CN115465862A - Agar-derived nitrogen-doped porous carbon material and preparation method and application thereof - Google Patents

Agar-derived nitrogen-doped porous carbon material and preparation method and application thereof Download PDF

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CN115465862A
CN115465862A CN202211148864.9A CN202211148864A CN115465862A CN 115465862 A CN115465862 A CN 115465862A CN 202211148864 A CN202211148864 A CN 202211148864A CN 115465862 A CN115465862 A CN 115465862A
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porous carbon
agar
carbon material
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沙靖全
张志明
王通
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Jining University
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Abstract

The invention discloses an agar-derived nitrogen-doped porous carbon material and a preparation method and application thereof, and belongs to the technical field of lithium battery cathode materials. The technical scheme is as follows: adding agar, urea and potassium hydroxide into distilled water, heating and stirring to promote the agar to dissolve to form hydrogel, and drying the mixture; and pyrolyzing the dried material in nitrogen at 720-780 ℃, washing the obtained material with an acid solution and distilled water, washing away residual potassium hydroxide, and drying to obtain the nitrogen-doped porous carbon material derived from agar. The method has the advantages of simple process and low energy consumption, and the prepared agar-derived nitrogen-doped porous carbon material has low cost and excellent electrochemical performance, and shows great potential as an LIB cathode.

Description

Agar-derived nitrogen-doped porous carbon material and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium battery cathode materials, in particular to a nitrogen-doped porous carbon material derived from agar and a preparation method and application thereof.
Background
The lithium ion battery energy storage technology is considered as the most promising large-scale energy storage technology due to the advantages of good stability, no memory effect, large energy density and the likeOne of the procedures is disclosed. It is believed that the properties of the electrode material largely determine the performance of LIBs, but conventional graphite-based cathode materials have low specific capacities (theoretical capacity 372mAh · g) -1 ) And rate capability, thereby limiting the wide application of graphite-based cathode materials. To date, many non-carbon based cathode materials (metal compounds) and carbonaceous materials (graphene, carbon nanotubes, porous carbon) have been carefully studied and expected to be able to replace graphite to achieve better LIB performance. Carbon materials are still considered to be the most commercially valuable negative electrode materials based on balancing specific capacity and process cost.
Porous Carbon (PC), a typical amorphous carbon material, is considered to have great potential as a commercial cathode material for LIBs batteries due to its high cost performance and environmental friendliness. To date, the preparation of PC using fossil fuels, polymers and biomass as precursors has been extensively studied and reported, but there have been few studies and reports on the preparation of PC using agar extracted from seaweeds, which is widely available, abundant in sources, inexpensive, and high in carbon content, as precursors and as LIBs negative electrode materials, and there has been no report on the improvement of the electrochemical properties of PC by N doping. The preparation of heteroatom-doped PC is generally achieved by templating and in situ pyrolysis (including physical and chemical activation), and the high process cost and energy consuming processes further limit their true commercial applications.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method overcomes the defects of the prior art, and provides the agar-derived nitrogen-doped porous carbon material, and the preparation method and the application thereof.
The technical scheme of the invention is as follows:
in a first aspect, the invention provides a method for preparing an agar-derived nitrogen-doped porous carbon material, comprising the steps of adding agar, urea and potassium hydroxide into distilled water, heating and stirring to promote dissolution of the agar to form a hydrogel, and then drying the mixture; and pyrolyzing the dried material in nitrogen at 720-780 ℃, washing the obtained material with an acid solution and distilled water, washing away residual potassium hydroxide, and drying to obtain the nitrogen-doped porous carbon material derived from agar.
Preferably, the mass ratio of the agar to the urea to the potassium hydroxide is 1: (0.5-2): (0.5-1.5).
Preferably, the heating and stirring temperature is 75-120 ℃ and the time is 1-2h.
Preferably, the temperature for the first drying is 90-120 ℃, and the drying time is 5-12h.
Preferably, the heating rate during pyrolysis is 2-4 ℃/min, and if the heating rate is too fast, a more appropriate pore diameter cannot be obtained.
Preferably, the temperature of the second drying is 80-150 ℃, and the drying time is not less than 12h.
In a second aspect, the present invention provides an agar-derived nitrogen-doped porous carbon material prepared by the above preparation method.
In a third aspect, the invention also provides the agar-derived nitrogen-doped porous carbon material applied to a lithium battery negative electrode material.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a nitrogen-doped porous carbon material based on agar derivation, a preparation method thereof and application thereof as a lithium ion battery cathode material. The invention adopts agar which is abundant in source, low in cost and sustainable as a precursor, urea as a nitrogen source and KOH as an activator, and successfully prepares the N-doped porous carbon material in batches by a one-pot pyrolysis method. Since the type of the activator can influence the morphology of the porous carbon, and the calcination temperature is one of the key factors influencing the activity of the activator and the morphology and the doping element content of the porous carbon, the invention systematically researches the type (H) of the activator 3 PO 4 And KOH) and carbonization temperatures (600 ℃, 750 ℃ and 900 ℃) on the morphology and doping elements of the porous carbon. The results show that when KOH is chosen as the activator, carbonThe electrochemical performance of the prepared nitrogen-doped porous carbon (NPC-750) is best when the temperature of the reaction is 750 ℃. NPC-750 has 2914m 2 ·g -1 The specific surface area, when used as the negative electrode material of the lithium ion battery, shows ultra-high reversible specific capacity, and is 0.1 A.g -1 The current density of (A) is 1019mA · h · g for 100 cycles -1 At 1 A.g -1 The current density of (A) is 837mA · h · g after 500 cycles -1 At 10A · g -1 Shows remarkable 281 mA.h.g at ultrahigh current density -1 The capacity retention rate after 5000 cycles is 87%, and the great potential of NPC-750 as an LIB cathode is shown. The ultra-low-cost and excellent lithium ion storage performance is extremely rare in the lithium ion battery negative electrode materials reported so far, so that the agar-derived nitrogen-doped porous carbon material prepared by the invention can be used as a potential valuable negative electrode material and can be used as a substitute of graphite.
Drawings
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is an SEM photograph of porous carbon materials prepared in example 1 and comparative examples 1 to 3 according to the present invention, wherein (a) is an SEM photograph of PC-750 prepared in comparative example 3, (b) is an SEM photograph of NPC-750 prepared in example 1, (c) is an SEM photograph of NPC-600 prepared in comparative example 1, and (d) is an SEM photograph of NPC-900 prepared in comparative example 2.
Fig. 2 is an XRD pattern of the porous carbon materials prepared in example 1 of the present invention and comparative examples 1 to 3.
Fig. 3 is a raman spectrum of the porous carbon materials prepared in example 1 of the present invention and comparative examples 1 to 3.
Fig. 4 is a nitrogen adsorption-desorption isotherm of the porous carbon materials prepared in example 1 of the present invention and comparative examples 1 to 3.
FIG. 5 is a porous body prepared according to example 1 of the present inventionCarbon material at 0.5mV s -1 Scanning rate, cyclic voltammetry in the voltage range of 0.01-3.0V.
FIG. 6 shows the measured value at 0.1A · g -1 The charge and discharge curves of the porous carbon material prepared in example 1 of the present invention were obtained in the first three rounds at current density.
FIG. 7 shows that the concentration of the compound is 0.1A · g -1 The charge and discharge curves of the porous carbon material prepared in comparative example 1 of the present invention were obtained in the first three rounds at current density.
FIG. 8 shows a value at 0.1A · g -1 The charge and discharge curves of the previous three rounds of the porous carbon material prepared by the comparative example 2 of the invention are shown under current density.
FIG. 9 shows the measured value at 0.1A · g -1 The charge and discharge curves of the porous carbon material prepared in comparative example 3 of the present invention were obtained in the first three rounds at current density.
FIG. 10 shows a value at 0.1A · g -1 The charge and discharge curves of the previous three rounds of the porous carbon material prepared by the comparative example 4 of the invention are shown under current density.
FIG. 11 shows the measured value at 0.1A · g -1 The charge and discharge curves of the previous three rounds of the porous carbon material prepared by the comparative example 5 of the invention are shown under current density.
FIG. 12 shows a value at 0.1A · g -1 The charge and discharge curves of the previous three rounds of the porous carbon material prepared by the comparative example 6 of the present invention were measured at current density.
FIG. 13 shows a value at 0.1A · g -1 The charge and discharge curves of the porous carbon material prepared in comparative example 7 of the present invention were obtained in the first three rounds at current density.
FIG. 14 shows a temperature at 0.1A · g -1 The cycle stability curve of the porous carbon material prepared in example 1 of the present invention was determined at current density.
FIG. 15 shows a value at 0.1A · g -1 The cycle stability curve of the porous carbon material prepared in comparative example 1 of the present invention was determined at a current density.
FIG. 16 shows a value at 0.1A · g -1 The cycle stability curve of the porous carbon material prepared in comparative example 2 of the present invention was determined at a current density.
FIG. 17 shows a value at 0.1A · g -1 The cycle stability curve of the porous carbon material prepared in comparative example 3 of the present invention at current density.
FIG. 18 is at 0.1A·g -1 The cycle stability curve of the porous carbon material prepared in comparative example 4 of the present invention at current density.
FIG. 19 shows a value at 0.1A · g -1 The cycle stability curve of the porous carbon material prepared in comparative example 5 of the present invention was determined at a current density.
FIG. 20 shows a value at 0.1A · g -1 The cycle stability curve of the porous carbon material prepared in comparative example 6 of the present invention at current density.
FIG. 21 shows a value at 0.1A · g -1 The cycle stability curve of the porous carbon material prepared in comparative example 7 of the present invention at current density.
FIG. 22 shows a graph at 1A · g -1 The cycle stability curve for the porous carbon material prepared in inventive example 1 at current density.
Fig. 23 is a graph of the rate capability of the porous carbon material prepared in example 1 of the present invention at different current densities.
FIG. 24 shows the porous carbon material prepared in example 1 of the present invention at 10A g -1 Cycling stability curve at current density.
Fig. 25 is a comparison of the cycle capacity and rate capacity of lithium batteries assembled with the porous carbon material prepared in example 1 of the present invention as a negative electrode material for lithium batteries and the negative electrode materials disclosed in the related articles.
Detailed Description
In order to make those skilled in the art better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Agar, urea and the activator KOH were added to 20mL of distilled water at a mass ratio of 1. The obtained material is washed by 2M hydrochloric acid and distilled water for several times, and then dried for 12 hours at 80 ℃, and the obtained product is the nitrogen-doped porous carbon material derived from agar, and is named as NPC-750.
Comparative example 1
Comparative example 1 differs from example 1 in that: the material was heated to 600 ℃ in a tube furnace at a heating rate of 3 ℃/min and pyrolysed for 2h under a nitrogen flow. The final product was named NPC-600.
Comparative example 2
Comparative example 2 differs from example 1 in that: the material was heated to 900 ℃ in a tube furnace at a heating rate of 3 ℃/min and pyrolysed for 2h under a nitrogen flow. The final product was named NPC-900.
Comparative example 3
Comparative example 3 differs from example 1 in that: comparative example 3 no urea was added and the final product was designated PC-750.
Comparative example 4
Comparative example 4 differs from example 1 in that: comparative example 4 the activator, phosphoric acid, was used instead of the activator, KOH, of example 1 and the final product was named NPPC-750.
Comparative example 5
Comparative example 5 differs from example 1 in that: in comparative example 5, the mass ratio of agar to urea to potassium hydroxide was 1:1:0.5, and the final product is named NPC-750-1.
Comparative example 6
Comparative example 6 differs from example 1 in that: in comparative example 6, the mass ratio of agar to urea to potassium hydroxide was 1:1:2, the final product is named NPC-750-2.
Comparative example 7
Comparative example 7 differs from example 1 in that: in comparative example 7, the mass ratio of agar to urea to potassium hydroxide was 1:2.5:1, the final product was named NPC-750-3.
Fig. 1 is a Scanning Electron Microscope (SEM) image of the porous carbon materials prepared in example 1 and comparative examples 1 to 3, and it can be seen from the SEM image that the porous carbon materials prepared in example 1 and comparative examples 1 to 3 both show a 3D interconnected network having micro-scale pores. Among them, the NPC-750 prepared in example 1 has a porous structure with thin carbon wall and high porosity, which is advantageous for rapid transportation of Li + between the electrolyte and the porous carbon. While, from the SEM image of NPC-600 prepared in comparative example 1, it can be seen that when the pyrolysis temperature is too low (600 ℃ C.), the porosity becomes very low due to the weak etching effect of the activator KOH at the low calcination temperature. From the SEM image of NPC-900 prepared in comparative example 2, it can be seen that when the pyrolysis temperature is too high (900 ℃), the etching effect of the activator KOH may be very strong (transition etching), and the generated N-containing gas may rapidly evaporate, resulting in pore collapse. From the SEM image of PC-750 prepared in comparative example 3, it can be seen that the absence of N-doped porous carbon results in thicker carbon walls and lower porosity due to the absence of urea etching.
Fig. 2 is an X-ray diffraction pattern of the porous carbon materials prepared in example 1 and comparative examples 1 to 3, and as can be seen from the XRD patterns, the XRD patterns of the porous carbon materials prepared in example 1 and comparative examples 1 to 3 all showed the same diffraction peak characteristics, and a broad diffraction peak at 23.6 ° and an insignificant peak at nearly 43 ° were observed on the (002) and (100) crystal planes of carbon, indicating that the structure of carbon was destroyed and amorphous carbon was formed. According to Bragg's law, the average d-spacing of the (002) plane of the NPC-750 prepared in example 1 is about 0.376 nm, and the interlayer spacing is larger compared with that of graphite (0.335 nm) after doping, so that the structure is favorable for enhancing the intercalation of lithium ions, thereby being favorable for improving the electrochemical performance. Meanwhile, it is noted that there is no significant difference in the XRD patterns of the porous carbon materials prepared in example 1 and comparative examples 1 to 3 at the peak position of 23.6 °, indicating that the calcination temperature has no influence on their amorphous properties.
As can be seen from the peak intensity (ID/IG) ratio of the D band and the G band of the raman spectrum of fig. 3, the peak intensity ratio (ID/IG = 0.96) of NPC-750 prepared in example 1 is higher than that of NPC-600 (0.84), NPC-900 (0.88) and PC-750 (0.82), indicating that NPC-750 defects are more induced by N doping and KOH, resulting in better electrochemical energy storage properties of NPC-750.
Finally by measuring N 2 Further, the pore structures of the porous carbon materials prepared in example 1 and comparative examples 1 to 3 were examined, and the measurement results are shown in fig. 4. As can be seen from FIG. 4The porous carbon materials prepared in example 1 and comparative examples 1 to 3 both showed large specific surface area and pore volume, and NPC-750 prepared in example 1 had large specific surface area and pore volume (2914 m) 2 ·g -1 2.3479 mL/g) and smaller average pore size (3.2224 nm). In addition, the adsorption capacity of NPC-750 in low-pressure zone and high-pressure zone is sharply increased, the existence of micropores and macropores is confirmed, the hysteresis loop of the medium-pressure zone has no obvious saturated adsorption platform, and the existence of extremely irregular mesopores is confirmed. In contrast, NPC-600 and NPC-900 do not have a significant increase in adsorption capacity in the high pressure zone, which means that their macropores disappear, which is not conducive to rapid wetting of the electrolyte, thereby limiting the improvement in performance.
The porous carbon materials prepared in example 1 and comparative examples 4 to 7 are used as lithium ion battery negative electrode materials, and are placed in an agate mortar together with Super-P conductive carbon and PVDF binder (poly (vinylidine fluoride)) according to a mass ratio of 7. Uniformly coating a certain amount of the solution on a copper sheet current collector, and drying the copper sheet current collector in a vacuum oven at 50 ℃ for 24 hours. And weighing and recording the dried electrode slice. A working electrode, a metallic Li sheet counter electrode and a lithium ion battery containing 1.0M LiPF 6 The assembled coin cells were subjected to charge-discharge cycling tests on a blue-ray device, and the cell was tested for cyclic voltammetry and electrochemical ac impedance spectra at room temperature using a princeton electrochemical workstation.
FIG. 5 is a negative electrode of the NPC-750 lithium battery prepared in example 1 at 0.5mV s -1 Sweep rate, cyclic Voltammetry (CV) curve over a voltage range of 0.01-3.0V. As can be seen from the figure, NPC-750 shows an observed peak at about 0.6V at the first cathodic scan, due to the formation of Solid Electrolyte Interphase (SEI). A prominent reduction peak was observed at 1.3V and then disappeared in subsequent cycles, which can be attributed to Li + Irreversible insertion into an interfacial storage site. NPC-750 shows two prominent oxidation peaks at about 1.91V for the first anodic scan, corresponding to Li + And (4) removing. In the subsequent cycles, the oxidation peak at 2.3V disappeared, indicating the end of the side reaction. Thereafter, the CV curves almost overlapped, indicating the stability and superior reversibility of NPC-750 as LIBs cathodes.
FIGS. 6 to 13 are graphs at 100mA · g -1 Under the current density, the initial discharge capacity and the charge capacity of NPC-750 are 1619mAh/g and 938mAh/g respectively, the initial Coulombic Efficiency (CE) is 57.9 percent, and the good first-round reversibility of NPC-750 is shown according to the charge-discharge curves of the porous carbon material lithium battery cathodes prepared in the example 1 and the comparative examples 1 to 7 in the previous three rounds.
FIGS. 14-21 are at 0.1A g -1 Under current density, the cycling stability curve of the porous carbon material lithium battery negative electrodes prepared in example 1 and comparative examples 1-7 is that NPC-750 still has the highest reversible capacity (1019 mAh/g) after 100 cycles, and the specific capacity is better than the performance of most of the porous carbon materials reported at present.
In summary, the first discharge capacity, the first charge capacity and the capacity after 100 cycles of the negative electrodes of the porous carbon lithium batteries prepared in example 1 and comparative examples 1 to 7 are shown in table 1:
TABLE 1
Figure DEST_PATH_IMAGE002
As can be seen from Table 1, when NPC-750 prepared in example 1 of the present invention is used as a negative electrode of a lithium battery, the charge/discharge performance and the cycle stability are far superior to those of the porous carbon materials of comparative examples 1-7, because NPC-750 of example 1 has a higher specific surface area and porosity than NPC-600 of comparative example 1 and PC-750 of comparative example 3, can provide an electrolyte-electrode contact interface and generate initial Li + Intercalation, thereby exhibiting higher lithium storage properties; an excessive specific surface area and porosity may lose more irreversible SEI-forming ability than NPC-900 of comparative example 2, and for Li + The intercalation causes adverse effects, thereby causing the lithium storage performance of NPC-900 to be reduced; the specific surface area and porosity, which are also caused by the weak etching ability, are larger than those of NPPC-750 of comparative example 4 and NPC-750-1, NPC-750-2, NPC-750-3 of comparative examples 5-7Low or too strong etching ability causes collapse of the channel, resulting in excessive specific surface area and porosity, thereby causing degradation of lithium storage properties.
FIG. 22 shows a variation in 1A · g -1 Under the current density, according to the cycle stability curve of the NPC-750 lithium battery cathode prepared in the embodiment 1, the initial reversible capacity of the NPC-750 is 714.2 mAh/g, after 500 times of circulation, the specific capacity is kept to be 837 mAh/g, and the CE can reach more than 99%, which shows that the cycle stability is very excellent.
In addition to excellent cycling stability, NPC-750 also exhibited excellent rate performance, as shown in FIG. 23, stable and higher discharge capacities of 989, 687, 375, and 283mAh/g were obtained at current densities of 0.1, 1, 5, and 10A/g, respectively. When the current density was restored to 0.1A/g, the specific capacity was also restored to 1030mAh/g. Furthermore, as can be seen from fig. 24, NPC-750 also exhibited excellent long-term cycling stability at very high current density (10A/g), i.e., initial reversible capacity of 205mAh/g, which then increased rapidly to 281mAh/g after about 30 cycles, reversible capacity remained at 219mAh/g (CE about 100%) after 5000 cycles, further indicating its excellent reversibility and utility, which are superior to all biomass-derived carbon materials and most graphene/carbon-based and metal oxide/sulfide materials reported so far.
In addition, the present invention further compares the cycle capacity and rate capacity of the lithium battery assembled by NPC-750 prepared in example 1 as a negative electrode material for a lithium battery with those disclosed in the related articles, and the comparison result is shown in fig. 25. In fig. 25, the control group is from the following articles from top to bottom, respectively:
1.Issatayev,N.;Kalimuldina,G.;Nurpeissova,A.;Bakenov,Z.,Biomass-Derived Porous Carbon from Agar as an Anode Material for Lithium-Ion Batteries. Nanomaterials (Basel) 2021, 12 (1)。
2.Jiang, Q.; Ni,Y.; Zhang, Q.; Gao, J.; Wang,Z.;Yin,H.;Jing,Y.;Wang,J., Sustainable Nitrogen Self-Doped Carbon Nanofibers from Biomass Chitin as Anodes for High-Performance Lithium-Ion Batteries. Energy & Fuels 2022, 36 (7), 4026-4033。
3.Yu, K.;Wang,J.;Wang,X.;Liang,J.;Liang,C.,Sustainable application of biomass by-products: Corn straw-derived porous carbon nanospheres using as anode materials for lithium ion batteries. Materials Chemistry and Physics 2020, 243。
4.Wan,H.;Ju,X.;He,T.;Chen,T.;Zhou,Y.;Zhang,C.;Wang,J.;Xu,Y.;Yao,B.;Zhuang,W.;Du, X.,Sulfur-doped porous carbon as high-capacity anodes for lithium and sodium ions batteries. Journal of Alloys and Compounds 2021, 863。
5.Dou,Y.;Liu,X.;Wang,X.;Yu,K.;Liang,C.,Jute fiber based micro-mesoporous carbon: A biomass derived anode material with high-performance for lithium-ion batteries. Materials Science and Engineering: B 2021, 265。
6.Gao,Y.;Piao,S.;Jiang,C.;Zou,Z.,Navel orange peel-derived hard carbons as high performance anode materials of Na and Li-ion batteries. Diamond and Related Materials 2022, 129。
7.Huang,G.;Kong,Q.;Yao,W.;Wang,Q.,Poly tannic acid carbon rods as anode materials for high performance lithium and sodium ion batteries. Journal of Colloid and Interface Science 2022。
8.Li,R.;Huang,J.;Li,J.;Cao,L.;Zhong,X.;Yu,A.;Lu,G.,Nitrogen-doped porous hard carbons derived from shaddock peel for high-capacity lithium-ion battery anodes. Journal of Electroanalytical Chemistry 2020, 862。
as can be seen from the comparison result of fig. 25, the agar-derived nitrogen-doped porous carbon material prepared by the present invention adopts a relatively simple synthesis process and a precursor with low price, and exhibits excellent reversible capacity and cycling stability when used as a negative electrode material of a lithium ion battery, particularly under a large current, which is far superior to the porous carbon materials of the same type reported in the prior art. Therefore, the invention realizes the great performance improvement of the lithium battery cathode on the premise of controlling the cost, and has higher commercial practical value compared with the reported porous carbon material.
Although the present invention has been described in detail by referring to the drawings in connection with the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (8)

1. A preparation method of a nitrogen-doped porous carbon material derived from agar is characterized in that the agar, urea and potassium hydroxide are added into distilled water, and after heating and stirring, the mixture is dried; and pyrolyzing the dried material in nitrogen at 720-780 ℃, washing the obtained material with an acidic solution and distilled water, washing away residual potassium hydroxide, and drying to obtain the agar-derived nitrogen-doped porous carbon material.
2. The method for preparing an agar-derived nitrogen-doped porous carbon material according to claim 1, wherein the mass ratio of the agar to urea to potassium hydroxide is 1: (0.5-2): (0.5-1.5).
3. The method for preparing an agar-derived nitrogen-doped porous carbon material according to claim 1, wherein the heating and stirring temperature is 75 to 120 ℃ for 1 to 2 hours.
4. The method for preparing an agar-derived nitrogen-doped porous carbon material according to claim 1, wherein the first drying temperature is 90 to 120 ℃ and the drying time is 5 to 12 hours.
5. The method for preparing an agar-derived nitrogen-doped porous carbon material according to claim 1, wherein the temperature rise rate during pyrolysis is 2 to 4 ℃/min.
6. The method for preparing an agar-derived nitrogen-doped porous carbon material according to claim 1, wherein the temperature of the second drying is 80 to 150 ℃ and the drying time is not less than 12 hours.
7. An agar-derived nitrogen-doped porous carbon material prepared by the preparation method as claimed in claims 1 to 6.
8. The agar-derived nitrogen-doped porous carbon material according to claim 7, applied to a negative electrode material of a lithium battery.
CN202211148864.9A 2022-09-21 2022-09-21 Agar-derived nitrogen-doped porous carbon material and preparation method and application thereof Withdrawn CN115465862A (en)

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CN108231425A (en) * 2017-12-28 2018-06-29 盐城工学院 It is a kind of for nitrogen-phosphor codoping porous carbon of electrode material for super capacitor and preparation method thereof
CN110451509A (en) * 2019-08-20 2019-11-15 江西省科学院应用化学研究所 A method of nitrogen-doped porous carbon material is prepared by activator of zinc nitrate
CN112522726A (en) * 2020-10-30 2021-03-19 徐州瑞鑫新材料研究院有限公司 Preparation method and application of nitrogen-doped porous carbon/molybdenum disulfide composite material derived from natural agar
WO2021229087A1 (en) * 2020-05-15 2021-11-18 Politecnico Di Milano Environmentally friendly zinc/aqueous polysulfide rechargeable flow battery with high energy efficiency
CN113967480A (en) * 2021-10-21 2022-01-25 天津理工大学 Preparation method and application of phosphorus-doped molybdenum disulfide/porous carbon composite material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108231425A (en) * 2017-12-28 2018-06-29 盐城工学院 It is a kind of for nitrogen-phosphor codoping porous carbon of electrode material for super capacitor and preparation method thereof
CN110451509A (en) * 2019-08-20 2019-11-15 江西省科学院应用化学研究所 A method of nitrogen-doped porous carbon material is prepared by activator of zinc nitrate
WO2021229087A1 (en) * 2020-05-15 2021-11-18 Politecnico Di Milano Environmentally friendly zinc/aqueous polysulfide rechargeable flow battery with high energy efficiency
CN112522726A (en) * 2020-10-30 2021-03-19 徐州瑞鑫新材料研究院有限公司 Preparation method and application of nitrogen-doped porous carbon/molybdenum disulfide composite material derived from natural agar
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