CN109573992A - A kind of nitrogen-doped graphene material and preparation method thereof and application as kalium ion battery negative electrode material - Google Patents
A kind of nitrogen-doped graphene material and preparation method thereof and application as kalium ion battery negative electrode material Download PDFInfo
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Abstract
The invention discloses a kind of nitrogen-doped graphene material and preparation method thereof and as the application of kalium ion battery negative electrode material.Nitrogen-doped graphene material the preparation method comprises the following steps: crystalline flake graphite and micro crystal graphite admixed graphite are carried out oxidation processes, obtain mixed oxidization graphite；After mixed oxidization graphite is ultrasonically treated, centrifuge separation obtains graphene oxide；After graphene oxide is mixed with nitrogen source, it is placed in nitrogenous gas atmosphere, is heat-treated, obtain nitrogen-doped graphene；This method uses micro crystal graphite substitution part crystalline flake graphite cheap and easy to get for raw material, low in cost, and simple process, and the nitrogen-doped graphene material property of preparation is excellent, can obtain the kalium ion battery of the high and good high rate performance of specific capacity.
Description
Technical field
The present invention relates to a kind of Heteroatom doping grapheme material, in particular to a kind of nitrogen-doped graphene material and utilization
The method that natural graphite prepares nitrogen-doped graphene material further relates to nitrogen-doped graphene material as potassium ion carbon negative pole material
Application, belong to secondary cell field.
Background technique
Graphene is a kind of laminar structured two-dimensional material that the hexatomic ring by carbon is made up of bonding action.Due to stone
Black alkene has high electric conductivity, and (conductivity is up to 10-6S/m) high-termal conductivity (thermal coefficient is about 5300W/mK), high electronics
Mobility (is greater than 15000cm under room temperature2/ Vs), big specific surface area (2630m2/ g), good chemical stability and heat are steady
It is qualitative, it is widely used in the fields such as semiconductor, solar battery, secondary cell and sensor.
The method of the common power production of graphene is mechanical stripping method, oxidation-reduction method, SiC epitaxial growth method, film
Production method is chemical vapour deposition technique (CVD).Graphene is considered as the kalium ion battery electrode material for having application prospect, so
And graphene surface does not have an active function groups, therefore the chemical properties such as battery capacity further increase and improvement is restricted.
Currently, it is the most commonly used and effective method that graphene is prepared by redox using crystalline flake graphite raw material, however, with
The consumption of the fast development of China's economy and science and technology, China's graphite product keeps rapid growth, leads to natural flake graphite resource
It is fewer and fewer.
Nitrogen-atoms is adulterated in graphene can form high local charge/spin density in its spatial induction and improve its change
Activity is learned, so that the chemical property and cyclical stability of graphene are improved, but the nitrogen of existing natural flake graphite preparation is mixed
There are still complex process, expensive raw material prices at present for miscellaneous graphene, and the grapheme material purity prepared is lower, performance compared with
The technical problem urgently to be resolved such as difference.
Summary of the invention
Existing crystalline flake graphite preparation graphene and nitrogen-doped graphene there are aiming at the problem that, the purpose of the present invention is
In providing a kind of nitrogen-doped graphene material for being provided simultaneously with high activity site and good electric conductivity, the material particularly suitable as
Kalium ion battery negative electrode material application.
Another object of the present invention is to be that providing one kind is led to by crystalline flake graphite and natural graphite admixed graphite for raw material
Peroxidating, ultrasound removing and the high temperature dopant nitrogen method for preparing nitrogen-doped graphene, this method simple process, it is reproducible, at
This is cheap, environmentally friendly, is suitble to large-scale production.
Third object of the present invention is to be to provide a kind of application of nitrogen-doped graphene, with high activity site and
Good electric conductivity, as kalium ion battery negative electrode material application, the kalium ion battery of acquisition shows high specific capacity and good
High rate performance.
In order to achieve the above technical purposes, the present invention provides a kind of preparation method of nitrogen-doped graphene material, packets
Include following steps:
1) crystalline flake graphite and micro crystal graphite admixed graphite are subjected to oxidation processes, obtain mixed oxidization graphite；
2) after being ultrasonically treated mixed oxidization graphite, centrifuge separation obtains graphene oxide；
3) it after mixing graphene oxide with nitrogen source, is placed in nitrogenous gas atmosphere, is heat-treated, obtain N doping stone
Black alkene.
Technical solution of the present invention key is to prepare using crystalline flake graphite and micro crystal graphite admixed graphite as raw material
Two kinds of different natural graphites of physical and chemical performance are carried out expanding treatment simultaneously and mechanical stripping are handled, formed by nitrogen-doped graphene
The graphene-structured of special appearance, during ultrasonic lift-off processing, crystalline flake graphite removing dispersion obtains large stretch of graphene, and micro-
Spar ink, which is then removed, to be formed floccule and is connected between crystalline flake graphite alkene lamella, and cotton-shaped graphene is mingled between Sheet Graphite alkene
Structure is more advantageous to interelectric conduction, and the high rate performance of mixed expanded graphite is greatly improved.Meanwhile to admixed graphite alkene
N doping processing has been carried out, by introducing nitrogen-atoms in admixed graphite alkene, the band gap of graphene can have been opened, and adjust and lead
Electric type changes the electronic structure of graphene, improves the free carrier density of graphene to improve the electrochemistry of graphene
Performance and chemical stability.Therefore, the N doping expanded graphite of preparation, while there is high active site and high conductivity, have
Conducive to the specific capacity and high rate performance for improving kalium ion battery.
Preferred scheme, the oxidation processes are as follows: crystalline flake graphite and micro crystal graphite admixed graphite are under condition of ice bath
After mixing with the concentrated sulfuric acid, potassium permanganate is added at a temperature of 15~25 DEG C, reacts 1~3h, then be warming up to 90~110 DEG C of reactions
0.5~1.5h is cooled to room temperature, and hydrogen peroxide solution is added, and reacts 6~8h.
The mass volume ratio of more preferably scheme, crystalline flake graphite and micro crystal graphite admixed graphite and the concentrated sulfuric acid be 1:15~
40g/mL。
The mass ratio of more preferably scheme, crystalline flake graphite and micro crystal graphite admixed graphite and potassium permanganate is 1:3~6.
The mass volume ratio of more preferably scheme, crystalline flake graphite and micro crystal graphite admixed graphite and hydrogenperoxide steam generator is 1:
10~25g/mL.Hydrogenperoxide steam generator is conventional commercially available hydrogen peroxide solution.
Preferred scheme, the nitrogen source include at least one of urea, melamine, L-AA.
The mass ratio of preferred scheme, the graphene oxide and nitrogen source is 1:5~8.
The mass ratio of preferred scheme, crystalline flake graphite and micro crystal graphite is 1:1~9.
Preferred scheme, in the ultrasonication, supersonic frequency is 40~80Hz, 30~60h of time.
Preferred scheme, the nitrogenous gas include ammonia and/or nitrogen.
Preferred scheme, the heat treatment temperature are 600~1000 DEG C, and the time is 0.5~20h.
Ultrasonication of the invention uses Ultrasonic wave industrial grade dispersing apparatus: 3000W ultrasound wave vibrating bar+ultrasonic wave
Numerical control driving power.
Crystalline flake graphite and micro crystal graphite of the invention is respectively by natural crystalline flake graphite and micro crystal graphite by conventional acid
Purification processes, carbon content reach 99% or more.
The present invention also provides a kind of nitrogen-doped graphene materials, are obtained by above-mentioned preparation method.
Preferred scheme, the N doping amount of nitrogen-doped graphene material nitrogen are 5wt%~20wt%.
The present invention also provides the applications of nitrogen-doped graphene material, are used as the application of kalium ion battery negative electrode material.
Preferred scheme mixes nitrogen-doped graphene with conductive agent and binder, is coated in copper foil collection by rubbing method
On fluid, as kalium ion battery cathode.
Nitrogen-doped graphene prepared by the present invention prepares method and the performance detection side of kalium ion battery as negative electrode material
Method: weighing the above-mentioned nitrogen-doped graphene of 80wt.%, 10wt.%Super P is added as conductive agent, 10wt.%PVDF is as viscous
Agent is tied, ground sufficiently a small amount of NMP, which is added, is mixed to form uniform black paste slurry later, these slurries are coated in copper foil
On collector as test electrode, be assembled into button cell using metallic potassium piece as comparison electrode, use electrolyte system for
1M LiPF6/ EC:DEC (1:1) is assembled into button electricity by battery case of CR2025 type stainless steel using polypropylene as diaphragm
Pond.
Compared with the prior art, the beneficial effects of the present invention are:
1) present invention is high by oxidation intercalation processing combination nitrogen source using crystalline flake graphite and micro crystal graphite admixed graphite for the first time
The method of warm solution prepares nitrogen-doped graphene, and the preparation process is simple, low in cost, purity is high, and function admirable is suitble to industry
Metaplasia produces.
2) nitrogen-doped graphene of the invention, introduces nitrogen-atoms in graphene, can open the band gap of graphene, and
Conduction type is adjusted, the electronic structure of graphene is changed, improves the free carrier density of graphene to improve graphene
Chemical property and chemical stability.Simultaneously during lift-off processing, crystalline flake graphite removes to obtain large stretch of graphene, and crystallite
Graphite then remove formed it is cotton-shaped be connected between crystalline flake graphite alkene lamella, cotton-shaped graphene is mingled between this graphene sheet layer
Structure be more advantageous to interelectric conduction, improve the high rate performance of mixed expanded graphite.
3) nitrogen-doped graphene of the invention is showed as kalium ion battery negative electrode material application, the kalium ion battery of preparation
Height ratio capacity and long circulating stability energy out.
Specific embodiment
Following embodiment is intended to be described in further details the content of present invention；And the protection scope of the claims in the present invention
It is not limited by the example.
Embodiment 1
It takes 10g micro crystal graphite and 10g crystalline flake graphite to be dissolved in the 400mL concentrated sulfuric acid, is sufficiently mixed under conditions of 0 DEG C of ice bath；
Addition 70g potassium permanganate in 20 DEG C of backward solution is then heated to, mixed reaction solution is obtained after reacting 2h, then heats to 100
DEG C isothermal reaction 1h, adds 300mL industry hydrogen peroxide reaction 6h after being cooled to room temperature, graphite oxide is obtained by filtration in purifying.It will
Resulting graphene oxide, which is dissolved in 200mL ethyl alcohol, is ultrasonically treated (frequency 40Hz, time 30h), is then centrifuged for separating
To graphene oxide.4g graphene oxide is uniformly mixed with 20g urea, is placed in tube furnace, under ammonia atmosphere, is warming up to
800 DEG C of heat preservation 2h carry out carbonization treatment, and heating rate is 5 DEG C/min, can obtain nitrogen-doped graphene.The nitrogen-doped graphene
The content of middle nitrogen is 15.7%.
It weighs 80wt.% nitrogen-doped graphene manufactured in the present embodiment, 10wt.%Super P is added as conductive agent,
10wt.%PVDF is as binder, and ground sufficiently a small amount of NMP, which is added, is mixed to form uniform black paste slurry later, will
These slurries are coated in copper foil current collector as test electrode, and with metallic potassium piece, electrode assembling becomes button electricity as a comparison
Pond uses electrolyte system for 1M KPF6/EC:DEC (1:1), and glass fibre is diaphragm, is electricity with CR2025 type stainless steel
Pond shell is assembled into button.Under the current density of 100mA/g, coulombic efficiency is tested；Under the current density of 2000mA/g
Test the cycle performance of battery.Test result show this example preparation kalium ion battery cathode have good coulombic efficiency and
Cycle performance: under the current density of 100mA/g, first circle coulombic efficiency is 67%, and first circle discharge capacity is 352mAh/g, is followed
After ring 100 encloses, it is still able to maintain the specific capacity of 336mAh/g；Under the power-discharging density of 2000mA/g, discharge capacity 314mAh/g,
Capacity residue 285mAh/g after 1000 circle of circulation.
Embodiment 2
It takes 15g micro crystal graphite and 5g crystalline flake graphite to be dissolved in the 500mL concentrated sulfuric acid, is sufficiently mixed under conditions of 0 DEG C of ice bath；So
After be warming up in 20 DEG C of backward solution addition 80g potassium permanganate, obtain mixed reaction solution after reacting 2h, then heat to 100 DEG C
Isothermal reaction 1h, adds 300mL industry hydrogen peroxide reaction 6h after being cooled to room temperature, graphite oxide is obtained by filtration in purifying.By institute
The graphene oxide obtained, which is dissolved in 200mL ethyl alcohol, is ultrasonically treated (frequency 60Hz, time 45h), is then centrifuged for isolated
Graphene oxide.4g graphene oxide is uniformly mixed with 25g urea, is placed in tube furnace, under ammonia atmosphere, is warming up to 800
DEG C heat preservation 2h carry out carbonization treatment, heating rate be 5 DEG C/min, nitrogen-doped graphene can be obtained.In the nitrogen-doped graphene
The content of nitrogen is 18.5%.
It weighs 80wt.% nitrogen-doped graphene manufactured in the present embodiment, 10wt.%Super P is added as conductive agent,
10wt.%PVDF is as binder, and ground sufficiently a small amount of NMP, which is added, is mixed to form uniform black paste slurry later, will
These slurries are coated in copper foil current collector as test electrode, and with metallic potassium piece, electrode assembling becomes button electricity as a comparison
Pond uses electrolyte system for 1M KPF6/EC:DEC (1:1), and glass fibre is diaphragm, is electricity with CR2025 type stainless steel
Pond shell is assembled into button.Under the current density of 100mA/g, coulombic efficiency is tested；Under the current density of 2000mA/g
Test the cycle performance of battery.Test result show this example preparation kalium ion battery cathode have good coulombic efficiency and
Cycle performance: under the current density of 100mA/g, first circle coulombic efficiency is 65%, and first circle discharge capacity is 358mAh/g, is followed
After ring 100 encloses, it is still able to maintain the specific capacity of 332mAh/g；Under the power-discharging density of 2000mA/g, discharge capacity 309mAh/g,
Capacity residue 287mAh/g after 1000 circle of circulation.
Embodiment 3
It takes 12g micro crystal graphite and 8g crystalline flake graphite to be dissolved in the 400mL concentrated sulfuric acid, is sufficiently mixed under conditions of 0 DEG C of ice bath；So
After be warming up in 20 DEG C of backward solution addition 90g potassium permanganate, obtain mixed reaction solution after reacting 2h, then heat to 100 DEG C
Isothermal reaction 1h, adds 300mL industry hydrogen peroxide reaction 6h after being cooled to room temperature, graphite oxide is obtained by filtration in purifying.By institute
The graphene oxide obtained, which is dissolved in 200mL ethyl alcohol, is ultrasonically treated (frequency 40Hz, time 30h), is then centrifuged for isolated
Graphene oxide.4g graphene oxide is uniformly mixed with 20g urea, is placed in tube furnace, under ammonia atmosphere, is warming up to 1000
DEG C heat preservation 2h carry out carbonization treatment, heating rate be 5 DEG C/min, nitrogen-doped graphene can be obtained.In the nitrogen-doped graphene
The content of nitrogen is 16.2%.
It weighs 80wt.% nitrogen-doped graphene manufactured in the present embodiment, 10wt.%Super P is added as conductive agent,
10wt.%PVDF is as binder, and ground sufficiently a small amount of NMP, which is added, is mixed to form uniform black paste slurry later, will
These slurries are coated in copper foil current collector as test electrode, and with metallic potassium piece, electrode assembling becomes button electricity as a comparison
Pond uses electrolyte system for 1M 1M KPF6/EC:DEC (1:1), and glass fibre is diaphragm, is with CR2025 type stainless steel
Battery case is assembled into button.Under the current density of 100mA/g, coulombic efficiency is tested；In the current density of 2000mA/g
The cycle performance of lower test battery.Test result shows that the kalium ion battery cathode of this example preparation has good coulombic efficiency
And cycle performance: under the current density of 100mA/g, first circle coulombic efficiency is 61%, and first circle discharge capacity is 364mAh/g,
After 100 circle of circulation, it is still able to maintain the specific capacity of 343mAh/g；Under the power-discharging density of 2000mA/g, discharge capacity 323mAh/
G, capacity residue 296mAh/g after circulation 1000 is enclosed.
Comparative example 1
It takes 20g crystalline flake graphite to be dissolved in the 400mL concentrated sulfuric acid, is sufficiently mixed under conditions of 0 DEG C of ice bath；Then heat to 20 DEG C
70g potassium permanganate is added in backward solution, obtains mixed reaction solution after reacting 2h, then heats to 100 DEG C of isothermal reaction 1h, it is cold
But to the reaction of 300mL industry hydrogen peroxide is added after room temperature, graphite oxide is obtained by filtration in purifying.Resulting graphene oxide is molten
It is ultrasonically treated (frequency 40Hz, time 30h) in 200mL ethyl alcohol, is then centrifuged for isolated graphene oxide.4g oxidation
Graphene is uniformly mixed with 20g urea, is placed in tube furnace, under ammonia atmosphere, is warming up to 800 DEG C of heat preservation 2h and is carried out at carbonization
Reason, heating rate are 5 DEG C/min, can obtain nitrogen-doped graphene.The content of nitrogen is 13.9% in the nitrogen-doped graphene.
It weighs 80wt.% nitrogen-doped graphene manufactured in the present embodiment, 10wt.%Super P is added as conductive agent,
10wt.%PVDF is as binder, and ground sufficiently a small amount of NMP, which is added, is mixed to form uniform black paste slurry later, will
These slurries are coated in copper foil current collector as test electrode, and with metallic potassium piece, electrode assembling becomes button electricity as a comparison
Pond uses electrolyte system for 1M KPF6/EC:DEC (1:1), and glass fibre is diaphragm, is electricity with CR2025 type stainless steel
Pond shell is assembled into button.Under the current density of 100mA/g, coulombic efficiency is tested；Under the current density of 2000mA/g
Test the cycle performance of battery.Test result show this example preparation kalium ion battery cathode have good coulombic efficiency and
Cycle performance: under the current density of 100mA/g, first circle coulombic efficiency is 61%, and first circle discharge capacity is 334mAh/g, is followed
After ring 100 encloses, it is still able to maintain the specific capacity of 311mAh/g；Under the power-discharging density of 2000mA/g, discharge capacity 278mAh/g,
Capacity residue 225mAh/g after 1000 circle of circulation.
Comparative example 2
It takes 20g micro crystal graphite (carbon content >=99%) to be dissolved in the 400mL concentrated sulfuric acid, is sufficiently mixed under conditions of 0 DEG C of ice bath；
Addition 70g potassium permanganate in 20 DEG C of backward solution is then heated to, mixed reaction solution is obtained after reacting 2h, then heats to 100
DEG C isothermal reaction 1h, adds the reaction of 300mL industry hydrogen peroxide after being cooled to room temperature, graphite oxide is obtained by filtration in purifying.By institute
The graphene oxide obtained, which is dissolved in 200mL ethyl alcohol, is ultrasonically treated (frequency 40Hz, time 30h), is then centrifuged for isolated
Graphene oxide.4g graphene oxide is uniformly mixed with 20g urea, is placed in tube furnace, under ammonia atmosphere, is warming up to 800
DEG C heat preservation 2h carry out carbonization treatment, heating rate be 5 DEG C/min, nitrogen-doped graphene can be obtained.In the nitrogen-doped graphene
The content of nitrogen is 15.6%.
It weighs 80wt.% nitrogen-doped graphene manufactured in the present embodiment, 10wt.%Super P is added as conductive agent,
10wt.%PVDF is as binder, and ground sufficiently a small amount of NMP, which is added, is mixed to form uniform black paste slurry later, will
These slurries are coated in copper foil current collector as test electrode, and with metallic potassium piece, electrode assembling becomes button electricity as a comparison
Pond uses electrolyte system for 1M KPF6/EC:DEC (1:1), and glass fibre is diaphragm, is electricity with CR2025 type stainless steel
Pond shell is assembled into button.Under the current density of 100mA/g, coulombic efficiency is tested；Under the current density of 2000mA/g
Test the cycle performance of battery.Test result show this example preparation kalium ion battery cathode have good coulombic efficiency and
Cycle performance: under the current density of 100mA/g, first circle coulombic efficiency is 65%, and first circle discharge capacity is 339mAh/g, is followed
After ring 100 encloses, it is still able to maintain the specific capacity of 308mAh/g；Under the power-discharging density of 2000mA/g, discharge capacity 298mAh/g,
Capacity residue 234mAh/g after 1000 circle of circulation.
Claims (10)
1. a kind of preparation method of nitrogen-doped graphene material, it is characterised in that: the following steps are included:
1) crystalline flake graphite and micro crystal graphite admixed graphite are subjected to oxidation processes, obtain mixed oxidization graphite；
2) after being ultrasonically treated mixed oxidization graphite, centrifuge separation obtains graphene oxide；
3) it after mixing graphene oxide with nitrogen source, is placed in nitrogenous gas atmosphere, is heat-treated, obtain N doping graphite
Alkene.
2. a kind of preparation method of nitrogen-doped graphene material according to claim 1, it is characterised in that: at the oxidation
Reason process are as follows: after crystalline flake graphite and micro crystal graphite admixed graphite mix under condition of ice bath with the concentrated sulfuric acid, in 15~25 DEG C of temperature
Lower addition potassium permanganate reacts 1~3h, then is warming up to 90~110 DEG C of 0.5~1.5h of reaction, is cooled to room temperature, and dioxygen is added
Aqueous solution reacts 6~8h.
3. a kind of preparation method of nitrogen-doped graphene material according to claim 2, it is characterised in that:
The mass volume ratio of crystalline flake graphite and micro crystal graphite admixed graphite and the concentrated sulfuric acid is 1:15~40g/mL；
The mass ratio of crystalline flake graphite and micro crystal graphite admixed graphite and potassium permanganate is 1:3~6；
The mass volume ratio of crystalline flake graphite and micro crystal graphite admixed graphite and hydrogenperoxide steam generator is 1g:10~25mL；
The mass ratio of crystalline flake graphite and micro crystal graphite is 1:1~9.
4. a kind of preparation method of nitrogen-doped graphene material according to claim 1, it is characterised in that: at the ultrasound
During reason, supersonic frequency is 40~80Hz, 30~60h of time.
5. a kind of preparation method of nitrogen-doped graphene material according to claim 1, it is characterised in that: the nitrogen source packet
Include at least one of urea, melamine, L-AA；
The graphene oxide and the mass ratio of nitrogen source are 1:5~8.
6. a kind of preparation method of nitrogen-doped graphene material according to claim 1, it is characterised in that: described to contain nitrogen
Body includes ammonia and/or nitrogen.
7. according to right want 1 described in a kind of preparation method of nitrogen-doped graphene, it is characterised in that: the heat treatment temperature is
600~1000 DEG C, the time is 0.5~20h.
8. a kind of nitrogen-doped graphene material, it is characterised in that: obtained by the described in any item preparation methods of claim 1~7.
9. a kind of nitrogen-doped graphene material according to claim 9, it is characterised in that: nitrogen-doped graphene material nitrogen
N doping amount is 5wt%~20wt%.
10. the application of the described in any item nitrogen-doped graphene materials of claim 8 or 9, it is characterised in that: as potassium ion electricity
Pond negative electrode material application.
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| CN110718687A (en) * | 2019-10-08 | 2020-01-21 | 中南大学 | Preparation method of fluorine-nitrogen doped lithium titanate/graphene composite material |
| CN114956063A (en) * | 2022-07-27 | 2022-08-30 | 湘潭大学 | Preparation method of nitrogen-doped fluorinated modified graphene potassium electrical anode material and battery |
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| CN115784204A (en) * | 2022-11-30 | 2023-03-14 | 中山大学 | Ultra-high-edge nitrogen-doped carbon nanosheet and preparation method and application thereof |
| CN116111087A (en) * | 2022-10-27 | 2023-05-12 | 武汉科技大学 | Three-dimensional hierarchical nitrogen-doped graphene microsphere material and preparation method and application thereof |
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| CN110718687A (en) * | 2019-10-08 | 2020-01-21 | 中南大学 | Preparation method of fluorine-nitrogen doped lithium titanate/graphene composite material |
| CN114956063A (en) * | 2022-07-27 | 2022-08-30 | 湘潭大学 | Preparation method of nitrogen-doped fluorinated modified graphene potassium electrical anode material and battery |
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| CN115520856B (en) * | 2022-08-19 | 2024-06-11 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nanocomposite with elemental iodine and sulfur particles anchored in axial plane of nitrogen-doped graphene |
| CN116111087A (en) * | 2022-10-27 | 2023-05-12 | 武汉科技大学 | Three-dimensional hierarchical nitrogen-doped graphene microsphere material and preparation method and application thereof |
| CN115784204A (en) * | 2022-11-30 | 2023-03-14 | 中山大学 | Ultra-high-edge nitrogen-doped carbon nanosheet and preparation method and application thereof |
| CN115784204B (en) * | 2022-11-30 | 2024-04-12 | 中山大学 | Ultra-high edge nitrogen doped carbon nano sheet and preparation method and application thereof |
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