | Biomass-based N, S and P-containing co-doped porous carbon and application thereof |
CN107369833A (en) * | 2017-07-01 | 2017-11-21 | 中国科学院兰州化学物理研究所 | A kind of preparation method of network-like carbon negative pole material |
CN107706403A (en) * | 2017-11-20 | 2018-02-16 | 中国科学院过程工程研究所 | A kind of complex carbon material and the modified electrode material and lithium ion battery using its preparation |
CN108493424A (en) * | 2018-04-11 | 2018-09-04 | 中科锂电新能源有限公司 | A kind of nitrogen phosphate and sulfur codope complex carbon material, preparation method and lithium ion battery |
CN109012749A (en) * | 2018-08-14 | 2018-12-18 | 青岛科技大学 | Nonmetallic difunctional VPO catalysts and its preparation method and application based on ZIF-8 phosphorus sulphur codope |
CN110038638A (en) * | 2019-05-17 | 2019-07-23 | 浙江工业大学 | A kind of iron load nitrogen-doped porous carbon material and its synthetic method and application with excellent electro-catalysis reduction nitrogen performance |
CN111082079A (en) * | 2019-12-30 | 2020-04-28 | 上海交通大学 | Bifunctional oxygen electrocatalyst material and preparation method and application thereof |
US10693139B2 (en) * | 2016-08-12 | 2020-06-23 | Korea Advanced Institute Of Science And Technology | Carbonaceous structure and method for preparing the same, electrode material and catalyst including the carbonaceous structure, and energy storage device including the electrode material |
CN114497593A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Phosphorus-boron doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof |
CN114715871A (en) * | 2022-04-26 | 2022-07-08 | 张粒新 | Modified lithium iron phosphate cathode material for lithium battery and preparation method |
CN116459857A (en) * | 2023-04-24 | 2023-07-21 | 安徽大学 | High-selectivity catalyst Co/NS800, preparation method thereof and method for selectively hydrogenating p-chloronitrobenzene in heterogeneous system |
WO2023160605A1 (en) * | 2022-02-23 | 2023-08-31 | 中国石油化工股份有限公司 | Sulfur-modified carbon material, preparation method therefor, and application thereof |
CN116459857B (en) * | 2023-04-24 | 2024-04-19 | 安徽大学 | High-selectivity catalyst Co/NS800, preparation method thereof and method for selectively hydrogenating p-chloronitrobenzene in heterogeneous system |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6751990B2 (en) * | 2001-03-06 | 2004-06-22 | Council Of Scientific And Industrial Research | Process for making rare earth doped optical fiber |
CN103714979A (en) * | 2013-12-20 | 2014-04-09 | 北京化工大学 | Phosphor-doped porous carbon material for super capacitor and preparation method thereof |
CN103911151A (en) * | 2014-04-14 | 2014-07-09 | 河南师范大学 | Sulfur phosphorus nitrogen co-doped carbon point with adjustable fluorescence property and preparation method of sulfur phosphorus nitrogen co-doped carbon point |
CN104987863A (en) * | 2015-06-25 | 2015-10-21 | 西安交通大学 | Nitrogen, phosphorus and sulphur doping or co-doping carbon dot and batch controllable preparing method and application thereof |
CN105206845A (en) * | 2015-08-20 | 2015-12-30 | 浙江工业大学 | Method for synthesizing an S and N synergistic mesoporous carbon material with excellent ORR and lithium-ion electric performance through one-step method |
CN105457666A (en) * | 2015-12-07 | 2016-04-06 | 北京理工大学 | Nitrogen and phosphorus co-doped porous carbon catalyst and preparation method thereof |
-
2016
- 2016-05-11 CN CN201610311775.XA patent/CN106006599B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6751990B2 (en) * | 2001-03-06 | 2004-06-22 | Council Of Scientific And Industrial Research | Process for making rare earth doped optical fiber |
CN103714979A (en) * | 2013-12-20 | 2014-04-09 | 北京化工大学 | Phosphor-doped porous carbon material for super capacitor and preparation method thereof |
CN103911151A (en) * | 2014-04-14 | 2014-07-09 | 河南师范大学 | Sulfur phosphorus nitrogen co-doped carbon point with adjustable fluorescence property and preparation method of sulfur phosphorus nitrogen co-doped carbon point |
CN104987863A (en) * | 2015-06-25 | 2015-10-21 | 西安交通大学 | Nitrogen, phosphorus and sulphur doping or co-doping carbon dot and batch controllable preparing method and application thereof |
CN105206845A (en) * | 2015-08-20 | 2015-12-30 | 浙江工业大学 | Method for synthesizing an S and N synergistic mesoporous carbon material with excellent ORR and lithium-ion electric performance through one-step method |
CN105457666A (en) * | 2015-12-07 | 2016-04-06 | 北京理工大学 | Nitrogen and phosphorus co-doped porous carbon catalyst and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
SHULIANG YANG等: "Nitrogen, Phosphorus, and Sulfur Co-Doped Hollow Carbon Shell as Superior Metal-Free Catalyst for Selective Oxidation of Aromatic Alkanes", 《ANGEW. CHEM. INT. ED.》 * |
YAO ZHOU等: "Phosphorus/sulfur Co-doped porous carbon with enhanced specific capacitance for supercapacitor and improved catalytic activity for oxygen reduction reaction", 《JOURNAL OF POWER SOURCES》 * |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10693139B2 (en) * | 2016-08-12 | 2020-06-23 | Korea Advanced Institute Of Science And Technology | Carbonaceous structure and method for preparing the same, electrode material and catalyst including the carbonaceous structure, and energy storage device including the electrode material |
CN106629723A (en) * | 2016-12-30 | 2017-05-10 | 扬州大学 | Biomass-based N, S and P-containing co-doped porous carbon and application thereof |
CN107369833A (en) * | 2017-07-01 | 2017-11-21 | 中国科学院兰州化学物理研究所 | A kind of preparation method of network-like carbon negative pole material |
CN107706403A (en) * | 2017-11-20 | 2018-02-16 | 中国科学院过程工程研究所 | A kind of complex carbon material and the modified electrode material and lithium ion battery using its preparation |
CN108493424A (en) * | 2018-04-11 | 2018-09-04 | 中科锂电新能源有限公司 | A kind of nitrogen phosphate and sulfur codope complex carbon material, preparation method and lithium ion battery |
CN108493424B (en) * | 2018-04-11 | 2020-11-03 | 中科锂电新能源有限公司 | Nitrogen, phosphorus and sulfur co-doped composite carbon material, preparation method thereof and lithium ion battery |
CN109012749A (en) * | 2018-08-14 | 2018-12-18 | 青岛科技大学 | Nonmetallic difunctional VPO catalysts and its preparation method and application based on ZIF-8 phosphorus sulphur codope |
CN110038638A (en) * | 2019-05-17 | 2019-07-23 | 浙江工业大学 | A kind of iron load nitrogen-doped porous carbon material and its synthetic method and application with excellent electro-catalysis reduction nitrogen performance |
CN111082079A (en) * | 2019-12-30 | 2020-04-28 | 上海交通大学 | Bifunctional oxygen electrocatalyst material and preparation method and application thereof |
CN111082079B (en) * | 2019-12-30 | 2021-01-22 | 上海交通大学 | Bifunctional oxygen electrocatalyst material and preparation method and application thereof |
CN114497593A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Phosphorus-boron doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof |
CN114497593B (en) * | 2020-10-23 | 2024-04-02 | 中国石油化工股份有限公司 | Phosphorus-boron doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof |
WO2023160605A1 (en) * | 2022-02-23 | 2023-08-31 | 中国石油化工股份有限公司 | Sulfur-modified carbon material, preparation method therefor, and application thereof |
CN114715871A (en) * | 2022-04-26 | 2022-07-08 | 张粒新 | Modified lithium iron phosphate cathode material for lithium battery and preparation method |
CN114715871B (en) * | 2022-04-26 | 2023-09-12 | 四川朗晟新材料科技有限公司 | Modified lithium iron phosphate positive electrode material for lithium battery and preparation method |
CN116459857A (en) * | 2023-04-24 | 2023-07-21 | 安徽大学 | High-selectivity catalyst Co/NS800, preparation method thereof and method for selectively hydrogenating p-chloronitrobenzene in heterogeneous system |
CN116459857B (en) * | 2023-04-24 | 2024-04-19 | 安徽大学 | High-selectivity catalyst Co/NS800, preparation method thereof and method for selectively hydrogenating p-chloronitrobenzene in heterogeneous system |
Also Published As
Publication number | Publication date |
---|---|
CN106006599B (en) | 2018-06-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106006599A (en) | Synthesizing method and application of high-S-content P-S-N-codoped mesoporous carbon material | |
Wang et al. | Unique MOF-derived hierarchical MnO 2 nanotubes@ NiCo-LDH/CoS 2 nanocage materials as high performance supercapacitors | |
Mao et al. | Large‐Area, Uniform, Aligned arrays of Na3 (VO) 2 (PO4) 2F on carbon nanofiber for quasi‐solid‐state Sodium‐Ion hybrid capacitors | |
Zhou et al. | Symmetric sodium-ion battery based on dual-electron reactions of NASICON-structured Na3MnTi (PO4) 3 material | |
Li et al. | Reversible aluminum‐ion intercalation in prussian blue analogs and demonstration of a high‐power aluminum‐ion asymmetric capacitor | |
CN103779564B (en) | High-performance vanadium phosphate sodium symmetric form sodium-ion battery material and its preparation method and application | |
CN101800131B (en) | Active carbon-based material and preparation method thereof | |
CN103441259B (en) | A kind of high magnification aquo-base metal electrochemical cells positive electrode and preparation method thereof | |
Dai et al. | Flexible Hierarchical Co‐Doped NiS2@ CNF‐CNT Electron Deficient Interlayer with Grass‐Roots Structure for Li–S Batteries | |
Chen et al. | In-situ thermally fabricated porous and heterogeneous yolk-shell selenides wrapped in carbon as anode for high-performance hybrid lithium-ion capacitors | |
Liang et al. | Epitaxial growth induced multilayer yolk-shell structured CoSe2 with promoting transport kinetics of sodium ion half/full batteries | |
CN105810912A (en) | Three-dimensional graded carbon-clad NaTi<2>(PO<4>)<3>/C micrometer flower electrode material and preparation method and application thereof | |
CN105900267A (en) | Tungsten-based material super battery and supercapacitor | |
CN108199041A (en) | A kind of modified phosphate iron lithium material, preparation method and application | |
CN106449128A (en) | Integrated heteropolyacid-modified polyaniline/titanium nitride core-shell nanowire array composite material and preparation method and application thereof | |
CN106784651A (en) | Connection nano-material and its preparation method and application in carbon-encapsulated iron potassium manganate | |
CN109037718A (en) | A kind of biomass carbon carried transition metal oxide composite and the preparation method and application thereof | |
CN108899522A (en) | A kind of high-volume silicon-carbon negative electrode material, preparation method and application | |
CN103474671B (en) | A kind of lithium-air battery carbon-lithium peroxide anode and preparation method thereof | |
Lan et al. | Structural engineering of metal-organic frameworks cathode materials toward high-performance flexible aqueous rechargeable Ni–Zn batteries | |
CN105206845B (en) | One-step synthesis method has the S of excellent ORR and lithium electrical property, the meso-porous carbon material method of N synergies | |
Wu et al. | Nanosized Ti4O7 supported on carbon nanotubes composite modified separator for enhanced electrochemical properties of lithium sulfur battery | |
Yang et al. | Engineering the electronic structure of Fe-N/C catalyst via fluorine self-doping for enhanced oxygen reduction reaction in liquid and all-solid-state Zn-air batteries | |
Zhang et al. | Multiplying Light Harvest Driven by Hybrid‐Reflections 3D Electrodes Achieves High‐Availability Photo‐Charging Zinc‐Ion Batteries | |
Dong et al. | Atomically dispersed Co-N4C2 catalytic sites for wide-temperature Na-Se batteries |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |