CN109694071A - A kind of method and application preparing nitrogen-doped porous carbon material using coconut husk as raw material - Google Patents
A kind of method and application preparing nitrogen-doped porous carbon material using coconut husk as raw material Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
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Abstract
The invention discloses a kind of methods and application that nitrogen-doped porous carbon material is prepared using coconut husk as raw material, using coconut husk as raw material, sift out Filamentous shredded coconut meat, material A is obtained after high temperature cabonization, material A successively obtains material B after alkali cleaning, pickling, material B is dispersed in the mixed solution of potassium hydroxide and saleratus and activates 1h, then melamine solution is added, continue to stir 2h, Solutions in Freeze-drying obtains material C again, after the processing of material C high temperature cabonization, nitrogen-doped porous carbon material is obtained through pickling, filtering, washing, drying.The present invention is using resourceful and low-cost agriculture and forestry organic waste material cocoanut shell as raw material, nitrogen-doped porous carbon material large specific surface area obtained, and there is hierarchical porous structure, wherein macropore is conducive to mass transport, micropore and it is mesoporous more active sites can be provided, improve catalytic activity；And the carbon material has very strong resistance to methanol solution, and cyclical stability is good, has potential application prospect on oxygen reduction catalyst.
Description
Technical field
The invention belongs to inorganic nano material and electrochemical fields, are related to a kind of nitrogen-doped porous carbon material, and in particular to
A kind of method and application preparing nitrogen-doped porous carbon material using coconut husk as raw material.
Background technique
Oxygen reduction reaction is an important mistake in the new energies reforming units such as fuel cell, metal zinc-air battery
Journey, because its dynamic process is slow, side reaction is more so the catalyst for needing to have excellent performance.Get up for a long time, it is practical to fill
Oxygen reduction reaction in setting is catalyzed with noble metal catalysts such as platinum, palladium, iridium, these noble metal catalysts not only cost
Valuableness, durability are poor and are easy to be poisoned by substances such as carbon monoxide and methanol, limit the new energy device such as fuel cell
Commercialized development.Therefore exploitation can substitute the low cost and high performance non-precious metal catalyst of conventional precious metal catalyst
Through the urgent task for becoming the development of the electrochemical energies reforming units such as fuel cell and metal-air.
Porous carbon materials have pore structure abundant, high-specific surface area and good electric conductivity, have become hot topic
Catalyst material.Miscellaneous element is introduced in porous carbon materials can increase the defect and active site of material surface, further change
The surface texture of kind material.Nitrogen-atoms can be provided because its atom size and electronegativity and carbon atom are closest to carbon atom
Electronics improves the electric conductivity of carbon material and promotes the overpotential of the charge transfer reduction hydrogen reduction process during hydrogen reduction, from
And improve the electrocatalysis characteristic of hydrogen reduction.
At present there are mainly two types of the synthetic methods of nitrogen-doped porous carbon material, one is the fabricated in situ of nitrogenous material, separately
One is after porous carbon synthesizes, high temperature ammoniated treatment is carried out to it.It is high that CN103922305A discloses a kind of high-specific surface area
Nitrogen content adulterates the preparation method of porous carbon, using biomass coconut husk as raw material, obtains carbide after high temperature cabonization processing, then will
Carbide is dispersed in potassium hydroxide saturated solution, obtains alkali carbon mix after dry；Alkali carbon mix is subjected to high-temperature activation
Processing, obtains porous carbon materials；Porous carbon materials are dispersed in the strong acid solution concentrated sulfuric acid and carry out oxidation processes, filtering,
Oxidized porous carbon material is obtained after washing, drying, finally carries out oxidized porous carbon material at high temperature ammonification under ammonia atmosphere
Reason obtains doping porous carbon.Although the method obtains the doped porous carbon material of high-specific surface area high nitrogen-containing, need to use
To concentrated sulfuric acid strong acid solution, environment is unfriendly, and ammonia injects under high temperature, and safety is low.
Therefore it is badly in need of developing the synthesis nitrogen-doped porous carbon of a kind of clean and environmental protection, low cost, high efficiency and safety at present
The method of material.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing nitrogen-doped porous carbon material as raw material using coconut husk, simple rings
It protects, it is low in cost.
It is a further object of the present invention to provide the applications of the above-mentioned nitrogen-doped porous carbon material prepared using coconut husk as raw material.
To achieve the above object, The technical solution adopted by the invention is as follows: one kind using coconut husk as raw material to prepare N doping more
The method of hole carbon material, comprising the following steps:
(1) coconut husk is smashed, sifts out Filamentous shredded coconut meat, clean dry is placed in tube furnace, under inert gas protection with 5
℃min-1Rate be warming up to 400 DEG C of holding 2h, be cooled to room temperature and obtain the material A of pre- carbonization；
(2) material A is used to potassium hydroxide solution alkali cleaning 8h under the conditions of 60 DEG C, filtering is washed to filtrate and is in neutrality；Exist again
Dilute hydrochloric acid solution pickling 1h is used under the conditions of 60 DEG C, filtering is washed to filtrate and is in neutrality, and drying obtains material B；
(3) 1:3 weighs potassium hydroxide and saleratus respectively in mass ratio, is configured to mixed solution, and material B is dispersed in
In mixed solution, 1h is stirred under the conditions of 60 DEG C, melamine solution is then added, continued to stir 2h, be transferred to culture later
In ware, it is put into freeze dryer freeze-drying, obtains material C；
(4) material C is placed in tube furnace, under inert gas protection with 2 DEG C of min-1Rate be warming up to 800 DEG C of holdings
2h, then with 5 DEG C of min-1Rate cool to 400 DEG C, then cooled to room temperature obtains material D；
(5) by material D dilute hydrochloric acid solution pickling 1h, filtering is washed to filtrate and is in neutrality, and it is porous that drying obtains N doping
Carbon material.
Preferably, in step (3), the mass ratio of the material B and potassium hydroxide in mixed solution is 1:1, the trimerization
The mass ratio of melamine and material B are 4:1 in cyanamide solution.
Preferably, in step (2), the concentration of the potassium hydroxide solution is 6molL-1。
Preferably, in step (2) and step (5), the concentration of the dilute hydrochloric acid solution is 1molL-1。
Preferably, in step (3), the stirring rate is 300r min-1。
Preferably, in step (1) and step (4), the inert gas is nitrogen or argon gas.
Preferably, in step (5), the temperature of the drying is 80 DEG C, time 12h.
The present invention also provides application of the nitrogen-doped porous carbon material made from above-mentioned preparation method in oxygen reduction catalyst.
By nitrogen-doped porous carbon material and deionized water, isopropanol, 5% perfluorinated sulfonic acid-teflon-copolymers
(Nafion) solution is uniformly mixed, ultrasonic 1h, takes 8 μ l mixed solutions drop in the rotating disk electrode (r.d.e) (RDE) of diameter 5mm, so
Working electrode is made in naturally dry in air afterwards.
Compared with prior art, the invention has the following beneficial effects:
(1) present invention prepares nitrogen-doped porous carbon using resourceful and low-cost natural biomass coconut husk as raw material
Material, realizes effective recycling to agriculture and forestry organic waste material；
(2) nitrogen-doped porous carbon material large specific surface area produced by the present invention, reaches 2126m2g-1, and there is multi-stage porous knot
Structure, total pore volume 1.084cm3g-1, wherein macropore is conducive to mass transport, micropore and mesoporous can provide more active sites
Point improves catalytic activity；X-ray photoelectron spectroscopy (XPS) analysis shows nitrogen content 5%；
(3) nitrogen-doped porous carbon material preparation method provided by the invention is simple and environmentally-friendly, and hydrogen reduction electrocatalysis characteristic is excellent,
It is suitable with business hydrogen reduction Pt/C catalyst performance；
(4) nitrogen-doped porous carbon material produced by the present invention has very strong resistance, and cyclical stability to methanol solution
Well, there is potential application prospect on oxygen reduction catalyst.
Detailed description of the invention
Fig. 1 is nitrogen-doped porous carbon material made from the embodiment of the present invention 1 in nitrogen saturation and oxygen saturation 0.1molL-1
Cyclic voltammetric (CV) curve in potassium hydroxide solution；
Fig. 2 is nitrogen-doped porous carbon material made from the embodiment of the present invention 1 in oxygen saturation 0.1molL-1Potassium hydroxide is molten
400-2025r min in liquid-1Scanning volt-ampere (LSV) curve；
Fig. 3 is nitrogen-doped porous carbon material made from the embodiment of the present invention 1 and comparative example 1-4 in oxygen saturation 0.1molL-1
1600r min in potassium hydroxide solution-1Scanning volt-ampere (LSV) curve；
Fig. 4 is isothermal (77K) nitrogen adsorption desorption curve of nitrogen-doped porous carbon material made from the embodiment of the present invention 1；
Fig. 5 is nitrogen-doped porous carbon material made from the embodiment of the present invention 1 with the calculating of discrete Fourier transform (DFT) model
Pore distribution curve；
Fig. 6 is field emission scanning electron microscope (SEM) electricity of nitrogen-doped porous carbon material made from the embodiment of the present invention 1
Mirror photo；
Fig. 7 is nitrogen-doped porous carbon material sample made from the embodiment of the present invention 1 and Pt/C in 0.1mol L-1Hydrogen-oxygen
Change potassium solution in 0.7V 400r min-1Methanol tolerance performance map；
Fig. 8 is nitrogen-doped porous carbon material sample made from the embodiment of the present invention 1 and Pt/C in 0.1mol L-1Hydroxide
In potassium solution in 0.7V 400r min-1Cyclical stability figure.
Specific embodiment
Invention is further described in detail in the following with reference to the drawings and specific embodiments.
Embodiment 1
(1) coconut husk is smashed, sifts out Filamentous shredded coconut meat, be washed with deionized water it is dry after be put into corundum boat and be placed in tube furnace
In, with 5 DEG C of min in nitrogen atmosphere-1Rate be warming up to 400 DEG C of holding 2h, naturally cool to room temperature after the completion of heating and obtain
The material A 1 being carbonized in advance；
(2) material A 1 is transferred in beaker, 100ml 6mol L is added under the conditions of 60 DEG C-1Potassium hydroxide solution,
300r min-18h is stirred, then filters, is washed with deionized water to filtrate and is in neutrality, filter cake is transferred in beaker, then at 60 DEG C
Under the conditions of be added 100ml 1mol L-1HCI, 300r min-11h is stirred, is filtered, is washed with deionized water to filtrate and is in neutrality, is dried
It is dry to obtain material B1；
(3) 0.15g potassium hydroxide and 0.45g saleratus is taken to be dissolved in the mixed solution for being made into 20ml in deionized water, so
After take 0.15g material B1 to put into the mixed solution, with 300r min under the conditions of 60 DEG C-11h is stirred, it is new that 20ml is then added
The solution dissolved with 0.6g melamine matched continue stir 2h, be subsequently poured into culture dish be put into freeze dryer freeze-drying obtain object for 24 hours
Expect C1；
(4) material C1 is transferred to corundum boat to be placed in tube furnace, under nitrogen protection with 2 DEG C of min-1Rate is warming up to
800 DEG C of holding 2h, then 5 DEG C of min-1Rate cools to 400 DEG C, then cooled to room temperature obtains material D1；
(5) material D1 is transferred in beaker, 100ml 1mol L is added-1HCI stir 1h, filter, then use deionization
It is washed to neutrality, then 80 DEG C of drying 12h obtain nitrogen-doped porous carbon material E1.
The nitrogen-doped porous carbon material E1 for weighing 3mg, by it with the deionized water of 170 μ l, the isopropanol of 70 μ l, 10 μ l
5% perfluorinated sulfonic acid-teflon-copolymers (Nafion) solution is uniformly mixed, ultrasonic 1h, takes 8 μ l mixed solutions drop in diameter
In the rotating disk electrode (r.d.e) (RDE) of 5mm, then working electrode is made in naturally dry in air；Using the electrode as working electrode,
Platinum filament is to electrode, and silver/silver chloride electrode of 3.5m is that reference electrode forms three-electrode system, in the 0.1mol of oxygen saturation
L-1Potassium hydroxide solution in scan cycle volt-ampere curve and linear volt-ampere curve, sweep speed be respectively 5mv s-1With 10mv s-1。
Fig. 1 is embodiment 1 in the 0.1mol L that nitrogen is saturated and oxygen is saturated-1Cyclic voltammetric in potassium hydroxide solution
(CV) curve, in the 0.1mol L of oxygen saturation-1Embodiment 1 has apparent hydrogen reduction peak in potassium hydroxide solution, and in nitrogen
Do not have in gas, shows that embodiment 1 has good catalytic performance to redox reactions.
Fig. 2 is embodiment 1 in oxygen saturation 0.1mol L-1400-2025r min in potassium hydroxide solution-1Scanning volt
Pacify (LSV) curve, it can be seen that initial potential of the embodiment 1 during oxygen reduction reaction very just, shows the overpotential of reaction
Very low, in addition curve has apparent carrying current platform and limiting current density is very big, further illustrates embodiment 1 to oxygen
Reduction reaction has good catalytic performance.
Fig. 4 is isothermal (77K) nitrogen adsorption desorption curve of embodiment 1, and specific surface area reaches 2126m after tested2g-1, total hole
Holding is 1.084cm3g-1, while as can be seen from Figure material just have when relative pressure is smaller very big adsorbance and
When relative pressure is greater than 0.5, curve has hysteretic loop, illustrates that material has micropore abundant and certain mesoporous and macroporous structure,
Embodiment 1 is demonstrated with hierarchical porous structure.
Fig. 5 is the pore distribution curve that embodiment 1 is calculated with discrete Fourier transform (DFT) model, and material as shown in the figure exists
1nm or so has the mesoporous of micropore and 2-10nm abundant, and there are also the presence of certain macropore, this result and figures in 50nm
4 is corresponding.
Fig. 6 is field emission scanning electron microscope (SEM) photo of embodiment 1, it can be seen that 1 material of embodiment has bright
Aobvious hierarchical porous structure, it is corresponding with Fig. 4 and Fig. 5.
Show that material prepared by the present invention mainly contains C, N, O element through XPS analysis, nitrogen content 5% further proves
Nitrogen-atoms is successfully doped in material.
Comparative example 1
(1) coconut husk is smashed, sifts out Filamentous shredded coconut meat, be washed with deionized water it is dry after be put into corundum boat and be placed in tube furnace
In, with 5 DEG C of min in nitrogen atmosphere-1Rate be warming up to 400 DEG C of holding 2h, naturally cool to room temperature after the completion of heating and obtain
The material A 2 being carbonized in advance；
(2) material A 2 is transferred in beaker, 100ml 6mol L is added under the conditions of 60 DEG C-1Potassium hydroxide, 300r
min-18h is stirred, then filters, is washed with deionized water to filtrate and is in neutrality, filter cake is transferred in beaker, under the conditions of 60 DEG C
100ml 1mol L is added-1HCI, 300r min-11h is stirred, then neutrality is washed with deionized water, drying obtains material B2；
(3) material B2 is transferred to corundum boat to be placed in tube furnace, under nitrogen protection with 2 DEG C of min-1Rate is warming up to
800 DEG C of holding 2h, then 5 DEG C of min-1Rate cools to 400 DEG C, then cooled to room temperature obtains nitrogen-doped porous carbon material
E2；
Electrochemical test method and embodiment 1 phase of the above-mentioned nitrogen-doped porous carbon material E2 as oxygen reduction catalyst
Together.
Comparative example 2
(1) coconut husk is smashed, sifts out Filamentous shredded coconut meat, be washed with deionized water it is dry after be put into corundum boat and be placed in tube furnace
In, with 5 DEG C of min in nitrogen atmosphere-1Rate be warming up to 400 DEG C of holding 2h, naturally cool to room temperature after the completion of heating and obtain
The material A 3 being carbonized in advance；
(2) 0.15g material A 3 and 0.15g potassium hydroxide, 0.45g saleratus, 0.6g melamine are taken, in revolving speed 300r
min-1Under the conditions of vacuum ball milling 30min, obtain material B3；
(3) material B3 is transferred to corundum boat to be placed in tube furnace, under nitrogen protection with 2 DEG C of min-1Rate is warming up to
800 DEG C of holding 2h, then 5 DEG C of min-1Rate cools to 400 DEG C, then cooled to room temperature obtains material C3；
(4) material C3 is transferred in beaker, 100ml 1mol L is added-1HCI stir 1h, filter, then use deionization
It is washed to neutrality, then 80 DEG C of drying 12h obtain nitrogen-doped porous carbon material E3.
Electrochemical test method and embodiment 1 phase of the above-mentioned nitrogen-doped porous carbon material E2 as oxygen reduction catalyst
Together.
Comparative example 3
(1) coconut husk is smashed, sifts out Filamentous shredded coconut meat, be washed with deionized water it is dry after be put into corundum boat and be placed in tube furnace
In, with 5 DEG C of min in nitrogen atmosphere-1Rate be warming up to 400 DEG C of holding 2h, naturally cool to room temperature after the completion of heating and obtain
The material A 4 being carbonized in advance；
(2) 0.15g potassium hydroxide and 0.45g saleratus is taken to be dissolved in the mixed solution for being made into 20ml in deionized water, so
After take 0.15g material A 4 put into the mixed solution in, with 300r min under the conditions of 60 DEG C-11h is stirred, it is new that 20ml is then added
The solution dissolved with 0.6g melamine matched continue stir 2h, be subsequently poured into culture dish be put into freeze dryer freeze-drying obtain object for 24 hours
Expect B4；
(3) material B4 is transferred to corundum boat to be placed in tube furnace, with 2 DEG C of min under nitrogen protection-1Rate is warming up to
800 DEG C of holding 2h, then 5 DEG C of min-1Rate cools to 400 DEG C, then cooled to room temperature obtains material C4；
(4) material C4 is transferred in beaker, 100ml 1mol L is added-1HCI stir 1h, filter, then use deionization
It is washed to neutrality, then 80 DEG C of drying 12h obtain nitrogen-doped porous carbon material E4.
Electrochemical test method and embodiment 1 phase of the above-mentioned nitrogen-doped porous carbon material E4 as oxygen reduction catalyst
Together.
Comparative example 4
The business 20%Pt/C that 1mg is weighed with electronic balance, by its deionized water with 170 μ l, the isopropanol of 70 μ l, 10
5% perfluorinated sulfonic acid-teflon-copolymers (Nafion) solution of μ l is uniformly mixed, ultrasonic 1h, and 8 μ l mixed solutions drop is taken to exist
In the rotating disk electrode (r.d.e) (RDE) of diameter 5mm, then working electrode is made in naturally dry in air；Using the electrode as work
Electrode, platinum filament are to electrode, 3.5mol L-1Silver/silver chloride electrode be reference electrode form three-electrode system, oxygen be saturated
0.1mol L-1Potassium hydroxide solution in scan cycle volt-ampere curve and linear volt-ampere curve, sweep speed be respectively 5mv s-1s
With 10mv s-1。
Fig. 3 is embodiment 1 and comparative example 1-4 in oxygen saturation 0.1mol L-11600r min in potassium hydroxide solution-1's
Scan volt-ampere (LSV) curve, it can be seen that initial potential, half wave potential and the limiting current density of embodiment 1 are substantially better than pair
Ratio 1-3, and it is suitable with the business Pt/C in comparative example 4, show that embodiment 1 there are and business Pt/C redox reactions
Excellent catalytic performance shoulder to shoulder, has a good application prospect.
Fig. 7 is with chronoamperometry in 0.1mol L-1In the potassium hydroxide solution of oxygen saturation, constant voltage (0.7V vs
RHE)400r min-1Under the conditions of lower test oxygen reduction reaction electric current, and 2.5ml methanol solution is added in the 100s of test
(99%).As shown, the current fluctuation after methanol is added of 4 business Pt/C catalyst of comparative example is violent, and 1 material of embodiment exists
Current fluctuation very little after addition methanol, illustrates that 1 material of embodiment has good resistance performance to methanol.
Fig. 8 is with chronoamperometry in 0.1mol L-1In the potassium hydroxide solution of oxygen saturation, constant voltage (0.7V vs
RHE)400r min-1Under the conditions of lower test oxygen reduction reaction electric current.As shown, after the test by 50000s, comparison
The current attenuation of 4 business Pt/C catalyst of example is to less than 60%, and the electric current of 1 material of embodiment remains at 90% or more, says
Bright 1 material of embodiment has good stability and patience.
Claims (8)
1. a kind of method for preparing nitrogen-doped porous carbon material as raw material using coconut husk, which comprises the following steps:
(1) coconut husk is smashed, sifts out Filamentous shredded coconut meat, clean dry is placed in tube furnace, under inert gas protection with 5 DEG C
min-1Rate be warming up to 400 DEG C of holding 2h, be cooled to room temperature and obtain the material A of pre- carbonization；
(2) material A is used to potassium hydroxide solution alkali cleaning 8h under the conditions of 60 DEG C, filtering is washed to filtrate and is in neutrality；Again at 60 DEG C
Under the conditions of use dilute hydrochloric acid solution pickling 1h, filtering, be washed to filtrate and be in neutrality, drying obtain material B；
(3) 1:3 weighs potassium hydroxide and saleratus respectively in mass ratio, is configured to mixed solution, and material B is dispersed in mixing
In solution, 1h is stirred under the conditions of 60 DEG C, melamine solution is then added, continued to stir 2h, be transferred in culture dish later,
It is put into freeze dryer freeze-drying, obtains material C；
(4) material C is placed in tube furnace, under inert gas protection with 2 DEG C of min-1Rate be warming up to 800 DEG C of holding 2h,
Then with 5 DEG C of min-1Rate cool to 400 DEG C, then cooled to room temperature obtains material D；
(5) by material D dilute hydrochloric acid solution pickling 1h, filtering is washed to filtrate and is in neutrality, and drying obtains nitrogen-doped porous carbon
Material.
2. a kind of method for preparing nitrogen-doped porous carbon material as raw material using coconut husk according to claim 1, feature exist
In in step (3), the mass ratio of potassium hydroxide is 1:1 in the material B and mixed solution, three in the melamine solution
The mass ratio of poly cyanamid and material B are 4:1.
3. a kind of method for preparing nitrogen-doped porous carbon material as raw material using coconut husk according to claim 1, feature exist
In in step (2), the concentration of the potassium hydroxide solution is 6molL-1。
4. a kind of method for preparing nitrogen-doped porous carbon material as raw material using coconut husk according to claim 1, feature exist
In in step (2) and step (5), the concentration of the dilute hydrochloric acid solution is 1molL-1。
5. a kind of method for preparing nitrogen-doped porous carbon material as raw material using coconut husk according to claim 1, feature exist
In in step (3), the stirring rate is 300r min-1。
6. a kind of method for preparing nitrogen-doped porous carbon material as raw material using coconut husk according to claim 1, feature exist
In in step (1) and step (4), the inert gas is nitrogen or argon gas.
7. a kind of method for preparing nitrogen-doped porous carbon material as raw material using coconut husk according to claim 1, feature exist
In in step (5), the temperature of the drying is 80 DEG C, time 12h.
8. nitrogen-doped porous carbon material answering in oxygen reduction catalyst made from the described in any item methods of claim 1 to 7
With.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110734063A (en) * | 2019-12-03 | 2020-01-31 | 武汉理工大学 | method for preparing rice hull based nitrogen-doped active carbon |
| CN112028052A (en) * | 2020-09-18 | 2020-12-04 | 西北大学 | Preparation method and application of biomass carbon-based Fe monatomic-N doped porous carbon material |
| CN112467109A (en) * | 2020-11-27 | 2021-03-09 | 西安建筑科技大学 | Activated carbon material, composite material, cathode material and cathode sheet of zinc ion energy storage device and zinc ion energy storage device |
| CN113998697A (en) * | 2021-11-03 | 2022-02-01 | 中国矿业大学 | Preparation method of leaf-based nitrogen-doped porous carbon and application of leaf-based nitrogen-doped porous carbon in oxygen reduction electrocatalysis in full pH range |
| WO2024082304A1 (en) * | 2022-10-21 | 2024-04-25 | 宁德时代新能源科技股份有限公司 | Carbonaceous material and preparation method therefor, secondary battery containing carbonaceous material, and electric apparatus |
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| CN107128918A (en) * | 2017-05-26 | 2017-09-05 | 桂林电子科技大学 | A kind of preparation and its application of N doping porous active Carbon Materials |
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| CN113998697B (en) * | 2021-11-03 | 2023-09-29 | 中国矿业大学 | Preparation method of leaf-based nitrogen-doped porous carbon and application of leaf-based nitrogen-doped porous carbon in oxygen reduction electrocatalysis in full pH range |
| WO2024082304A1 (en) * | 2022-10-21 | 2024-04-25 | 宁德时代新能源科技股份有限公司 | Carbonaceous material and preparation method therefor, secondary battery containing carbonaceous material, and electric apparatus |
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