CN107857253A - A kind of three-dimensional porous graphene of N doping and preparation method thereof - Google Patents
A kind of three-dimensional porous graphene of N doping and preparation method thereof Download PDFInfo
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- CN107857253A CN107857253A CN201711260869.XA CN201711260869A CN107857253A CN 107857253 A CN107857253 A CN 107857253A CN 201711260869 A CN201711260869 A CN 201711260869A CN 107857253 A CN107857253 A CN 107857253A
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Abstract
The invention discloses a kind of three-dimensional porous graphene of N doping, the weight percentage of total nitrogen is 6%~10% in the three-dimensional porous graphene of N doping, and conductance is 232~427Sm‑1.The doped forms of nitrogen are pyridine nitrogen, pyrroles's nitrogen and graphite nitrogen in the three-dimensional porous graphene of N doping；Pyridine nitrogen percentage composition in total nitrogen is 15%~26%；Pyrroles's nitrogen percentage composition in total nitrogen is 39%~52%；Graphite nitrogen percentage composition in total nitrogen is 26%~41%.The three-dimensional porous graphene of N doping of the present invention, provides more avtive spots for electric charge storage, increases effective contact area of material, is advantageous to improve chemical property, is advantageously used for the specific capacitance of electrode material and the raising of cycle performance；Preparation method is not simple to operate harsh, and reaction condition is not high to equipment requirement gently without dangerous hidden danger, reduces raw material and equipment cost；It is adapted to industrialization large-scale production and application.
Description
Technical field
The present invention relates to field of nanometer material technology, more particularly to three-dimensional porous graphene of a kind of N doping and preparation method thereof.
Background technology
In recent years, the graphene of " king of new material " is described as, is led as the most thin, maximum intensity that has now been found that, conduction
The most strong novel nano-material of hot property, have in catalysis, bio-sensing, battery, capacitor and Aero-Space numerous areas wide
Wealthy application prospect.Graphene is made up of single layer of carbon atom, by sp2 hybridized orbit bondings between carbon atom.Due to graphene
Unique structure and outstanding intrinsic physical characteristic, such as electric conductivity is high and surface area is big, and graphene-based material is in super capacitor
Application in device has great potentiality.
Graphene easily occurs serious agglomeration in application and stacked again, cause to compare table because Van der Waals force interacts
Area, diffusion rate and electrical conductivity decline to a great extent, and influence application performance.Using the miscellaneous other elements of Erbium-doped, by graphene correlation material
To the graphene sheet layer of nano-scale, stone can effectively be changed by changing the pattern (size, shape and thickness) of graphene for material dissociation
The property of black alkene, be advantageous to improve its application performance defect.The graphene of the miscellaneous other elements of Erbium-doped includes phosphorus doping at present, boron adulterates
With N doping etc..Phosphorus doping rate is relatively low, causes electro catalytic activity to reduce, and the specific surface area of material is smaller after doping.And boron adulterates
Afterwards, the electronegativity of material is smaller than N doping.In the graphene of N doping, nitrogen-atoms can induce more positive charges to adjacent
Carbon atom on, effectively improve anion exchange performance and electro catalytic activity, and there is more excellent stability, but at present
Nitrogen-doped graphene stills need to improve on the chemical properties such as avtive spot quantity, effective contact area, to improve its application
The needs of performance.In addition, the existing disclosed preparation method for carrying out N doping in graphene also has many deficiencies, one need to be entered
Step optimization.
The method for preparing nitrogen-doped graphene at present has direct synthesis method and post-processing approach.Direct synthesis method includes
Vapour deposition process, nitrogen plasma electric discharge, arc discharge method, segregation growth method etc..Post-processing approach includes heat treatment, solvent
Hot method, plasma processing method etc..Existing method has the following disadvantages：(1) synthesis technique is complicated, and preparation condition is harsh, right
Equipment requirement is higher；(2) N doping amount is not high and unstable, and production cost is high；(3) severe reaction conditions, raw material are dangerous
Potential safety hazard；(4) need cumbersome special installation, process, conversion ratio and yield low, it is difficult to realize industrialized production etc..Though in the recent period
So there are the nitrogen-doped graphene new preparation process such as microwave solid source, microwave spoke vapor phase method, but above-mentioned deficiency is not still fine
Solve.Therefore, finding one kind has more avtive spots, bigger effective contact area, more excellent chemical property
Nitrogen-doped graphene and have the advantages that technique be simple and convenient to operate, be cheap, it is easy realize industrialization large-scale production
Nitrogen-doped graphene preparation method become the study hotspot in the field.
Therefore, those skilled in the art is directed to developing three-dimensional porous graphene of a kind of N doping and preparation method thereof,
To improve deficiency of the prior art.
The content of the invention
In view of the drawbacks described above of prior art, the technical problems to be solved by the invention are to provide the nitrogen of more excellent properties
Doped graphene, optimize preparation method, meet the needs of industrialized production.
To achieve the above object, first aspect present invention provides a kind of three-dimensional porous graphene of N doping, wherein, it is described
The weight percentage of total nitrogen is 6%~10% in the three-dimensional porous graphene of N doping.
Further, the conductance of the three-dimensional porous graphene of the N doping is 232~427Sm-1；
Further, in the three-dimensional porous graphene of the N doping nitrogen doped forms for pyridine nitrogen (pyridinicN),
Pyrroles's nitrogen (pyrrolicN) and graphite nitrogen (graphiticN)；
Further, the pyridine nitrogen (pyridinicN) percentage composition in total nitrogen in the three-dimensional porous graphene of N doping
For 15%~26%；
Further, pyrroles's nitrogen (pyrrolicN) percentage composition in total nitrogen in the three-dimensional porous graphene of N doping
For 39%~52%；
Further, the graphite nitrogen (graphiticN) percentage composition in total nitrogen in the three-dimensional porous graphene of N doping
For 26%~41%；
Further, the three-dimensional porous graphene of the N doping, disorder distribution interlaced in three dimensions, formed more
Pore network structure.
In the better embodiment of the present invention, the weight percentage of total nitrogen in the three-dimensional porous graphene of N doping
For 6.1%；
In another better embodiment of the present invention, the weight percent of total nitrogen in the three-dimensional porous graphene of N doping
Content is 7.7%；
In another better embodiment of the present invention, the weight percent of total nitrogen in the three-dimensional porous graphene of N doping
Content is 9.2%；
In another better embodiment of the present invention, in the three-dimensional porous graphene total nitrogen of N doping, pyridine nitrogen
(pyridinicN) percentage composition is 26%, pyrroles's nitrogen (pyrrolicN) percentage composition is 40%, graphite nitrogen (graphiticN)
Percentage composition is 35%；
In another better embodiment of the present invention, in the three-dimensional porous graphene total nitrogen of N doping, pyridine nitrogen
(pyridinicN) percentage composition is 22%, pyrroles's nitrogen (pyrrolicN) percentage composition is 51%, graphite nitrogen (graphiticN)
Percentage composition is 26%；
In another better embodiment of the present invention, in the three-dimensional porous graphene total nitrogen of N doping, pyridine nitrogen
(pyridinicN) percentage composition is 16%, pyrroles's nitrogen (pyrrolicN) percentage composition is 43%, graphite nitrogen (graphiticN)
Percentage composition is 41%；
In another better embodiment of the present invention, the conductance of the three-dimensional porous graphene of N doping is 232S
m-1、；
In another better embodiment of the present invention, the conductance of the three-dimensional porous graphene of N doping is 388S
m-1；
In another better embodiment of the present invention, the conductance of the three-dimensional porous graphene of N doping is 427S
m-1。
Second aspect of the present invention provides a kind of preparation method of the three-dimensional porous graphene of N doping, comprises the following steps：
Step 1, graphite oxide is scattered in deionized water, ultrasonic disperse forms suspension, obtains 1mg/ml oxidation
Graphene suspension；
Step 2, nitrating agent is added in the suspension that step 1 obtains, stir to obtain mixed liquor；
Step 3, mixed liquor prepared by step 2 heating reacted, reaction, which is cooled to room temperature after terminating and obtains solid-liquid, to be mixed
Compound；
Step 4, by the solidliquid mixture of step 3 precipitated product separation, washing, dry, obtain nitrogen-doped graphene and receive
Rice material.
Further, in the step 1, ultrasonic time 0-30min, ultrasonic power 200W-600W；It is preferred that ultrasonic work(
Rate is 540W；
Further, in the step 2, the nitrating agent is hydrazine hydrate, ethylenediamine, ammoniacal liquor, urea；Preferably urea；
Further, in the step 2, the nitrating agent of addition and the weight (gram) of graphite oxide are than being 20:1~40:1；
Preferably 30:1；
Further, in the step 2, mixing time is 20~50min；It is preferred that 30min；
Further, in the step 3, reaction temperature is 120 DEG C~220 DEG C；It is preferred that 120 DEG C, 140 DEG C, 160 DEG C, 180
DEG C, 200 DEG C, 220 DEG C；Most preferably 180 DEG C；
Further, in the step 3, the reaction time is 4~6 hours；It is preferred that 5 hours；
Further, in the step 4, wash as acidic aqueous solution, neutral aqueous solution washing；It is separated into centrifugation；
Further, in the step 4, the drying mode is vacuum drying and freeze-drying；Preferably it is freeze-dried；
Further, in the step 4, the drying time is 10~20 hours；It is preferred that 15 hours.
" room temperature " of the present invention is without referring to 18 DEG C~28 DEG C in the case of specified otherwise.
Third aspect present invention provides the three-dimensional porous graphene of N doping described in any of the above-described and is used for electrode in preparation
Purposes in material；
Electrode material described further is the electrode material of ultracapacitor.
Using the three-dimensional porous graphene of N doping described above and ptfe emulsion and acetylene black (AR) proportionally
Mixing, is tuned into pasty state after grinding, equably smearing is bonded in nickel foam and is dried in vacuo afterwards on the net, and tabletting obtains electrode slice, is used for
Electrode material as ultracapacitor.
Using the electrode slice of above-mentioned preparation as electrode to be tested is studied, platinum plate electrode (15mm × 15mm) and saturation calomel are electric
Pole (SCE) is respectively as auxiliary electrode and reference electrode；Electrochemical property test is carried out to above-mentioned electrode material, evaluates its property
Energy.
In the present invention, the pyridine nitrogen (pyridinicN), pyrroles's nitrogen (pyrrolicN) and graphite nitrogen
(graphiticN) three kinds of Bonding Types in the graphene lattice of carbon atom are referred to；Pyridine nitrogen (pyridinicN) refers to connect
The nitrogen-atoms being connected on two carbon at graphite face edge, the nitrogen-atoms to conjugatedπbond system in addition to an electronics is provided, and also one
, can adsorption of oxygen molecule and its intermediate during hydrogen reduction to lone pair electrons；Pyrroles's nitrogen (pyrrolicN) refers to carry two
Individual p electronics and the nitrogen-atoms being conjugated with pi bond system；Graphite nitrogen (graphiticN) is also referred to as " four " nitrogen, expression and graphite-based
The connected nitrogen of three carbon atoms in face.
Using above scheme, three-dimensional porous graphene of N doping disclosed by the invention and preparation method thereof, have following excellent
Point：
1st, the three-dimensional porous graphene of N doping of the invention, the overlapping of graphene sheet layer is effectively prevented, improves graphene
The hydrophily of nanometer sheet, extra n-type carrier is introduced in graphene and changes electron donor/receptor property, is deposited for electric charge
Storage provides more avtive spots, increases effective contact area of material, is more beneficial for improving chemical property and N doping three
Tie up specific capacitance and cycle performance that porous graphene is used for electrode material；
2nd, the three-dimensional porous graphene of N doping of the invention, the type content of the nitrogen adulterated in graphene, doping are optimized
To the nitrogen-atoms in graphene lattice by " pyridinic N ", " pyrrolic N ", " in the form of three kinds of graphitic N " exist,
Different nitrogen sources and different reaction temperatures will form different nitrating forms, the nitrogen-doped graphene of different nitrogen contents, N doping
The difference of form and content can regulate and control the physical property of graphene, be advantageous to change the electron acceptor characteristic of graphene, help
In improving its specific capacitor and circulation ability, multiple use and field are advantageously applied to；
3rd, the preparation method of the three-dimensional porous graphene of N doping of the invention, optimizes each Parameter Conditions, passes through high content nitrogen
Doping, has broken graphene symmetrical structure, has formd three-dimensional porous conductive network, the band gap for opening graphene and adjustment is led
Electric type, change the electronic structure of graphene, improve the free carrier density of graphene, so as to improve the electric conductivity of graphene
Energy and specific surface area, further improve its chemical property；
4th, the preparation method of the three-dimensional porous graphene of N doping of the invention, using green and inexpensive hydro-thermal
Method, by changing hydrothermal temperature and nitrogen source, high nitrogen content and the N doping stone with three-dimensional porous network structure are synthesized
Black alkene material, realize that graphite oxide (GO) reduction and the step of graphene N doping self assembly one are completed.Preparation method is simple to operate not
Harshness, reaction condition is not high to equipment requirement gently without dangerous hidden danger, reduces raw material and equipment cost；It is adapted to industrialization big
Large-scale production application；
In summary, the three-dimensional porous graphene of N doping of the invention, more avtive spots are provided for electric charge storage, increased
Effective contact area of big material, it is more beneficial for improving chemical property, is advantageously used for specific capacitance and the circulation of electrode material
The raising of performance；Preparation method is not simple to operate harsh, and reaction condition is not high to equipment requirement gently without dangerous hidden danger, lowers
Raw material and equipment cost；It is adapted to industrialization large-scale production and application.
Below with reference to embodiment to the present invention design, concrete technical scheme and caused technique effect make into
One step illustrates, to be fully understood from the purpose of the present invention, feature and effect.
Brief description of the drawings
Fig. 1 is the SEM spectrograms of the three-dimensional porous graphene of N doping of the embodiment of the present invention 1；
Fig. 2 is that nitrogen-doped graphene is used for electrode material in the electric capacity that current density is 0.3A/g in test example 4 of the present invention
Cycle performance figure.
Embodiment
Below with reference to multiple preferred embodiments of the present invention, make its technology contents more clear and readily appreciate.The present invention
It can be emerged from by many various forms of embodiments, protection scope of the present invention is not limited only to the reality mentioned in text
Apply example.
Embodiment 1：
Using the graphite powder of 325 mesh as raw material, graphene oxide is prepared using improved Hummers methods are freeze-dried
(GO).100mg puff shape GO are weighed, by being ultrasonically treated in 100ml deionized waters, ultrasonic time 30min, ultrasonic power
For 540W, 1mg/ml suspension is obtained, by GO：Urea is 1：3g urea is slowly added into above-mentioned suspension by 30 mass ratio
In, after magnetic agitation 30min, resulting solution is transferred in the hydrothermal reaction kettle of polytetrafluoroethyllining lining, reacts 5h at 180 DEG C
After naturally cool to room temperature, after being washed with watery hydrochloric acid (content 5%) and filtered 3 times, neutrality is washed with deionized and centrifuges
Separate, the three-dimensional porous graphene product of N doping is obtained after freeze-dried 15h.
As shown in figure 1, the SEM spectrograms of the three-dimensional porous graphene of N doping for embodiment 1；The nitrogen obtained to the present embodiment
Adulterate three-dimensional porous graphene to be tested and analyzed, show the percentage of total nitrogen in the three-dimensional porous graphene of N doping of embodiment 1
Content is 9.2%；Wherein the hundred of pyridine nitrogen (pyridinicN), pyrroles's nitrogen (pyrrolicN) and graphite nitrogen (graphiticN)
Point content is respectively 26%, 40% and 35%, electrical conductivity 427Sm-1。
Embodiment 2：
Using the graphite powder of 325 mesh as raw material, graphene oxide is prepared using improved Hummers methods are freeze-dried
(GO).100mg puff shape GO are weighed, by being ultrasonically treated in 100ml deionized waters, ultrasonic time 30min, ultrasonic power
For 600W, 1mg/ml suspension is obtained, by GO：Urea is 1：2g urea is slowly added into above-mentioned suspension by 20 mass ratio
In, after magnetic agitation 50min, resulting solution is transferred in the hydrothermal reaction kettle of polytetrafluoroethyllining lining, reacts 6h at 140 DEG C
After naturally cool to room temperature, after being washed with watery hydrochloric acid (mass fraction 5%) and filtered 3 times, be washed with deionized it is neutral simultaneously
Centrifuge, the three-dimensional porous graphene product of N doping is obtained after freeze-dried 10h.
The three-dimensional porous graphene of N doping obtained to the present embodiment tests and analyzes, and shows the N doping of embodiment 2
The percentage composition of total nitrogen is 6.1% in three-dimensional porous graphene；Wherein pyridine nitrogen (pyridinicN), pyrroles's nitrogen
(pyrrolicN) and the percentage composition of graphite nitrogen (graphiticN) is respectively 22%, 51% and 26%, electrical conductivity 232S
m-1。
Embodiment 3：
Using the graphite powder of 325 mesh as raw material, graphene oxide is prepared using improved Hummers methods are freeze-dried
(GO).100mg puff shape GO are weighed, by being ultrasonically treated in 100ml deionized waters, ultrasonic time 10min, ultrasonic power
For 200W, 1mg/ml suspension is obtained, by GO：Ethylenediamine mass ratio is 1：40 by 4.5ml ethylenediamines (density 0.90g/
cm3) solution is slowly dropped to above-mentioned suspension, after magnetic agitation 20min, resulting solution is transferred to the water of polytetrafluoroethyllining lining
In thermal response kettle, room temperature is naturally cooled to after reacting 4h at 220 DEG C, is washed with watery hydrochloric acid (mass fraction 5%) and filters 3
After secondary, neutrality is washed with deionized and centrifuges, the three-dimensional porous graphene production of N doping is obtained after freeze-dried 20h
Product.
The three-dimensional porous graphene of N doping obtained to the present embodiment tests and analyzes, and shows the N doping of embodiment 2
The percentage composition of total nitrogen is 7.7% in three-dimensional porous graphene；Wherein pyridine nitrogen (pyridinicN), pyrroles's nitrogen
(pyrrolicN) and the percentage composition of graphite nitrogen (graphiticN) is respectively 16%, 43% and 41%, electrical conductivity 388S
m-1。
Test example 4：
The three-dimensional porous graphene of N doping that embodiment 1 is obtained is with ptfe emulsion and acetylene black (AR) according to matter
Measure ratio 8:1:1 mixing, is tuned into pasty state after grinding, equably smear that to be bonded in nickel foam online, 60 DEG C of vacuum drying 0.5h after
20MPa pressure lower sheetings, and 2min is kept, it is pressed into the electrode slice that area is 1cm2.
The electrode material chemical property that above-mentioned electrode slice is used for ultracapacitor is tested, electrochemical property test is using mark
Accurate three-electrode system, Electrode are the electrode slice of above-mentioned preparation, platinum plate electrode (15mm × 15mm) and saturated calomel electrode
(SCE) respectively as auxiliary electrode and reference electrode.Electrolyte is 6molL-1 KOH solution, and electrode needs to balance before test
24h。
Electrochemical property test is carried out to above-mentioned electrode material, as shown in Fig. 2 be 0.3A/g in current density, circulation
2000 times, the specific capacity of electric capacity is more than 170Fg-1, with specific capacity 190Fg during beginning-1Compare, capacity retention be 90~
95%.
Illustrate, the three-dimensional porous graphene of the N doping that embodiment 1 obtains shows in the electrode material for ultracapacitor
Excellent chemical property is shown.
The three-dimensional porous graphene of N doping that other embodiments of the invention obtain has and above-mentioned similar chemical property.
The three-dimensional porous graphene of N doping obtained in the above-mentioned other embodiment of the present invention and technical scheme have and on
State similar chemical property.
Preferred embodiment of the invention described in detail above.It should be appreciated that the ordinary skill of this area is without wound
The property made work can makes many modifications and variations according to the design of the present invention.Therefore, all technician in the art
Pass through the available technology of logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Scheme, all should be in the protection domain being defined in the patent claims.
Claims (10)
- A kind of 1. three-dimensional porous graphene of N doping, it is characterised in that the weight of total nitrogen in the three-dimensional porous graphene of N doping It is 6%~10% to measure percentage composition；The conductance of the three-dimensional porous graphene of N doping is 232~427Sm-1。
- 2. the three-dimensional porous graphene of N doping as claimed in claim 1, it is characterised in that the three-dimensional porous graphene of N doping The doped forms of middle nitrogen are pyridine nitrogen, pyrroles's nitrogen and graphite nitrogen；Wherein, the pyridine nitrogen is in the three-dimensional porous graphene of N doping Percentage composition is 15%~26% in total nitrogen；Percentage composition is pyrroles's nitrogen in total nitrogen in the three-dimensional porous graphene of N doping 39%~52%；Percentage composition is 26%~41% to the graphite nitrogen in total nitrogen in the three-dimensional porous graphene of N doping.
- 3. a kind of preparation method of the three-dimensional porous graphene of N doping, it is characterised in that comprise the following steps：Step 1, graphite oxide is scattered in deionized water, ultrasonic disperse forms suspension, obtains 1mg/ml graphite oxide Alkene suspension；Step 2, nitrating agent is added in the suspension that step 1 obtains, stir to obtain mixed liquor；Step 3, mixed liquor prepared by step 2 is heated up and reacted, reaction is cooled to room temperature after terminating and obtains solidliquid mixture；Step 4, by the solidliquid mixture of step 3 precipitated product separation, washing, dry, obtain nitrogen-doped graphene nanometer material Material.
- 4. preparation method as claimed in claim 3, it is characterised in that in the step 1, ultrasonic time 0-30min, ultrasonic work( Rate is 200W-600W.
- 5. preparation method as claimed in claim 3, it is characterised in that in the step 2, the nitrating agent is hydrazine hydrate, second two Amine, ammoniacal liquor, urea；The weight of nitrating agent and graphite oxide ratio is 20:1~40:1；Mixing time is 20~50min.
- 6. preparation method as claimed in claim 3, it is characterised in that in the step 3, reaction temperature is 120 DEG C~220 DEG C； Reaction time is 4~6 hours.
- 7. preparation method as claimed in claim 3, it is characterised in that in the step 4, wash as acidic aqueous solution, neutral water Solution washs；It is described to be separated into centrifugation；The drying mode is vacuum drying and freeze-drying；The drying time is 10 ~20 hours.
- 8. preparation method as claimed in claim 6, it is characterised in that in the step 3, reaction temperature be 140 DEG C, 160 DEG C, 180℃；Reaction time is 5 hours.
- 9. the three-dimensional porous graphene of N doping that a kind of any one of claim 3~8 preparation method obtains, its feature exist In the weight percentage of total nitrogen is 9.2% in the three-dimensional porous graphene of N doping；The three-dimensional porous graphite of N doping The conductance of alkene is 232~427Sm-1；The doped forms of nitrogen are pyridine nitrogen, pyrroles in the three-dimensional porous graphene of N doping Nitrogen and graphite nitrogen；Percentage composition is 15%~26% to the pyridine nitrogen in total nitrogen in the three-dimensional porous graphene of N doping；It is described Percentage composition is 39%~52% to pyrroles's nitrogen in total nitrogen in the three-dimensional porous graphene of N doping；The graphite nitrogen is in N doping three Percentage composition is 26%~41% in total nitrogen in dimension porous graphene.
- 10. any one of the three-dimensional porous graphene of any one of claim 1~2 N doping or claim 3~8 system Purposes of the three-dimensional porous graphene of N doping that Preparation Method obtains in preparing for electrode material.
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| CN109368618A (en) * | 2018-11-07 | 2019-02-22 | 中科院合肥技术创新工程院 | The method of low temperature plasma preparation different type nitrogen-doped graphene |
| CN109768261A (en) * | 2019-01-25 | 2019-05-17 | 东北大学 | A kind of novel cathode material for lithium ion battery N doping porous graphene preparation method and application |
| CN109817471A (en) * | 2018-12-26 | 2019-05-28 | 中国电子科技集团公司第十八研究所 | Modification method of graphene-based lithium ion capacitor positive electrode material |
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| WO2022062836A1 (en) * | 2020-09-27 | 2022-03-31 | 东莞理工学院 | Pyrrolic nitrogen-dominated nitrogen-doped graphene synthesis method and pyrrolic nitrogen-dominated nitrogen-doped graphene prepared by method |
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| CN108899216A (en) * | 2018-07-09 | 2018-11-27 | 杭州高烯科技有限公司 | A kind of high density azepine graphene film and preparation method thereof |
| CN109336092A (en) * | 2018-10-17 | 2019-02-15 | 湖南大学 | A kind of three-dimensional grapheme and preparation method |
| CN109336092B (en) * | 2018-10-17 | 2021-05-14 | 湖南大学 | Three-dimensional graphene and preparation method thereof |
| CN109368618A (en) * | 2018-11-07 | 2019-02-22 | 中科院合肥技术创新工程院 | The method of low temperature plasma preparation different type nitrogen-doped graphene |
| CN109817471A (en) * | 2018-12-26 | 2019-05-28 | 中国电子科技集团公司第十八研究所 | Modification method of graphene-based lithium ion capacitor positive electrode material |
| CN109768261A (en) * | 2019-01-25 | 2019-05-17 | 东北大学 | A kind of novel cathode material for lithium ion battery N doping porous graphene preparation method and application |
| CN111943179A (en) * | 2020-08-21 | 2020-11-17 | 江苏省特种设备安全监督检验研究院 | Nitrogen-doped three-dimensional porous graphene-based electrode material and preparation method and application thereof |
| CN111943179B (en) * | 2020-08-21 | 2021-12-17 | 江苏省特种设备安全监督检验研究院 | Nitrogen-doped three-dimensional porous graphene-based electrode material and preparation method and application thereof |
| WO2022062836A1 (en) * | 2020-09-27 | 2022-03-31 | 东莞理工学院 | Pyrrolic nitrogen-dominated nitrogen-doped graphene synthesis method and pyrrolic nitrogen-dominated nitrogen-doped graphene prepared by method |
| CN113479872A (en) * | 2021-07-19 | 2021-10-08 | 常州大学 | Preparation method of nitrogen-doped three-dimensional porous graphene hydrogel electrode material, electrode and application thereof |
| CN114195136A (en) * | 2022-01-05 | 2022-03-18 | 郑州大学 | Preparation method and application of 3D printing nitrogen-doped high-pyrrole graphene aerogel |
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Application publication date: 20180330 |